ECJ_Dossier_2019_Additives_BYK

EUROPEAN
C OATINGS
www.european-coatings.com dossier 2019
ADDITIVES
The best technical papers on additives for
coatings published in the European Coatings
Journal within the past three years.
PRESENTED BY
54 BIOCIDES 76 DISPERSIONS
Multifunctional organoclay composition for Versatile amino alcohols for improving paint
clean-tech protection performance
ABOUT BYK:
BYK is one of the world’s leading suppliers in the
field of additives and measuring instruments.
BYK offers additives for almost all needs and
application fields from a single source: wet-
ting and dispersing additives, surface addi-
tives, rheology additives, defoamers and air
release additives, wax additives, adhesion
promoters and coupling agents, viscosity
depressants, and processing additives. With
its constant research on modern, environ-
mentally friendly systems, BYK is close to its
customers, scoring with its technological and
applications expertise.
The coatings, inks, and plastics industries are
among the main consumers of BYK additives.
Yet, with the production of oil and gas, the ma-
nufacture of care products, the production of
adhesives and sealants, and construction che-
mistry too, BYK additives improve the product
characteristics and production processes.
Testing and measuring instruments from BYK

can effectively evaluate the quality of color,
gloss, and appearance as well as the physi-
cal properties of paint, plastic, and paper
products, and they are an important part of
quality control.
As a globally operating specialty chemicals
company, BYK has production sites in Germa-
ny (Wesel, Kempen, Moosburg, Schkopau, and
Geretsried), the Netherlands (Deventer, Njiver-
dal, and Denekamp), the UK (Widnes), the USA
(Wallingford, Chester, Gonzales, Louisville, and
Earth City) as well as in Tongling, China.
The company currently employs around
2,300 members of staff worldwide and forms
part of the ALTANA Group.
BYK-Chemie GmbH
Abelstraße 45, 46483 Wesel
Deutschland
Tel +49 281 670-0, Fax +49 281 65735
info@byk.com, www.byk.com
EDI T OR IAL 3
Join our Group

“European Coatings Industry”
Source: Photographee.eu - AdobeStock.com

BURSTING WITH
KNOWLEDGE
As a formulator, you don’t need me to tell you that additives are key coatings in-
gredients. They are hugely efficacious and can determine some of the properties
of the end coating. Additives are incorporated into formulations in tiny quantities.
Silke Karl Whether of the wetting, dispersing, rheological or defoaming type, they are all
Editor
T +49 511 9910-218 capable of transforming paints and coatings into truly high-tech products. As a
silke.karl@vincentz.net formulator, you also know only too well that this is a science in itself. And that it
can be very difficult to keep track of the latest developments.
This is where European Coatings Journal comes in. This handy dossier on “Addi-
tives”, compiled especially for you, is bursting with knowledge. Boasting a selec-
tion of technical articles on additives that have appeared in the European Coat-
ings Journal over the past three years, it will put you back on track and bring
you up to speed on various new advances in automotive, functional, wood, and
UV-curable coatings.
Naturally, the dossier also contains market and product surveys – one of these
even makes a welcome market forecast for the five most important additive
classes.
I trust you will find this an exciting and informative read!
E U R OP E AN COAT I NGS JO UR N A L 2019

4 C ON T E N T S
Source: Jan Felber - stock.adobe.com

MARKET REPORT
The demand for coat-
ings raw materials to
2022
6
Source: yujismilebituke - Adobe.Stock.com
PRODUCT
OVERVIEW
No gloss
wanted
16 26 EASY-TO-CLEAN
Giving dirt the brush-off
EUROPEAN COATINGS JOURNAL 2019
6 MARKET REPORT 20 WETTING AGENTS

The demand for coatings raw matierals to 2022 Stickung to polymers
Rainer Erhardt, Dr Sascha Oestreich, BASF
10 MARKET REPORT
The big five in the scope 26 EASY-TO-CLEAN
Giving dirt the brush-off
Majdi Al-Masri, Wolfgang Griesel, Lin Xie, Byk
12 PRODUCT OVERVIEW
Welcome foam? 32 FUNCTIONAL COATINGS
Power at its core
14 PRODUCT OVERVIEW Dr Claus Jurisch, Koehler Innovative Solutions
Dry and durable
38 2K POLYURETHANES
All-round gains for polyurethanes
16 PRODUCT OVERVIEW
Nayeem Soad, Dean Kondos, Dmitry Chernyshov, Vi-
No gloss wanted
kram Kumar, Martin Wusik, Momentive Performance
Materials
18 EXPERT VOICES
Susanne Struck, Evonik 44 ALKYDS
Aidan Mernin, Santiago Arias, Hempel Solving a volatile problem
Anne-Sophie Hesry, Stacey Syron, Malcolm McInnes,
Synthomer
E U R O P E AN CO AT I NGS J O UR N AL 2019
C O NT E N T S 5
Source: Andrei Merkulov - stock.adobe.com
Source: Сake78 (3D & photo) - stock.adobe.com
Source: dja65 - stock.adobe.com

SURFACE
Giving films
a smoother
profile
50
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MARINE
COATINGS
Cooler options
for spray coat- PIGMENT EFFICIENCY
ings Why small is beautiful
60 66
50 SURFACE 70 WATER-BORNE
Giving films a smoother profile Keeping up the suspension
Juliane Fichtner, Steffen Günther, Benjamin Butsch- Peter Klug, Jörg Rüger, Clariant Germany, Silvia Zie-
kau, Fraunhofer Institute FEP bold, Clariant Switzerland
54 BIOCIDES 76 PIGMENT DISPERSION

Eco-shield for paints Painting a more stable picture
Solvita Kostjukova, Julija Karasa, Karlis Kostjukovs, Dr Romain Severac, Yoann Fernandes, Angus Chemi-
Juris Kostjukovs, Davids Stebelis, Alina cal
60 MARINE COATINGS
Cooler options for spray coatings
Udo Schonhoff, Carlos Feito, Frank Abschlag, Elke
Piron, Elementis
66 PIGMENT EFFICIENCY
Why small is beautiful
Mark Ortalano, Sun Chemical
Source cover: kwanchaift - stock.adobe.com

6 M A R K E T R E P OR T
Source: Jan Felber - stock.adobe.com
THE DEMAND FOR COATINGS

RAW MATERIALS TO 2022
An analysis of and outlook for the market in the years to come. By George R. Pilcher, The ChemQuest Group (published
in ECJ 04/2018).
The global coatings raw material market is estimated to be val- value, is somewhat different than distribution based on volume.
ued at approximately EUR 51.19 billion on 34.3 million metric
tons of materials. RESINS
R aw materials used in the manufacturing of paints and coatings rep-

resent a relatively small (~5%) but extremely important component
of the EUR 3.63 trillion global chemicals industry. All of the world’s leading
Total global sales of resins for use in coatings systems are estimated to
be EUR 25 billion on roughly 15.2 million metric tons. Globally, acrylic
resins are the most commonly-used binder in paint and coatings sys-
chemical producers are active in the coatings market and many coat- tems. This is particularly true for decorative paints, and includes all acryl-
ings raw materials are used in other industries, as well, including plastics; ics, both pure and modified, such as styrene-acrylics and vinyl-acrylics. It
synthetic lubricants; adhesives; sealants; household, industrial and insti- is estimated that acrylic systems, both solvent-borne and water-borne,
tutional cleaners (“HI&I”); personal care products; paper; plastics; water comprise approximately 27% of total coatings binder demand. It should
treatment and many others. The basic chemical components that are be no surprise then, that acrylic resins tend to be the most susceptible
used to produce coatings chemical constituents can also be used to pro- to periodic disruptions in supply, accompanied by price fluctuations. In
duce a wide array of other chemical compounds. This can be a problem 2017, for example, shortages of methyl methacrylate (MMA), due to a va-
at times, since this diversity of uses can create competitive situations for riety of causes, including a shortage of acetone and two major U.S. sup-
raw materials and their pre-cursors that are typically used in coatings, pliers of MMA being down (for different reasons) at the same time, led to
particularly during periods of tight supply. nearly-monthly increases, with MMA climbing roughly EUR 0.40/pound,
Resins (“binders”), pigments & fillers represent over 75% of the global from EUR 0.65/pound in February, 2017 to EUR 1.05/pound in January,
coatings raw materials market. Figure 1 shows the estimated distribution 2018. Prices on both the spot market and the black market during 2017
of coatings’ raw materials value by type. Figure 2 shows the estimated were reported to be “sky high.” While supplies are somewhat more stable
distribution of coatings raw materials volume by type. As might be readily going into 2018, price increases were announced for both January and
anticipated, the distribution of the types of raw materials, based upon February, and there are still likely to be additional increases.
MA R KE T R EP O R T 7
Figure 1: Coatings raw materials value by type (2017).
13%
borne epoxy resin technology has improved, even accounting for higher
consumption due to its improved performance, it has only attained a
small technology share, albeit with major usage in metal can coatings.
12%
These are, however, coming under increasingly close scrutiny in the U.S.,
where there continue to be BPA toxicity concerns.
49%
Additional binders that are used as coatings raw materials include amino,
polyester (with low-bake versions as the growth area), cellulosic, silicone/
polysiloxane, silicate and vinyl resins. Fluoropolymers are another inter-
esting type, with water-borne versions now being offered for high-end
26% architectural exteriors and other applications. Also included in this sub-
segment are hydrocarbon resins and natural resins such as rosins and
shellacs. While technically not resins, linseed oil, tung oil and similar prod-
ucts are also included, since they act as film formers. This sub-segment
comprises approximately 16% of total resin demand in the global coat-
ings markets. Another small but growing resin chemistry is that of ra-
 Resins  Solvents diation cure, with the current greatest volume used in wood and plastic
 Pigments & fillers  Additives coatings—where sometimes even dual WB/UV cure technology is used.
See Figure 2 for a breakdown of the major resin types.
PIGMENTS
The value and volume of pigments, both primary and secondary, for use
On a global basis, alkyds are used to some degree in virtually every end- in coatings formulations were estimated to be EUR 13.3 billion on 11
use coatings segment, and represent the second most common type million metric tons of product. On a volume basis, fillers and extenders
of resin system used in coatings formulations. Alkyds comprise roughly are the largest sub-set of the pigments category and represent roughly
20% of resin demand in the global coatings market (≤10% in the U.S.). 56% of all demand for pigments in the coatings market. Compounds that
Although alkyd resins have been steadily declining in use, particularly in comprise this sub-segment include clay, calcium carbonate, talc, silica
North America and EU, as VOC limits continue to drop, and the market and other inorganic materials.
has been moving to other resin types for water-based and higher-solids The second largest sub-set of the pigments category is titanium dioxide
formulations, newer water-based alkyd systems are being introduced (TiO2), which is the single highest-volume pigment used in coatings. Its
into the market, at least in part due to the increasing interest in resins largest use is in decorative coatings, but it is widely used in a variety of
made with higher renewable resource content. industrial OEM coatings and industrial maintenance/protective coatings,
Polyurethane coatings, either 1K, 2K (or occasionally 3K) are widely used as well. Titanium dioxide represents approximately 31% of all pigments
in the automotive OEM, other transportation, automotive refinish, wood, used as coatings raw materials, and this is likely to be somewhat problem-
industrial finishes, decorative coatings and even severe-service marine atic in 2018, with Q1 lead-times of 60-90 days, and scattered instances of
and high-performance industrial segments. Urethane resins currently allocation, as well. The global economic climate currently favours all mar-
comprise roughly 21% of the global demand for resins in coatings. Usage ket segments that use titanium dioxide, most notably the building and
of polyurethane resins has been growing over the past several years due construction segment. This will, therefore, be a year of continued price in-
to their performance properties and their ability to be used in lower VOC creases, which could easily take titanium dioxide as high as EUR 2,500/mt,
formulations. An important, and growing, sub-segment of polyurethanes albeit still significantly short of its 2011-2012 historic high price of ~EUR
in the U.S. are 2K polyureas. To comply with increasingly stringent VOC 3,630/mt. Increases in Chinese chloride-process TiO2 production are es-
requirements, polyurethane water-borne dispersions (PUDs) have been sentially being offset by continued closure of sulfate-process plants, and
developed and used to formulate single-component coatings with im- Huntsman’s plant in Finland is not scheduled to be back to full production
proved abrasion resistance compared to water-borne acrylics. They can until the end of the year. If the acquisition of Cristal by Tronox is finalised
also be combined with other water-borne resins to meet cost targets and (the U.S. Government filed a complaint aimed at stopping the deal on 5
performance needs. December 2017), it is unlikely to unleash any additional pigment into the
Approximately 16% of total demand for binders used in coatings is sup- market during 2018, although might be reasonably be expected to add an
plied by epoxy resins. Various resins in the epoxy family are widely used additional 100Kmt to global output in subsequent years.
in electrodeposition (ED) coatings and in industrial coatings particularly For certain end-use applications such as decorative, automotive OEM
in the transportation, industrial maintenance and marine markets. Epoxy and automotive refinish, colour is a primary driver of product selection.
resins are also widely-used in powder coatings. In recent years, high sol- Hence, colour pigments play a vitally important role in the coatings indus-
ids and ultra-high solids formulas using liquid epoxy resin dominate and try. Despite the importance of these materials, colour pigments represent
continue to grow. Liquid epoxy resin is also used for 100% solids epoxy only a small component of pigment demand. Included in this segment
formulas applied as concrete surfacers, tank linings and for other select are both inorganic and organic pigments. Inorganic colour pigments
applications, often augmented with phenoxy and novolac resins to en- such as iron oxide are the most frequently used and represent over 80%
hance certain performance features. While the performance of water- of the volume of colour pigments. Organic colour pigments are among

Figure 2: Coatings raw materials volume by type in 2017. Figure 3: Coatings pigments volume by type (2017)
4%
44%
12% Acrylic Extenders/
20% 19%
fillers
9% Alkyd
44% 32%
9% Urethane
10% TiO 2
7% Epoxy 4% Colour
32% 2% pigments
7% Other 20% 2% Other
 Resins  Solvents  Resins  Solvents

 Pigments & fillers  Additives  Pigments & fillers  Additives
the highest-priced raw materials and thus, despite their relatively low vol- from solvent-based to water-based technologies, ultra-high solids,
ume, represent a significant portion of the market value. Organic colour and 100% solids, overall usage of solvents is declining as a percent-
pigments are likely to increase 3-4% in 2018, as a result of competition age of the
seeable future.
total Similarly,
coatings raw
within
materials
solvents.
usage. Unfortunately,
While solvent usage VOC
for the basic chemicals from which they are built, and that largely come as a of
the solvents
total raw
family,
materials
shifts
continues
are regulations—and
to decline, however, themanyconcept
end-
out of the Asia Pacific region—production of which can be affected at use segments
ongoing as formulators
that use solvent-based
seek to of coatings
“what is continue
exempt and to grow.
whatAs
is
almost any time as the Chinese Government becomes increasingly pro- a result,
find less total
toxic solvent
and moreusagecom-
has been
not”—differ
relativelyaround
flat overthetheglobe.
past
active about shutting down chemical processes in an effort to improve air decade environmentally-friendly
pliant, or so, and this trend is expected
For example,
to extend into 2,2,4-trime-
the fore-
quality. Complex inorganic colour pigments (often referred to as “CICPs”
or “ceramic pigments”) are growing in importance due to the fact that thyl-1,3-pentanediol monoisobutyrate (“Texanol”), historically the
they meet the higher performance demands of chemical inertness and most effective coalescing agent for latex paints, is listed as non-
heat stability, along with light fastness and excellent weathering proper- exempt by the U.S. Environmental Protection Agency, but in the EU
ties. Moreover, with only a few exceptions (such as perylene black), CICPs it is listed as exempt. This can make formulating “global coatings
comprise the majority of IR-reflective pigments that now enable formula- formulations” anywhere from tricky to impossible, depending upon
tion of various colours with energy efficiency properties. Colour pigments the coating, application and performance requirements.
represent >6% of the volume of all pigments used in coatings.
In addition to the pigments listed above, there is a wide array of other ADDITIVES
specialty pigments such as anticorrosive pigments, metallic pigments,
pearlescent pigments, carbon black and zinc oxide. While some of these Additives comprise a broad category that covers a wide array of chem-
pigments play an important role in coatings volume, none individually icals used as raw materials for coatings. Recent innovations include
represents a significant volume. These other pigments represent roughly multi-functional additives to simplify the number of formula ingredi-
>6% of the total pigment demand. See Figure 3 for a breakdown of the ents and also include those that help to achieve low-to-zero VOC for-
major pigment types. mulations. Total revenue for additives used in coatings is estimated to
be EUR 6.77 billion on approximately 1.25 million metric tons.
SOLVENTS Rheology modifiers are the largest sub-segment representing over
Solvents are the key contributors to the volatile organic content of 30% of demand, and are used the film, and may also be used
paints and coatings emitted into the atmosphere and, as a result, to control viscosity and to affect at times for their coalescent
are regulated by various local, regional, state and country regula- flow and leveling. Plasticizers properties. Biocides are added
tory agencies around the world. Global revenues for solvents used are incorporated into formula- to formulations to prevent the
in coatings formulations in 2017 were approximately EUR 6.45 bil- tions to improve the flexibility of growth of bacteria and other mi-
lion on 6.5 million metric tons. Oxygenated solvents comprise over
60% of demand within coatings formulations, and include chemical croorganisms while the coating is being stored, and also as a dry film
components such as alcohols, ketones, esters, glycols and glycol preservative. Biocides, including special chemical components that
ethers. Hydrocarbon solvents are either aliphatic or aromatic and are used to minimize marine fouling, comprise approximately 22% of
comprise less than 40% of total usage within coatings formulations. total additives used in coatings. Surfactants represent approximately
As a result of the continuing shift in paint and coating formulations 19% of additive demand on a volume basis, with foam control addi-
tives at 15%. ąą Silberline Synthopol

The list of other additives is quite long. While none represents a ąą Specialty Resins
significant component of coatings raw materials individually, “Other ąą OPC Polymers
Additives” collectively comprise a significant portion of all additives ąą Orion Engineered Carbons
and include adhesion promoters; antifoaming agents; anti-skinning ąą Many, many others
agents; corrosion inhibitors; driers; flatting aids; flood control agents;
sag control agents; slip aids; and UV absorbers, to name a few. While none of the local and regional suppliers have significant share on
their own, collectively they are an important source of coatings raw mate-
REGIONAL DISTRIBUTION AND COMPETITIVE LANDSCAPE rials. Competitors in this group offer an assortment of value propositions
tailored to their customer mix. In some cases, due to lower overheads,
Globally, regional distribution of coatings raw materials generally fol- local/regional suppliers are able to provide lower cost alternatives to the
lows overall production of coatings. The competitive landscape is quite major suppliers. In other cases, they are able to provide unique products
complicated. In general, there are three types of competitors that op- or services that allow them to effectively compete. Significant consolida-
erate in this market. tion is anticipated among this group.
The first type of competitor is large, multinational chemical companies
serving many industries that compete across coatings raw material END-USE MARKETS
categories. Examples include:
ąą BASF Demand for coatings raw materials is directly linked to coatings de-
ąą Celanese mand. Over the coming five years, demand for coatings is anticipated
ąą Allnex to grow at a rate of 4-5% annually. This would result in a 2022 de-
ąą Dow/DuPont mand for raw materials of approximately 42 million metric tons. Asia
ąą Eastman Chemical Pacific is forecast to experience the greatest volume growth (5-6%)
ąą Evonik to 2022. Europe is likewise forecast to experience moderate growth
ąą Huntsman of perhaps 3-4%. North America is forecast to post somewhat more
ąą Lanxess robust growth of 4-5%, but the exact mix of raw materials consumed
ąą Momentive within each region will depend on specific end-use market growth.
ąą W.R. Grace, et al.
ECONOMIC INFLUENCES
Large, multinational chemical companies play a significant role in the
coatings raw material market and command a considerable share of Significant numbers of raw materials used in coatings formulations
the raw material demand. The scale, degree of integration, and broad are either derived directly from oil for their chemical composition,
product portfolios of these competitors are perceived as key advan- or indirectly as a result of energy derived from oil for their mining
tages. Merger and acquisition activity among the large, multinational and/or processing. The price of oil can be highly volatile and many
chemical companies has had a significant impact on the coatings raw factors can impact this forecast, driving the price/barrel either up or
materials market, and acquisitions are forecast to continue. Private down. As a result, oil prices have a significant impact on the price of
equity firms continue to show an interest in acquiring raw materials coatings raw materials. ChemQuest estimates that there is a “pass-
suppliers. through factor” of roughly 50%—i.e., if the price of oil doubles, raw
The second type consists of multinational product specialists that fo- material prices will increase by 50%. A realistic worst-case scenario
cus on a limited product offering. These companies tend to specialise might see prices of 50% higher than the forecast, which would in-
in a specific product or chemistry niche(s), and are frequently innova- crease raw materials for paints and coatings roughly 25%. Over the
tion drivers in the market. Competitors of this type vary widely in size, coming five years, the price of oil is forecast to remain relatively
based upon geographic scope, product breadth and market focus. Ex- stable, within the range of EUR 48.4 - EUR 56.4/barrel according to
amples include: the U.S. Energy Information Administration (EIA). The implication for
ąą Cathay (Pigments) raw material suppliers and coatings formulators is that the price of
ąą Heubach (Pigments) the base materials that comprise coatings will likely rise at a rate
ąą Nubiola (Pigments) similar to the rate of inflation to 2022. 
ąą Alberdingk & Boley (W/B Resins)
ąą Reichhold (Resins)
ąą Worlee-Chemie (Resins) George R. Pilcher
ąą Altana (Byk—Additives) Vice President
ąą Troy Corporation (Additives) The ChemQuest Group
ąą Michelman (Additives) gpilcher@chemquest.com
As is the case with multinational chemical companies, mergers and ac-

quisitions are anticipated to continue, impacting the specialist competi-
tors as they are acquired by either larger chemical companies to comple-
ment their portfolio, or by other specialists to gain scope and share.
The final type of competitor is the local/regional suppliers. These gener-
ally focus on a limited product offering. Examples among the numerous
local/regional suppliers:
ąą Optimal Chemicals
ąą Organik Kimya

Source: Pedrosala - Stock.adobe.com
THE BIG FIVE IN THE SCOPE

The global market for coating and ink additives in 2017. By Mike Growney, Kusumgar, Nerlfi & Growney, Inc (published
in ECJ 06/2018).
Additives are critical components for the successful formula- ADDITIVE TYPES
tion of modern day coating and inks. Numerous additives are
used in coatings and inks; this article focuses on five of the Although the five leading additive categories are categorized in this
leading types, which include rheology modifiers, dispersants, paper they include over two dozen broad chemical and product form
foam control products, slip & rub materials and wetting agents. categories which comprise thousands of individual products. There are
some large volume additive types but there exists many highly special-
C onsumption of these five additives was 1.15 million tonnes in 2017

valued at EUR 4.38 billion. They represent some 70 % of the addi-
tive volume consumed in coatings and inks and 60 % of the value. Other
ized additives which can improve the properties of an individual coat-
ing or ink formulation. Additives for small volume and highly specialized
formulations command a price premium.
additive types include biocides, driers, fire retardants, light stabilizers, Usage of the five leading additives roughly tracks that of coating and
plasticisers, etc. ink volume with 92 % of the tonnes used in coatings and the rest in
inks. Table 1 outlines the consumption of additives by type and industry
COATING & INK INDUSTRIES in 2017. Rheology modifiers are the leading type with nearly 40 % of
the tonnes and 36 % of the dollars. The broad categories for rheology
Global coating consumption was 43 million tonnes worth EUR 115.26 bil- modifiers include synthetic water-based (46 % of the volume, including
lion in 2017 while ink demand was nearly 4 million tonness valued at USD water), inorganic (25 %), cellulosic (17 %) and other solvent-based syn-
15.37 billion. Coating growth is placed at 4 % per year while ink volume is thetic types (11 %). Some formulations employ combinations of rheol-
projected to increase at a 2 % annual rate. Water-based technology com- ogy modifiers for optimum stability and application properties.
prises 55 % of the coating volume with 85% of the tonnes for architectural Dispersants are second with 20 % of the volume and 18 % of the dol-
applications and the rest for industrial. In contrast, only 15 % of the ink vol- lars. Dispersants are used to stabilise and optimize the appearance of
ume was water-based. Water-based coatings are increasing 5% per year the 5.5 million tonnes of pigments and a smaller quantity of fillers used
while water-based inks are advancing at a 3 % annual rate. in coatings and inks. They vary from high volume polyacrylic acid types
Solvent-based technology was 38 % of the coating tonnes and one-third of for stabilizing TiO2 in architectural house paints to specialized polymeric
the ink total. Oil-based inks (hydrocarbon, vegetable, etc.) were the leading types which account for over 55 % of the value.
ink technology with 48 % of the tonnes. About 30 % of the solvent-based Foam control agents were 16 % of the additive volume and value. Tech-
coatings were used in architectural paints which are growing 2 % per year nologies used include the high volume and older mineral oil based for-
while 70 % was consumed in industrial end uses which are increasing 3 mulations to those based on surfactants, polymers or silicones. Over
% per year. Solvent and oil-based inks are growing only 1 % annually. 100 three-quarters of the foam control additive volume was used in water-
% solid technologies for coatings include radcure, powder coating and based formulations.
other 100 % solid liquids while for inks they are primarily radcure types. Slip & rub additives are used to modify the abrasion resistance, slip
The technology comprised 7 % of the coating and 3 % of the ink volume. properties, blocking and release characteristics of a coating or ink. They
Table 01: Additives by type and industry In 2017. Figure 01: Additives volume by technology in
2017 (total: 1.15 million tonnes).
Type Thousand tonnes EUR (million)
34,000
Coatings Inks Total 31,000
Rheology 439 16 455 1,580

57,000
Disper- 217 13 230 777
sants
234,000
Foam 182 7 189 717

797,000
control
Slip/rub 97 46 142 683
Wetting 129 7 136 623

agents
 Water-based coating  Water-based ink
Total 1,065 88 1,153 4,380
 Solvent-based coating  100%-Solid
 Solvent-based ink
represent 12 % of the additive volume and 16 % of the value. Wax- 1 % per year while water-based types are growing at a 3 % annual rate.
based products were 87 % of the volume and the more costly silicones Powder, radcure, and other 100 % solid liquid coatings and inks were
13 %. Silicones and waxes can be combined to optimize a formulation. an outlet for 2% of the coating and ink additive volume and 5 % of the
Wax based products are incorporated as micronized powders or as value. Additives for these 100 % solid technologies are increasing at a
water-based or solvent based dispersions/emulsions. Some two-thirds 5 % annual rate.
of the wax used was polyolefin types with polyethylene the predomi-
nate kind. Fischer-Tropsch, PTFE and petroleum are the other larger ADDITIVES BY REGION
wax types.
Wetting agents were 12 % of the additive tonnes and 14 % of the dol- The Asia-Pacific region consumed 40 % of the additive volume in 2017
lars. They are surfactants that help reduce surface tension which af- and 38 % of the value and is led by China which took 57 % of the region’s
fords pigment and substrate wetting, improves flow and leveling, and tonnes. Additive volume in the region is growing 7 % per annum with
can contribute to other property improvements. Some 55 % of the China expanding at an 8 % yearly rate. India took only 5.5 % of the re-
wetting agent volume was alkoxylated surfactant such as alkyl phenol gion’s additive volume but is increasing 11 % per year. Japan and South
ethoxylates, secondary alcohol ethoxylates, etc. These surfactants are Korea combined for 17 % of the tonnes but are growing sluggishly.
typically added during pigment grinding. Other wetting agents include Europe took 28 % of the global additive volume and 29 % of the val-
acetylenic glycol derivatives, silicones, acrylic polymers and fluorosur- ue. Europe is a mature outlet for coatings and inks and a 2 % per year
factants. Some 78 % of the wetting agent volume was employed in wa- rate of increase is forecast for additives. North America represented
ter-based formulations. 23-24 % of the additive tonnes and value and like Europe has mature
growth prospects. However, despite low growth in Europe and North
ADDITIVES BY TECHNOLOGY America there is fierce competition among the various additive chemis-
tries and new products are constantly being introduced.
As shown in Figure 1, water-based coatings were an outlet for 797,000 South and Central American countries took 5 % of the additive volume.
tonnes of the five additive types, 69 % of the total volume. Water-based Additive growth in the region has been hurt by the recession in Brazil. A
coating additives are growing at a 5 % annual rate. Architectural paints modest 3 % annual increase for additives is now projected.
took 84 % of the water-based coating additive tonness and industrial
coatings the rest. Additives for industrial coatings generally cost more ADDITIVE SUPPLIER STRUCTURE
and comprised one-quarter of the USD 3 billion water-based coating
additive value. Industrial water-based coating applications such as auto The supplier structure for coating and ink additives is diverse with sev-
OEM and refinish, overprint varnishes, wood furniture, etc. typically use eral large suppliers and numerous medium and smaller ones. Some
more specialized additives. Solvent-based coatings consumed one-fifth suppliers participate in only a single additive type and chemistry while
of the additive tonnes with 80 % for industrial coatings and the rest for others provide a wide variety of products. There has been several large
architectural. Solvent-based coating additives were about one-quarter acquisitions in recent years which have concentrated the market and
of the value as high performance types are in demand for end uses include Altana’s (Byk) acquisition of Rockwood’s rheology additive busi-
such as automotive. Solvent-based coating additives are projected to ness, Dow Chemical acquiring the 50 % of Dow Corning that it did not
increase 3 % per year. already own, and Evonik’s acquisition of Air Products’ Specialty Coating
Oil and solvent-based inks utilized 5 % of the additive volume and wa- & Additives business.
ter-based inks 3 %. They combined for 10% of the total additive dollars. The top five suppliers of coating and ink additives include Byk, Evonik,
Over one-half of the ink additive volume was slip/rub products. Rheolo- DowDuPont, Elementis and Ashland. These companies now garner just
gy modifiers and dispersants are the other larger volume additive types over one-half of the sales which is up from a 42 % share five years ago.
for inks. Oil and solvent-based ink additives are forecast to increase only Each of these companies sells all of the five additive types. 

12 P R O D U C T O VE R VIE W
WELCOME FOAM?
Foam is welcome when you’re taking a nice relaxing bath.
Source: Igor - stockAdobe.com
It’s not so welcome in paints and coatings, though. In this

over view, we present a selection of common defoamers
(published in ECJ 11/2017).
R educed gloss, less transparency and imperfections that can even

destroy the protective properties: these and other problems can
be caused by foam in water-borne paints and coatings. Foam has many
causes, among them mechanical introduction of air during mixing and
application, displacement of air on surfaces during dispersing, and
over-rapid drying (blistering) of a paint. But no matter what the precise
underlying details are, it’s always unwelcome. Careful mixing and slow
drying can suppress it, but that still leaves too much room for human
error, especially as the processing time would be unnecessarily long.
Fortunately, relief is available in the form of defoamers. These are
highly effective destroyers of foam, and ensure that surfaces end up
Active ingredi-
Company Product Chemistry Density Viscosity Non-volatile content
ent
Foamstar ED Polymer emulsion with small 1.00 g/ml 2,000 mPa.s

- -
2523 amounts of modified PDMS (25 °C) (23 °C, Brookfield)
BASF
Foamstar SI Compound of modified polydi- 1.00 g/ml 600 mPa.s

- -
2240 methylsiloxanes (20 °C) (20 °C)
silicone-free polyamide particles 1.00 g/ml 62 %

Byk-1640 - -
and highly branched polymers (20 °C) (60 min, 105 °C)
Byk
Polyether-modified polydi-
1.00 g/ml
Byk-1781 methylsiloxane with hydropho- - 100% 100%
(20 °C)
bic particles
1.02
800 mPa.s
Additive 8590 Silicone (specific weight, 100% -
(25 °C)
25 °C)
Dow
Additive 108F Silicone - 1,600 mm²/s - 25.5%
Blend of hydrophobic silica, 0.90 450 mPa.s

Dapro DF 21 - -
emulsifiers and mineral oil (specific weight) (Brookfield)
Elementis
950-1,000 g/ml 600 - 3,000
Dapro DF 9030 vegetable oil based defoamer 50% -
(25 °C, ISO 2811-2) mPa.s
Blend of organic modified poly- 0.98 g/cm³

Agitan 158 5,000 mPa.s 25% -
siloxanes (20°C)
Münzing
Blend of vegetable oils and
0.98 g/cm³
Agitan 352 alkoxylated compounds, silica 800 mPa.s - -
(20°C)
and emulsifiers
P R O DU C T O V ER VIE W 13
with a high-class finish and, above all, are properly protected.

The range of active ingredients employed is vast, with silicones or
polysiloxanes being the most popular due to their good compatibility
with many formulations. Silicone chemistry is so versatile that all kinds

of polysiloxanes are available for use with defoamers.
Also suitable are mineral-oil-based defoamers such as high-purity par-
affin oils. More environmentally acceptable are vegetable oils, which
can also have good defoaming properties. Exemplars here are triglyc-
erides of saturated and unsaturated fatty acids. Other important cat- BOOK TIP: UNDERSTANDING ADDITIVES
egories are polar oils, geminii surfactants and hydrophobic particles.
The foremost considerations governing the correct choice of defoam- This book covers everything about the mode of action,
er are the binder and the emulsifiers. In most cases, the composition application and possible side effects of the most impor-
of the binder is not known down to the very last detail, but defoam- tant coatings additives - in a single volume, presented in
ers of weak to medium hydrophobicity tend to be used for straight a textbook style. It reflects the needs of practical work.
acrylic dispersions, whereas medium to highly hydrophobic types are
needed for acrylo-styrene or vinyl acetate dispersions. Polyurethanes, Understanding Additives, Bodo Müller, 160 pages, ISBN:
on the other hand, get by with defoamers of low hydrophobicity. 9783866308688
Other influential factors to consider are the pigment volume concen- www.european-coatings.com/books
tration (PVC), incorporation of the defoamer, shear forces during ap-
plication or the surfactant content of the formulation. Selecting the
right product, then, calls for intuition and proper testing. For better re-
sults, it can be worth while trying out different out different defoamer
combinations.
Recom-
Carrier material Area of application Properties
mended dsage
VOC-free according to EU Directive 2004/42/EC and EPA

Method 24
Recommended for high-PVC systems based on acrylic,
- 0.2-0.6 % Good foam suppression during grinding as well as applica-
styrene-acrylic, vinyl and vinylacrylic emulsions.
tion
Retains antifoam efficiency during extended storage of paint
Pigment concentrates, pigmented aqueous coatings, Broad food contact compliance

- 0.1-0.5%
printing inks and adhesives Excellent stability at high shear conditions
Suitable for food contact applications Stable to acids and

Aqueous coatings, printing inks, adhesives, paper coat-
Water 0.05-0.5 % alkalis
ings and construction chemicals
Easy to incorporate
Does not impact the transparency Little or none reduction

Aqueous systems to remove microfoam generated dur- of gloss
- 0.3-1.0%
ing application. Especially suited for systems with airless or airmix ap-
plication
Acrylic styrene emulsion paint for architectural wall coat- No impact on surface gloss
- 0.05-1.0% ings, water-based flexo gravure inks, acrylic over print Performs over wide temperature range Performs at low
vanishes and acrylic urtehane emulsion paints for wood dosages
Water-based paints, coating and inks APEO free

Water 0.1-1.0% Acrylics, VAE dispersions, polyurethane dispersions and Easy to dose and disperse
alkyd emulsions Low tendency to cause surface defects, like craters
Particularly useful for gloss paints and clear acrylic coat-

- 0.1-1.0% Water-based inks, adhesives and industrial coatings ings
Readily dispersible in water
Universal waterborne applications with good emulsifying Bio-based
Water 0.2-0.6%
properties Good scrub resistance
Industrial and wood coatings, printing inks, adhesives Miscible with water in any ratio
Water 0.05-0.5%
and emulsion manufacturing Low tendency to cause craters
Alkali and acid resistant (can be used in a pH-range

Architectual coatings, building products, industrial and between 3 and11)
- 0.05-0.5%
wood coatings, printing inks, adhesives, paper coatings Free of mineral oil and silicone
Susatainable raw materials used

DRY AND DURABLE

Source: Charly Lipper - stock.adobe.com
e humans can make ourselves comfortable in our own

W
houses when it’s wet and foggy outside. Our houses
themselves are less fortunate and remain exposed to the
damp. To prevent this from causing too much damage,
architectural paints should possess good water-repellent
properties. This is where the right additive comes in.
(published in ECJ 01/2018)
A good architectural paint has to meet many requirements. As a

façade paint, for example, it should look good and be as durable
as possible. For which of us wants to keep painting our house over
and over? One of the most important functions, however, is how the
paint responds to wet conditions. A good coating, for example, will
be sufficiently hydrophobic to ensure that water flows off as quickly
as possible in rain or fog, thus depriving algae and fungi of their “life’s
blood”. At the same time, the coating has to remain permeable to wa-
ter vapour to allow moisture to evaporate from the façade.
The first of these requirements, namely water-repellence, can be im-
proved by incorporating hydrophobic additives into the formulation. A
Apperi- Wax melt- Recommend-

Company Product Chemistry Viscosity Density Solid content pH
ance ing point ed dosage
Emulsion of amino 200 mPa.s 0.98 g/cm³

Tego Phobe White 6-8
Evonik functionalised poly- (25 °C, DIN (25 °C, DIN 55% - 2-4%
1409 liquid (25 °C)
siloxane 53015) 12791)
Tego Phobe Emulsion of modified White 100 - 350 mPa.s 5.0 - 9.0
0.995 g/cm³ 50% - 4-8%
1659 polysiloxane binder liquid (25 °C) (25 °C)
Yellowish
Keim Ultralube E-340 Anionic paraffin wax
to white - - 50% 56 - 58 °C 9.5 1-4%
Additec FM emulsion
liquid
Paraffin wax emul- White

Ultralube E-325 - - 40% 60 °C 7 2-7%
sion liquid
Modified paraffin White 0.95 g/cm³

Lubrizol Aquaslip 677 - 54-56 % 64 °C 8.5 - 9.5 2-5%
wax emulsion liquid (25 °C)
Lanco Glidd Blend of waxes and Smooth

- 0.810 g/cm³ 59-60 % 62-65 °C - 3-5%
4370 oils paste
Nanoscale wax Semi- < 1,000 mPa.s

Michem Lube 0.96-0.98
Michelman emuslion (paraffin, viscous (Spindle 3, RPM 38.5 - 39.5 % - 9.0 - 10 -
270R (specific gravity)
carnauba etc.) liquid 60)
Anionic paraffin/ Semi- < 100 mPa.s

Michem Emus- 0.95-0.97
polyethylene wax viscous (Spindel 1, RPM - - -
lion 66035 (specific gravity)
coemulsion liquid 60)
“The global architectural

selection of these is presented in the table. A wide variety of coatings coatings market
are applied to buildings to help keep water at bay. Primers, for exam-
ple, are normally employed in diluted form and serve to prevent salt
efflorescence while protecting against moisture.
is expected to grow
Impregnating compounds are much more water-repellent as a rule.
These are mostly dilute solutions of water-repellent agents. Unlike
over 5 % annually
until 2023.“
primers, they are not usually painted over again. They are not nor-
mally suitable for non-absorbent substrates as their functionality de-
pends on good penetration.
Exterior plasters and façade paints must also be water-repellent, be-
cause they are directly exposed to the elements. The most commonly
employed types are aqueous emulsions based on styrene and pure
acrylate. Silicone resin emulsion paints and siloxane façade paints are
also very popular due to their high water vapour permeability and low
water absorption.
At any rate, good water-repellent properties ensure less algal and fun-

gal growth. Precisely in an age when biocides are being increasingly BOOK TIP: UNDERSTANDING ADDITIVES
regulated and being viewed critically by consumers, water repellence
is a key way to at least cut down on biocide use.  This book covers everything about the mode of action,
application and possible side effects of the most impor-
tant coatings additives - in a single volume, presented in
a textbook style.
Understanding Additives, 160 pages, Bodo Müller

ISBN: 978-3-86-630868-8
Shelf life Properties
www.european-coatings.com/books
Improves water resistance

1 year Suitable for Ecolabel conform formualtions
Easy incorporation

1 year Low dirt pick-up
Good tinting performance

1 year Increases scratch resistance
increases open time

1 year Increases scratch resistance
Early water resistance

1 year High block resistance
Lower friction

1 year Nearly odorless
Enhances gloss

2 years Good blocking resistance

2 years
Good blocking resistance

NO GLOSS WANTED
Source: yujismilebituke - Adobe.Stock.com
Radiation curing is one of the fastest growing technolo-

gies in coatings industry. The technology is especially
suited for high-throughput applications and is known
to display excellent gloss. However, not in all cases
a glossy coating is favoured. Our over view provides
examples of matting agents that can help formulators to
achieve a matt finish. (published in ECJ 05/2018)
R adiation cured varnishes and inks are known to display excellent

gloss. Nevertheless, some UV-curable coatings can be difficult to
matt, especially if they so not contain any solvents or water. If this is
the case, there is no emission-induced vertical shrinkage during the
curing process which can lead to extremely even and smooth surfac-
es. However, low gloss goes along with a more diffuse light scattering,
Company Product Chemistry Appearance Oil absorption Density Particle size pH
Granulate or fine 2.65 g/cm³

Hydrophilic fumed
Silica 200 powder (white to light - (LV3, DIN EN ISO - -
silica
grey) 1183)
Deurex
0.95 g/cm³
Masterwax Wax additive con-
Fine white powder - (LV3, DIN EN ISO < 150 µm -
Matting centrate
1183)
Thermosetting plastic 251g/100g 1.47 g/cm³ D50: 3.5 µm

MK-F6 Fine white powder -
powder (DIN ISO 787/5) (20 °C) D90: 6.5 µm
Deuteron
Compount of different 0.92 g/cm³ D50: 8.0 µm
UV RMP Fine white powder - -
waxes (20 °C) D90: 17.0 µm
2g/cm³ D50: 5 µm 6.6

Acematt 3600 Silica White powder -
(DIN ISO 787 / 10) (Laser diffraction, ISO 13320) (5 % in water, ISO 787-9)
Evonik 2.2 g/cm³
D50: 9.5 µm 6.5
Acematt TS 100 Silica White powder - (20°C, DIN / ISO
(Laser diffraction, ISO 13320) (5 % in water, ISO 787-9)
787 / 10)
6.0 - 8.0
Synthetic amorphous White free flowing 120 g/100g 4.8 - 5.8 µm
Syloid Rad 2005 - (5 % in aqueous suspen-
silica powder (Grace Q 015) (Grace Q 013)
sion, Grace Q 014)
Grace
2.8 - 3.6
Synthetic amorphous White free flowing 280 g/100g 6.5 - 8.0 µm
Syloid Rad 3007 - (5 % in aqueous suspen-
silica powder (Grace Q 015) (Grace Q 013)
sion, Grace Q 014)
Proprietary combina- Yellowish low viscous

Carbocure 7000 - - - -
tion liquid
Lubrizol
Free flowing white 0.9 g/cm³ D50: < 13 µm
Lanco 1394 F Polypropylene wax - -
powder (25 °C) D90: < 25 µm
Micronized ethylene- D50: < 5 µm

Ceretan MA 1 g/cm³
bis-stearamide-wax - - D90: < 20 µm -
7020 (relative density)
Münzing (EBS) (LV 5, ISO 13320)
Chemie Spherical, micronized 0.95 g/cm³ D50: < 7 µm
Ceretan MO Fine white powder
and oxidized polyeth- - (20 °C, DIN EN ISO D90: < 20 µm -
3220 (slightly yellow)
ylene wax 1183) (LV 5, ISO 13320)
so it is important to create a certain micro roughness at the interface

coating/air.
As you can see in our exemplary table there is quite the variety of
different matting agents that can be used. Most matting agents are “420 Million EUR
based on synthetic silicas or waxes. Not included in the table are
coarse fillers and pigments that can lead to a rougher surface, since
this overview is merely focused on additives.
was the value of
OPTICAL PROPERTIES the matting agent
In the case of clear coatings this matting effect should not affect any
other optical properties, especially the transparency. Therefore it is
market in 2016“
important that the matting particles need to have a refractive index
close to the one of the cured coating film. The closer the refractive
indexes are the more transparent appears the final film.
Generally speaking, the matting agents in radiation curing coatings
are similar to the ones used in common wet coatings. Because of
the more or less missing shrinkage mechanism it is common to use
a significantly higher dosage of additives. Even though formulators

are normally keen to keep their recipes simple it is not uncommon GEL POINT AND MATTING
that waxes and silicas are used together to achieve specific haptical
properties.  The gel point is described by various criteria based on
the solubility when insoluble material first occurs. The
gel point can also be defined via an increase in molar
mass or with rheological parameters.
Storage Properties (all: matting) From this time onward the matting agent agglomerates
are fixed in the developing polymer network and can
Improvement of free flow characteristics of powders no longer contribute to roughness during the further
- Prevents sticking of premix shrinkage process. With a high degree of probability,
Food contact approved the time when the gel point occurs is influenced by vari-
ous factors, such as the rate at which the molar mass in-
Minimised slightly dusting behaviour
- Good anti-blocking
creases, changes in the segment movability of the chain
Degasing agent molecules.
Small binder demand leads to only non-essential viscosity influence

24 months
Good Heat and wheather resistance
Good transparncy
24 months Good mechanical and chemical resistance
Supports soft-feel effects
Very low thickening effect

24 months
Particularly suitable for very thick or very thin UV-coatings
Combines matting with high transparency

24 months Particulary suitable for systems that are difficult to matte
Good resistance to houshold chemicals
Easily dispersible
12 months Only low thickening effect
Consistent gloss over varying coating weights
Easily dispersible
12 months Only low thickening effect
Good film clarity
No significant increase of viscosity

6 months (RRD) Improved soft feel properties
Good wood grain enhancment
No or only little reduction of coefficient of friction

- Good re-coatability
Scratch resistance and surface hardness
Also acts as an degassing agent

12 months Improved slip and abrasion resistance
Good temperature stability (no yellowing)
Improved slip and antiblocking

24 months Soft feel effect
Easy to disperse

18 E X P E R T V O ICE S
Source: Cpro - Fotolia

Two questions, two answers (published in ECJ 06/2018):
1 Do you see potential in the develop-

ment of multi-functional additives and
what challenges do you expect?
2 What trends do you think will influence

the additive market in the next 5 to 10
years?
1 Multi-functional additives are highly in-

teresting products. Let me start by stat-
Market analysts forecast a continuously
growing share of environmentally friendly
ing that today, there are already several
multi-functional additives available on the “Multi-function- coating technologies. Sometimes this trend is
additionally supported by regulatory chang-
market. There are wetting agents that also
help deaeration and defoaming, dispersants al additives es. Additives are needed to improve the ap-
plication and film properties of water-borne,
that also aid substrate-wetting, anti-settling radiation-curing, and high solid coatings; in
agents that improve your coating’s water re- which are able some cases, they even become true enablers
sistance, etc. for new coating technologies.
In these examples, we speak about a com- to replace t wo Along with that goes the trend of sustainabil-
bination of properties, which are generally ity. And this means far more than just VOC
perceived as positive by coating formula-
tors. This makes these multi-functional addi-
or three others reduction. Increasing the performance – and
thus the lifetime – of a coating is very sus-
tives widely and safely usable. Even if coating
formulators are looking for only one of the
can be a great tainable. A lot of development work is being
done to make coatings more resistant, more
aforementioned properties, the other is seen
as a welcome add-on.
contributor.“ durable, or stay clean longer. So there will be
new additives developed supporting or ena-
There are other types of multi-functional bling the use of new binder systems. More-
additives with very pronounced properties over, any additives that increase the lifetime
which, on one hand, may limit their broad us- of coatings will play a major role.
age. On the other hand, they add a very high Also, there is a strong trend toward modu-
value to the formulations for which they are lar coating manufacture. The use of pigment
suitable. concentrates, slurries, and other semi-fin-
And this brings me to the challenges of the ished components is and will be increasing.
approach of developing multi-functional ad- We believe that additives for these applica-
ditives. tions will continue to grow over-proportional-
Additive suppliers need to clearly define ly and that innovation on the additive side will
which applications they are aiming for when strongly support this trend.
developing such multi-functional additives. Last but not least: Working with larger coating
The more pronounced and specific the de- producers, we encounter a lot of complexity-
sired effects are, the more application-spe- reduction projects. Additives that cater to the
cific the resulting products become. We have resulting needs, e.g. by being broadly appli-
found it extremely valuable to develop such cable, non-hazardous, and globally available
products in close collaboration with our cus- will benefit here. Multi-functional additives
tomers. which are able to replace two or three oth-
To finally answer your question: Yes, we con- ers in an existing coating formulation can be
tinue to see potential in the development of a great contributor to such projects. 
multi-functional additives, including function-
alities that so far have not been achieved.
Susanne Struck
2 We see some strong trends in the coat-

ings industry that will impact the additive
market for the years to come.
VP Applied Technology EMEA
Evonik Resource Efficiency
susanne.struck@evonik.com
E XP ER T V OIC E S 19
Source: imagosrb - adbobe.stock.com

1 Modern high performance coatings pro-
vide levels of corrosion prevention and
“As the levels of fuel needed to power the ship through
the water. Coatings have been developed to
durability way in excess of what has been
historically possible. With advances in coat- of additional prevent fouling and also reduce the frictional
drag of the hull in the water. These coatings
ings has come the expectation that systems
will last for extended periods of time with, functionality now allow additional fuel savings of 6% to 9%
with up to 40% fuel saving being targeted in
for example, the recent ISO12944 standard further developments.
introducing a new requirement for very high become more A challenge operating in cold climates is ice
durability systems that can last more than 25 build-up; icicles falling from overhead pipes
years. Much of what contributes to coatings’ extreme, it is poses a hazard to workers below; ice for-
long term performance is certainly to do with mation on wind blades adds weight causing
surface preparation and application, but the
expectation is that modern coating systems
unlikely that damage to the wind tower mechanism. Coat-
ings are being developed that in addition to
will be capable of extended performance in
harsh environments – if applied correctly.
simple formula- corrosion protection and abrasion resist-
ance, produce a low energy surface that pre-
Developments in all areas of coatings formu-
lation has made this possible including bind-
tion approach- vents ice formation.
Corrosion is a major problem with repairs
ers, pigmentation and additives. Although
used in small quantities, the role of additives
es will be suc- costing billions of euros a year. Often cor-
rosion is hidden, not possible to see when it
has played a major part in the advancement
of coating formulations helping to design
cessful and starts and by the time it is visible, the areas
affected are considerably greater than the
high performance, low VOC coatings that
have great appearance and are easy to use. industry col- initial breakdown. By incorporating sensors
into the coating that can measure electro-
Used correctly, additives allow improvement
in properties, optimised use of coating com- laborations will chemical or physical changes in the coating
early on, targeted repair work can be carried
ponents and improved coating appearance out in a timely manner to prevent spread of
especially flow, levelling and gloss levels. be needed with corrosion, reducing the cost of repair and ex-
Further advances in coatings development tending the life time of the coating system. As
are taking these sophisticated products and contributions the challenges in the industry become ever
incorporating additional functionality into the more complex and the levels of additional
formulation to provide added customer ben-
efits way beyond the original intention. This
required from functionality become more extreme, it is un-
likely that simple formulation approaches will
has already happened in a number of areas
and the successful coating suppliers of the
all players.“ be successful and industry collaborations will
be needed with contributions required from
future will be the ones who can serve the in- all players.
dustry by addressing these previously unmet
and sometimes hidden needs.
The fouling of ships’ hulls by marine organ-
isms is a major issue in the shipping industry
Aidan Mernin and
Director of Protective R&D
Santiago Arias
2 Many of the future properties of coatings
are going to come from the use of a new
generation of additives and not just from bind-
with a fouled hull increasing the drag of the Director of Decorative & Floor er and formulation modifications. Increasingly
ship through the water, leading to increased Coating R&D we are going to see a need for additives that
fuel use and resulting in higher operating Hempel will be capable of altering surface characteris-
cost. The key function of antifouling paints Contact: Sara Stendevad tics, film morphology and electrochemical and
is to prevent fouling and reduce the amount savst@hempel.com physical properties of the coating. 

20 W E T T I N G A G E NT S
Source: Oleksandr Delyk - stock.adobe.com
STICKING TO POLYMERS
Wetting agent and substrate interactions in water-borne finishes for the automotive industry.
By Rainer Erhardt and Sascha Oestreich, BASF (publsihed in ECJ 06/2016).
Good substrate wetting may be par- manding in terms of wetting, especially for substrate to be coated. As a general rule,
ticularly difficult to achieve on plastic water-borne coatings. The study reported wetting takes place if the surface tension of
substrates, which are increasingly used below was set up to investigate in detail the the liquid is lower than the surface energy of
in the automotive industry. Tests with influence of different wetting agent chemis- the substrate’s surface. This criterion for wet-
a range of different types of wetting tries on water-borne coating formulations. ting is also known as the wetting condition.
agents showed pronounced and possi- Poor wetting (such as ‘de-wetting’) will occur
bly unexpected differences. A fluorinat- SURFACE DEFECTS AND SUBSTRATE if the surface tension of the paint is higher
ed acrylic polymer gave the best overall WETTING ISSUES than the surface tension of the substrate.
results. Thus, substrates with low surface tensions
Formulating a defect-free coating is a chal- are not easy to wet with water or water-
A ppearance and adhesion are key per-

formance characteristics for any coat-
ing, but in automotive coatings they are
lenge. It needs careful control of the surface
chemistry of the coating. More specifically,
local surface tension differences are the
borne coatings. Special substrate wetting
agents are required to lower the surface
tension of the coating.
especially crucial. In this market segment in primary cause of many surface defects (for Therefore an effective wetting agent for
particular plastic substrates are becoming example, craters). These local differences a coating formulation should have sur-
increasingly important for both interior and can be minimised by the use of special wet- factant characteristics in order to lower
exterior parts. ting agents. the surface tension of the liquid to allow
Because of their rather low surface energies, Substrate wetting depends primarily on the the liquid to wet the surface. This is
plastic substrates are usually much more de- surface tensions of the coating and of the especially important if hydropbic subtrates
WE T T I N G A G E N T S 21
(e.g. plastics) have to be coated with water- Organo-modified silicones like Product 3221
borne formulations. are a widely used class of polymers. Depend-
ing on the degree of modification and on
RESULTS AT A GLANCE MAIN WETTING AGENT TYPES AND THEIR their overall silicone content they can be em-
KEY PROPERTIES ployed as substrate wetting agents, flow- and
űű Good substrate wetting is essential leveling agents and/or slip agents.
for good appearance and adhesion. For this study, various wetting agents of dif- In general, silicone-based additives reduce
This may be particularly difficult to ferent chemical structures were selected as the surface tension of a formulation rather
achieve on plastic substrates, such as shown in Table 1. The advantages and dis- drastically. Silicone surfactants, due to their
those which are increasingly used in the advantages of the main chemical types have short chain lengths, will not provide surface
automotive industry. been briefly summarised. slip in most paint systems.
Sulfosuccinates like Product 3475 are highly Fluorinated polyacrylates (Products 3370
űű Wetting agents of varying chemi- dynamic, cost-effective wetting agents. Due and 3500) are another very versatile class
cal nature show large differences in to their excellent dynamic surface tension re- of interfacially active additives. They are well
surface tension and dynamic surface duction and broad food contact compliance represented in the coating industry as sub-
tension reduction if examined in water they are commonly used as substrate wetting strate wetting agents and flow- and levelling
dilution. In combination with an acrylic agents in the printing and packaging indus- additives. 
dispersion however, these differences try. However, sulfosuccinates are also known
are less pronounced. to promote foam stabilisation.
Alkoxylated surfactants (Products 3120, 3650
űű Different types of plastic substrates and 3322) are usually cost-effective, non-ion- Table 1: Over view of the selected wetting
which have very similar surface energy ic wetting agents. Depending on the alcohol agents and their chemistries.
yield large differences in adhesion. In used in their synthesis, the ratio of ethylene
this case, on average the best results oxide to propylene oxide and the overall Wetting Agent Chemistry
were achieved on PA and worst results degree of alkoxylation their hydrophilic-li-
on ABS/PC. pophilic balance (HLB) can be varied widely.
Product 3475 Sulfosuccinate
Some alkoxylated surfactants are particularly
űű From all the wetting agent technolo- low-foaming wetting agents. Product 3120 Fatty alcohol
gies tested, a fluorinated acrylic poly- Star-shaped polymers, here represented alkoxylate
mer gave the best overall results. by Product 3322, form a special class of
alkoxylated surfactants The hyperbranched Product 3650 Synergistic blend
structure of these non-ionic surfactants was including alcohol
modified to give them additional wetting and alkoxylates
defoaming properties. Product 3322 Star-shaped polymer
based on alkoxylated
fatty alcohol
Product 3221 Silicone-based

wetting agent
Figure 1: Dynamic surface tension at different bubble frequencies of various wetting
agents in water. Product 3370 Fluorinated
polyacrylate
Product 3500 Fluorinated

Wetting agents 0.5% in demineralised water polyacrylate
80
Dynamic Surface Tension [mN/m]
70
Table 2: Coating formulation used in
60 Testing
50 Coating formulation Parts by weight
40 Dispersion 8211 100.0
30 Butyl glycol 7.0
20 Texanol 3.0
8
6
4
6
3
10 7
01
03
05
08
14
71
97
19
29
44
64
06
49
96
57
40
,1
Wetting agent (see 0.5

0,
0,
0,
0,
2,
3,
0,
0,
0,
0,
1,
1,
1,
5,
7,
Frequency [Hz] Table 1)
Defoamer (silicone) 0.4

Demin. water Fluorinated polyacrylate Sulfosuccinate
Fatty alcohol alkoyxlate Silicone surfactant Ammonia 25 % If necessary, add to
adjust pH to 8-9

Table 3: Initial adhesion and appearance tests.
Tests after ageing Target value Substrate WE 3221 Silicone WE 3500 Fluor. WE 3650 Surfactant WE 3322 Star WE 3370 Fluor.
(48 h @ 60 °C) (Norm) acrylate blend polymer acrylate
Adhesion 0-2 PA 0 1 0 1 0
GT (crosscut) DIN ISO
PC 0 0 0 0 0
2409
ABS 0 1 0 1 0
ABS / PC, T65 0 1 0 1 1
K (knife test)
PC 0 0 0 1 1
DBL7399-5.1
ABS 4 4 4 3 4
ABS / PC, T65 3 3 3 3 3
Gloss 20°/60° ** 0-2 ABS 90/96 88/96 90/97 92/97 87/97
ABS / PC, T65 90/98 90/98 92/99 94/99 90/98
Haze ** ABS 144 221 87 88 131
ABS / PC, T65 109 127 87 67 149
Appearance PA 2 2 2 2 2
Specks
PC 2 2 2 2 2
ABS 2 2 2 2 2
ABS / PC. T65 3 3 3 3 3
Levelling 0-2 PA 1 1 1 1 1
PC 1 1 1 1 1
ABS 1 1 1 1 1
ABS / PC, T65 0 0 0 0 0
** Gloss and haze not measured over PA and PC substrates. Note: Cratering 0 for all samples; norm specifies 0-2 rating
Table 4: Test results after Condensation Water Test according to DIN EN ISO 6270-2: 240 h duration; all tests after 1 h regeneration
time unless shown otherwise. Note: degree of blistering (DIN EN ISO 4628-2): 0 for all samples; norm specifies zero.
Tests after Conden- Target value Substrate WE 3221 WE 3500 Fluor. WE 3650 WE 3322 Star WE 3370 Fluor.
sation Water test (Norm) Silicone acrylate Surfactant blend polymer acrylate
GT (crosscut)
PC 2 0 1 1 1
DIN ISO 2409
ABS 2 2 2 2 1
ABS / PC, T65 0 2 0 2 1
Adhesion K 0-3 PA 3 2 2 4 1
(knife test)
PC 4 3 3 3 1
DBL7399-5.1
ABS 4 4 4 4 2
ABS / PC, T65 4 5 3 3 5
Appearance after PA clear clear clear clear clear
humidity test + 1 h
PC whitish whitish whitish whitish whitish
regeneration
ABS whitish whitish whitish whitish partially whitish
ABS / PC, T65 whitish whitish whitish whitish whitish
Appearance after PA clear clear clear clear clear
humidity test + 24 h
PC slightly turbid slightly turbid slightly turbid slightly turbid slightly turbid
regeneration
ABS partially whitish clear partially whitish partially whitish clear
ABS / PC, T65 whitish, whitish, after whitish, whitish, after whitish,
after 48h clear 48h clear after 48h clear 48h clear after 48h clear
WE T T I N G A G E N T S 23
 These polymers have a polyacrylic backbone tion if wetting agents are used in a new coat-
with fluorinated side chains which lower the ing formulation. Figure 3 provides an example
WE 3120 FA WE 3475 surface tension of a formulation. They com- in which different surfactants lead to very dif-
ethoxylate Sulfo-succinate bine excellent flow and leveling with anti-cra- ferent foam levels. The results show density
tering and good wetting behaviour. values after stirring of binder emulsions with
0 0 wetting agents (180 sec at 5000 rpm). Higher
APPLICATION TECHNIQUE MAY AFFECT densities indicate better defoaming and low-
0 0
SURFACTANT CHOICE er densities indicate foam stabilisation.
0 1 As can be seen from Figure 3, sulfosucci-
1 1 It should not be overlooked that diffusion and nate surfactants stabilise foam in this case,
adsorption of surfactants at interfaces is a whereas products such as the star-shaped
0 1
time-dependent process. New interfaces are wetting agent 3322 used here have pro-
0 0 produced extremely rapidly during spraying, nounced defoaming characteristics. The
3 3 printing or other coating application tech- defoaming effect of star-shaped wetting
niques and the mobility of the surfactants is agents has also been found by other scien-
3 3
an important factor here. tific groups [2].
91/97 86/96 For fast-changing processes the use of highly
91/98 88/97 dynamic surfactants is recommended, in TEST FORMULATION AND APPLICATION
order to ensure that the surface tension re- DETAILS
102 163
mains low even if new surfaces are formed
93 136 very quickly. The different dynamic behaviour Clearcoat formulations based on the RC dis-
2 2 of wetting agents is illustrated in Figure 1. persion and wetting agents were prepared
The ability to lower the surface tension even next. The dispersion has a solids content of
2 2
under highly dynamic conditions (high bub- 44%, a Brookfield viscosity of 150 mPa•s at
2 2 ble frequency) depends on the mobility of 25 °C and a minimum film forming tempera-
3 3 the surfactants. It can clearly be seen in Fig- ture of 57 °C.
ure 1 that low molecular weight sulfosucci- As shown in Table 2, the formulation was
1 1
nates and alkoxylated surfactants can cover deliberately kept rather simple. Besides the
1 1 newly formed interfaces very quickly. On the dispersion it only contains the appropriate
1 1 other hand, the fluorinated polyacrylate and cosolvent, approximately 0.5% wetting agent
the silicone surfactants are slower due to plus defoamer. The liquid coating was filtered
0 0
their higher molecular weight and different before application using an 80 µm metal filter
aggregation behaviour. mesh (to remove possible coagulum).
Unfortunately, surface tension measure- The coatings were applied by drawdown us-
ments in pure water reveal little about the ing a 150 µm applicator bar resulting in a dry
behaviour of wetting agents in real coating film thickness of about 50 µm. After a flash-
formulations. In ‘real life’ coating formula- off time of 10 min at room temperature, the
tions the wetting agents interact with all the coatings were dried for 30 minutes at 60 °C.
WE 3120 FA WE 3475 other ingredients such as emulsifiers and The films were routinely aged for 48 h at
ethoxylate Sulfo-succinate polymer dispersion particles. If the dynamic 60 °C before testing (which is a common pro-
surface tension behaviour is measured in cedure for automotive plastic testing, e.g. ac-
2 1 polymer dispersions, the results show that cording to Volkswagen TL226 3.5).
the differences between surfactant types are Four plastic substrates relevant to the auto-
1 3
reduced, as revealed in Figure 2. motive industry were used for this screening:
1 1 polyamide (PA), polycarbonate (PC), acryloni-
0 1 WETTING AGENTS SHOW PRONOUNCED trile-butadiene-styrene copolymer (ABS) and
DIFFERENCES IN FOAMING a PC/ABS blend known as T65.
2 3
Prior to using these substrates, they were
3 3 Dispersion 8211 is a rheology controlled wiped with isopropanol in order to remove
2 2 dispersion or ‘RC dispersion’ [1]. In this sty- dust and possible other contamination. No
rene-acrylic polymer dispersion a special other forms of pre-treatment were applied.
5 5
acid-containing oligomeric emulsifier is used. The surface tension of the plastic substrates
clear clear Compared to conventional systems, RC dis- ranges between 41.4 mN/m and 45.1 mN/m.
whitish whitish persions impart enhanced stability (both
steric and ionic stabilisation), good compat- TEST PROCEDURES SUMMARISED
partially whitish partially whitish
ibility with formulation additives and a nearly
whitish whitish Newtonian flow behaviour. The films were evaluated in terms of gloss (at
clear clear The particle sizes of RC dispersions are gen- 20° and 60°), haze and optical appearance as
erally smaller than for conventional disper- well as for adhesion (crosscut adhesion and
slightly turbid slightly turbid
sions. The results discussed below are all knife test). Crosscut adhesion was performed
clear partially whitish based on the use of this product. and rated according to DIN ISO 2409.
whitish, whitish A much undesired side effect of wetting The knife test was performed according to
after 48h clear (even after 48h) agents can be foam stabilisation. It is there- DBL7399-5.1, a Daimler Benz test procedure.
fore recommended to check foam stabilisa- In this test a round knife blade is used to 

 scratch the coating on the plastic substrate limited influence on (intercoat) adhesion. tested (transparent) PC substrate some tur-
while applying pressure on the blade. Accord- Exposure to humid climate conditions and bidity does remain.
ing to how hard it is to scratch off the coat- subsequent drying may have a significant
ing and what the residual appearance of the impact on both appearance (whitening) and ADDITIONAL TESTS CONFIRM BEST
scratch is, the results are rated from 0 to 5, adhesion (through swelling and shrinking). PRODUCT
with 0 being the best result and 5 the worst. That is why it should be routinely tested as
The initial results are summarised in Table well, using the humidity test according to In a further test series spray application tri-
3. Significant differences could be observed DIN EN ISO 6270-2. Results after this expo- als were also performed (not shown). In par-
with regards to the influence of wetting sure test are presented in Table 4. ticular, what is called the wetting limit (the
agents on adhesion. The knife test in particu- Here the same picture is observed, the minimum film thickness where a complete
lar proved to be a very valid differentiation same fluorinated surfactant performed best. film is formed) was evaluated. In this respect,
criterion. Despite swelling of the polymer by water va- too, the same fluorinated product showed
In this test the fluorinated polyacrylic wetting pour, adhesion must not be affected. Water excellent results. The wetting limit could be
agent Product 3370 performed best. Fluori- uptake might also lead to whitening which decreased to about 14 micrometres.
nated acrylic polymers are known for their has to be reversible. This reversibility was The RC acrylic dispersion already shows ex-
excellent wetting performance and their very indeed observed for this system; only on the cellent gloss and appearance with only a very
limited impact of the wetting agent, due to its
chemical nature and very small particle size.
Only some differences in haze are observed,
Figure 2: Dynamic surface tension at different bubble frequencies of various wetting especially on ABS, with values ranging from
agents in polymer dispersion 8211 (4:1). 87 to 221 indicating slight differences in com-
patibility of the polymer matrix with the re-
spective wetting agent.
Wetting Agents 0.5% in Dispersion 8211 and demineralised water 4:1 In general it is evident that the interaction of
wetting agents with the given polymer disper-
80 sion is a key factor in order to achieve excel-
lent adhesion and appearance characteris-
70
Dynamic Surface Tension [mN/m]
tics. Wetting agents not only influence the

wetting behaviour by lowering the surface
60
tension, they also have significant influence
on film formation and leveling. In addition
50
they also have an effect on foam formation.
40 From all the wetting agents tested, a fluori-
nated acrylic polymer gave the best overall
30 results. Product 3370 combines good wet-
ting characteristics with very little influence
20 on adhesion and defoaming characteristics.

8

4
6
3
10 7
01
03
05
08
14
71
97
19
29
44
64
06
49
96
57
40
,1
REFERENCES
0,
0,
0,
0,
2,
3,
0,
0,
0,
0,
1,
1,
1,
5,
7,
Frequency [Hz]
[1] Baah F, New Water based Polymers for
Blank Product 3221 Product 3500 Product 3650 Industrial Wood Finishing, 7th European Coatings
Congress, 7-8 April, 2003.
Product 3322 Product 3370 Product 3120 Product 3475
[2] Mojgan N.et al, Caught on camera, Europ.
Coat. Jnl., 2015, No. 10, pp 30-36.
Figure 3: Results of foam tests with wetting agents and Dispersion 8211.
Foaming behavior 0.5% Wetting agent in Dispersion 8211
0,95
0,90
0,85
Density (g/cm3)
0,80 EUROPEAN COATINGS LIVE

0,75
Learn more about wetting agents
0,70
on water-borne plastic coatings at
0,65 European Coatings Live
0,60 on 28 June 2016, 15.00 CET
Blank Product Product Product Product Product Product Product at www.european-coatings.com/live
3221 3500 3650 3322 3370 3120 3475
WE T T I N G A G EN T S 25
“The influence of
emulsifiers should not be
underestimated. “
Dr Sascha Oestreich
Head of Regional Technical Marketing
Formulation Additives
BASF
sascha.oestreich@basf.com
3 questions to Sascha Oestreich
In many cases the fluorinated polyacrylates seem to perform best. But what are their
main limitations?
Indeed, fluorinated polyacrylates are a very versatile group of interfacially active additives. They
combine excellent flow & leveling with anti-cratering and good wetting behavior. Additionally,
they have clear advantages with respect to intercoat adhesion and foam stabilization. There
are fluorinated polyacrylates with different fluorine content available on the market. This allows
the formulator to select the right product for a specific binder type and application. Fluorinated
polyacrylates are limited when strong surface slip and anti-blocking effects are required. Slip and
anti-blocking effects can better be achieved by organomodified silicones, for example.
Your study used a well-defined rheology controlled dispersion with enhanced stability.
In what way could your findings differ in “real life” coatings?
In this study we evaluated our wetting agents in increasingly complex formulations: We started
with simple water, then we used a commercially available polymer dispersion and finally we used
a simplified coating formulation based on the dispersion which additionally contained defoamer
and coalescing solvents. The application tests with these coating formulations showed best re-
sults with fluorinated polyacrylates. We think that the biggest difference can be observed between
measurements in pure water and measurements in a polymer dispersion. A wetting agent should
always be evaluated in the respective binder system or in the final coating formulation. The influ-
ence of emulsifiers and internal surfaces (e.g. latex particles) on the behavior of the wetting addi-
tive should not be underestimated.
Your study shows that substrates with very similar surface energy yield large differ-
ences in adhesion. What is the explanation for this behavior?
Good wetting is only one prerequisite for good adhesion. Certainly the chemical composition
of the substrate, the surface structure, possible pretreatment and many other factors influence
adhesion of a coating film, too. It is essential to ensure optimal interaction of the polymer film
with the substrate. Wetting is supporting physical and chemical adhesion because it increases the
surface area of the coating which comes into contact with the substrate. On the other hand, a
wetting agent should not have a negative effect on the (intercoat) adhesion. Also here, fluorinated
polyacrylates are well known in the market for their marginal influence on (intercoat) adhesion.
26 E A S Y - T O - C L E AN
Source: Andrei Merkulov - stock.adobe.com
GIVING DIRT THE BRUSH-OFF

Easy-to-clean properties now available for epoxy resin systems. By Majdi Al-Masri, Wolfgang Griesel and Lin Xie, Byk
(published in ECJ 12/2016).
A new hydrophobising additive for 2-pack epoxy systems has clean surfaces bring huge economic and time advantages [1, 2].
a polymer structure containing functional groups that lead to
chemical bonding with the coating matrix. The additive reduc- TWO VERY DIFFERENT EASY-TO-CLEAN TECHNOLOGIES
es the effects of soiling and resisted repeated contamination/
hot cleaning cycles. Improvements were noted in several other The easy-to-clean effect can be achieved, for example, by using self-
properties. cleaning or easy-to-clean coatings. These easy-to-clean surfaces are
created using two different technologies: there are (super) hydrophilic
E poxy resin coatings (EP coatings) are characterised by their high

chemical and mechanical resistance, and are generally applied in
thick layers. The cured EP coatings also exhibit extremely high adhesion
and (super) hydrophobic surfaces.
(Super) hydrophilic surfaces are characterised by a contact angle to
water from 0° (‘super’) to 30° [3]. The water wets the surface, thus
to the substrate. Epoxy resins generally refer to diglycidyl ethers of bis- infiltrating the deposited dirt. These surfaces are manufactured ei-
phenol A or bisphenol F. In this structure lies the reason for the limited ther by embedding defined structures on the surface, for example us-
UV resistance of EP coatings. This is why they are recoated for outdoor ing self-assembling monolayers, or by the best-known method, using
applications with a UV-stable topcoat such as polyurethane (PU). photocatalytic TiO2 [4]. In comparison, (super) hydrophobic surfaces
Wherever the need for such a topcoat can be avoided, the benefits have a contact angle of at least 140° to water, and water therefore
of EP coating compared with PU coatings are uncontested. They are simply drips off [5]. This behaviour means that the deposited dirt will
admirably suited to coating machinery, plant, railway car parts, pipe- be removed with the water. This effect can be achieved by creating
line and tanks and for construction parts and concrete floors which hierarchical structures (‘Lotus effect’) which, however, is characterised
experience high mechanical or chemical stress. For this reason, it is of by a time-consuming application process and may only last a short
great interest to develop customised surface additives for one-coat EP time due to loss of the surface structure [6].
coatings. In addition to levelling additives, which are used to improve
film formation, additives to prevent dirt pick-up and to simplify surface IMPROVING THE PERFORMANCE OF HYDROPHOBIC ADDITIVES
cleaning are becoming increasingly important. Particularly in applica-
tions where clean surfaces play a major role in preventing contamina- It is a little simpler to use powerful surface tension reducing and
tion, such as in containers, tanks and conveyor systems, or for safety or hydrophobising additives for coatings, which include fluorinated hy-
aesthetic reasons such as in tunnels and corridors (Figure 1), easy-to- drocarbon compounds and silicone oils. However, because of the ad-
E A S Y-T O -CLE AN 27
powder-water suspension and with 1% carbon black powder in hand

cream. The carbon black powder was sprinkled on the surfaces. The
RESULTS AT A GLANCE aqueous carbon black suspension and the carbon black hand cream
were applied to the surface using a laboratory paper towel that was
űű Existing easy-to-clean additives for epoxy topcoats tend to wetted with the suspension or hand cream. After being washed using
have only short-term benefits. A new hydrophobising additive a standard dishwasher program (2.5 h at 50 °C), the samples were
for 2-pack epoxy systems has been developed, with a polymer visually assessed, photographed and re-contaminated and washed
structure containing functional groups that are compatible with again as described above. This process was repeated several times.
epoxy resins and lead to chemical bonding with the coating ma- In addition to the ‘control’ (coating without additive) a conventional
trix. silicone additive was used in the tests as a comparison. Figures 3, 4
and 5 show the exceptional easy-to-clean effect and durability of the
űű The additive reduced the effects of both hydrophobic and new additive, regardless of the polarity of the contamination. The ef-
hydrophilic contamination and resisted repeated cleaning in a
dishwasher at 50 °C much better than a commercial silicone
additive. Figure 1: Some possible applications of EP monolayer coatings
(i.e. areas with limited UV light exposure). Source: 3dmentat/Fo-
űű Significant improvements were found in a number of other tolia Pavel L Photo and Video/Shutterstock and Kekyalyaynen/
properties, including reduced carbamate formation, decreased Shutterstock
ice adhesion and improved de-icing and greater UV resistance.
űű Levelling was not affected and there was no evidence of cra-

tering or increased foaming. Pot life is unaffected, and there is
no reduction in intercoat adhesion.
verse environmental impact of fluorinated hydrocarbons, their use is

undesirable [7].
Traditional silicone oils only display a short-term effect and may also
cause levelling problems [8]. Silicones that are modified with polar
groups result in better levelling. However, the easy-to-clean effect is
only short term. These silicone additives lose their effect after a few
(generally no more than two) cleaning cycles.
By making a wise and well-balanced structural selection such as the
ratio of polar to non-polar groups, an additive was recently developed
that combines the two properties of being easy to clean and having
optimum levelling. Using silicone macromonomer technology, and by
introducing groups that are compatible with epoxy resin that form
covalent bonds with the coating (Figure 2), an additive with long-lasting
easy-to-clean properties could be developed.
This additive is characterised by a strong surface orientation, so
that the polar portion of the copolymer remains in the inside of the
polymer film and the reactive groups form a covalent bond with the
binder, thereby embedding themselves. The additive has also shown
compatibility with most EP systems, whether conventional, high-solids
or solvent-free.
COATINGS RESIST REPEATED SOILING AND CLEANING
The strong hydrophobic effect generated by the surface enrichment

of the silicone block results in a surface that strongly repels dirt in
solid, liquid or mixed form irrespective of whether the contamination
is of a hydrophobic (oil-based) or hydrophilic (aqueous) nature. Metal
sheets were coated with a conventional EP topcoat. In some sheets,
the coating contained up to 2% of the new additive (all specified per-
centages are by weight). The sheets were contaminated in different
ways, stored for one hour at 50 °C and then washed in a commer-
cially available dishwasher on its standard program. The contamina-
tion was simulated with carbon black powder, with a 2% carbon black 

 fect could be demonstrated after up to ten cleaning cycles. Even if Figure 6, right illustrates the result. Cohesive failure occurred only in
these simulated contamination and cleaning cycles do not entirely the primer, which indicates extremely good adhesion between primer
correspond to real-life conditions, they are nevertheless proof of and topcoat.
the effectiveness of the additive under harsh conditions. In addition,
these tests were able to demonstrate significant differences from the SMOOTHNESS IS UNAFFECTED AND SLIP INCREASED
conventional silicone additives.
Another key property of coatings is film formation or film integrity,
PULL-OFF TESTS SHOW INTERCOAT ADHESION IS RETAINED which is especially ensured by optimum levelling. Silicone additives
can cause levelling issues as a result of high incompatibility with the
The new additive was developed as an easy-to-clean additive and is system.
therefore recommended for use in topcoats. However, as it is also For this reason, the new additive was used at different concentra-
a surface-active substance, it is important that there should be no tions in the EP coating systems, and the levelling was tested. Levelling
adverse influence on the intercoat adhesion, i.e. no reduction in adhe- measurements for the samples without the additive (control) and with
sion between the topcoat and the base coat. 0.5% to 2% of the new additive show similar values. An additive quan-
A pull-off test in accordance with DIN EN ISO 4624 was used to con- tity of up to 2% did not cause any levelling issues. Larger quantities
firm that the additive caused no intercoat adhesion problems. A red, were not tested as the easy-to-clean effect can be fully achieved at the
conventional 2-pack EP primer was applied at 200 µm wet film thick- 2% addition rate. To test surface slip, experiments were conducted
ness to sand-blasted steel (Sa 2½) and, after 30 days drying, it was with the same range of samples as for the levelling test. The results in
coated with 100 µm of a white 2-pack EP topcoat containing 2% of Figure 7 show, based on the coefficient of friction, a strong increase
the new easy-to-clean additive (Figure 6, left). After a further 14 days of in slip even with a low quantity of additive. Even as little as 0.5% was
drying, the pull-off test was performed according to DIN EN ISO 4624. sufficient to significantly improve the slip.
Figure 2: Schematic diagram of the modified silicone polymer structure.
Figure 3: Easy-to-clean effect in conventional EP topcoat Figure 4: Easy-to-clean effect in conventional EP topcoat
without additive, with 0.5% conventional silicone additive and without additive, with 1% conventional silicone additive and
with 0.5% new additive after contamination with carbon black with 1% new additive after contamination with 2% carbon black
powder and cleaning in washing machine. suspension in water and cleaning in washing machine.
Cleaning Conventional Cleaning Conventional

cycles Control silicone additive New additive cycles Control silicone additive New additive
1 1
3 3
8 6
E A S Y-T O -CLE AN 29
SOME IMPROVEMENTS FOUND IN OTHER PROPERTIES Figure 6: Schematic coating structure for the pull-off test (left)
and pull-off test according to DIN EN ISO 4624 (right). No ad-
The defoaming property of epoxy systems is very significant as a reverse impact on the intercoat adhesion.
sult of their often relatively high viscosity. The additive was used at a
proportion of 2% in a 2-pack epoxy system. A defoaming effect was
observed in comparison with the sample without the additive. As a 30d 2%
result of its specifically low incompatibility, the additive does not sta-
bilise foam and can even improve defoaming.
In two-component systems, the pot life always plays an important
role. When using the new additive, there may initially be a slight in-
crease in viscosity. However, it has no impact on the pot life. When
curing epoxy/amine two-component coatings, a significant reduction
was observed in carbamate formation. Carbamates, which are also Reverse of dolly Cohesive failure
in the primer
referred to as ‘amine blush’, are chemical compounds that form from
air, especially with ambient curing EP systems under the influence
of high air humidity and carbon dioxide. They result in haziness on
Figure 5: Easy-to-clean effect in conventional EP topcoat with- Top coat (white)

out additive or with 2% silicone after contamination with 1% Epoxy primer (red)
carbon black powder in hand cream. A = directly after wiping B = Blasted steel sheet
after 10 contamination and cleaning cycles.
Conventional silicone
Control additive New additive
Figure 7: Influence of the new additive on slip for a conventional

EP coating without additive (control) and with 0.5 – 2% additive.
0.6
1
0.5
Coefficient of friction
0.4
0.3
0.2
3 0.1
0
Control 0.5% 1% 2%
Additive Additive Additive
Figure 8: Use of the surface additive prevents ice formation in topcoats – immediately after sprinkling with ice water (A1 without ad-
ditive, B1 with 2% additive) and five minutes after sprinkling with ice water (A2 without additive, B2 with 2% additive).
A1 B1 A2 B2

 black or brilliant surfaces [9]. Three panels were coated with a black
EP/amine coating. The samples were cured at room temperature and
at an air humidity of 85%. Following curing, the colour of the sheet
metal without the additive displayed strong greying. Adding 2% of a
common silicone additive slightly reduced the grey discoloration. Us-
ing 2% of the new additive meant that there was virtually no greying.
This visual evaluation was also confirmed using measurements taken
with the Byk-Gardner “colour guide” spectrophotometer. The white-
ness L* values (in the CIELab system) of the control, of the sample
with the silicone additive and of the sample with the new easy-to- Dr Majdi Al-Masri
clean additive are 33.7, 29.5 and 27 respectively, indicating that the Head of Research
new additive retained the darkest shade. Surface
Byk-Chemie
RESISTANCE TO UV EXPOSURE CONSIDERABLY IMPROVED Majdi.AlMasri@
altana.com
In addition to protection against carbamate formation, the EP coat-
ing with the new additive also survives 550 hours of QUV-B exposure
with only minor alteration. The ∆YI values (the difference between the
yellowness indices in accordance with ASTM E313) were determined
with the same spectrophotometer for the samples without additive,
with the conventional silicone additive and with the new additive, be-
fore and after QUV exposure. The differences were 17, 11 and 8.57
“The system can be
respectively.
The strong reduction in surface tension by the new additive led to
readjusted by reducing the
another test, which was performed by an independent institute.
A low surface tension can reduce the ice adhesion to coating films rheology additive level.“
or improve the de-icing of the surface. For this purpose, investiga-
tions were performed in a defined atmosphere, in which ice water
was sprinkled on the samples at -5 °C and a defined wind speed of
11.5 m/s and humidity of 66%.
Instantly and after five minutes, an image of the sprinkled samples
was taken to evaluate the degree of icing (Figure 8). The sample that
contained the additive displayed a considerably lower degree of icing. 3 questions to Dr M ajdi Al-Masri
This phenomenon also suggests the additive could be used for surfac-
es that require de-icing for technical, economic or safety reasons.  Does the slight increase in viscosity show an impact on the
spray application performance or levelling? It depends on the
REFERENCES coating system. As most coating systems contain rheology additives,
the system can be readjusted by reducing the rheology additive level or
[1] Lienhard J. et al, Atlas Kunststoffe und Membranen, Institut für internation- other spray application parameters in order to maintain the coating
ale Architektur-Dokumentation, Munich 2013, p 47. performance.
[2] Gniecko J., Helfand D., Modern Paint & Coatings, 1994, Vol. 84, No. 3, pp What methods of testing for easy-to-clean effects were used?
26–28. Does the use of a standard dish washer program for testing
[3] Tölke T., Photokatalytische Schichtsysteme für hochtransparente selb- entail the use of detergents? The test was carried out by contami-
streinigende Gläser, Dissertation, Friedrich Schiller University, Jena, 2009. nation with carbon black in different media, followed by visual evalu-
[4] Mortimer C E., Müller U., Chemie, 9th edition, Stuttgart, 2007, p. 469. ation. The results were documented by photographs. We believe that
[5] Greßler S. et al., Selbstreinigende, schmutz- und wasserabweisende the long-term and recurring cleanliness of the coated panels is evi-
Beschichtungen auf Basis von Nanotechnologie, nano trust dossiers, 20, dence for the presence of the surface additive over multiple cleaning
2010, p 3. cycles involving a common market detergent.
[6] Solga A. et al, The dream of staying clean, IOP Publishing Ltd, 2007, p Does a higher content than 2% of the product affect the sur-
126. face similarly to regular silicones? The addition of more additive
[7] AssTech. Newsletter – Perfluorierte Kohlenwasserstoffe (PFC), http,// is not always helpful. An excess of the additive in this case may form
www.asstech.com/de/downloads/newsletterPFC.pdf (14.05.2014). a liquid layer on the surface which is not chemically bonded to the
[8] Bieleman J., Lackadditive, Wiley-VCH Verlag, Weinheim, 1998, p 177. matrix. This layer will act as regular silicon and could leave a greasy
[9] Bell J.P., Reffener J.A., Petrie S., Jnl. Appl. Polym. Sci., 1977, Vol. 21, pp surface. In addition, it could also affect the appearance of the coating
1095–1102. or its adhesion.
BYK Additives
World-class in
water-based formulations
Acting in an eco-friendly and sustainable manner is a responsibility and obligation we all have. As the
leading global supplier of additives for water-based systems, BYK takes this challenge seriously. No
matter whether paints, plastics or industrial applications, our products for water-based formulations
help to care for our environment and to protect our health. And these solutions are equally high-
performance, economic and easy to work with as solvent-based additives. The future is in aqueous
systems – for a better future for every one of us.
www.byk.com
32 FUN C T ION A L C OAT I NG S
Source: somrerk - stock.adobe.com
POWER AT ITS CORE

Using microencapsulation to produce smart coatings. By Claus Jurisch, Koehler Innovative Solutions (published in ECJ
04/2017).
Core-shell microencapsulation technology offers a number of the aim of protecting and releasing these ingredients. [1]
advantages for the paints and coatings industry. It helps over- In principle, there are two types of microcapsules:
come incompatibilities in coating systems and can be used with ąą a) capsules in which the content is dispersed in a basic mass (ma-
a variety of release mechanisms to suit different applications. trix capsules)
Accelerating the development phase and understanding the ąą b) microcapsules, in which the ingredient is uniformly surrounded
key parameters will pave the way for future growth in this field. by a defined sheath (core-shell capsules (Figure 2).
The focus in this paper is exclusively on microcapsules with a core-
S ince its humble beginnings in carbonless paper some 60 years

ago, chemical microencapsulation has made great strides in the
past decade to enable new industrial chemical benefits. Early appli-
shell structure containing a lipophilic active compound. For the en-
capsulation of lipophilic core materials the most common process is
the preparation of an oil-in-water emulsion. Based on this principle,
cations following capsules for carbonless paper included agricultural various capsule types have been developed to envelop the finely dis-
pesticides and perfume oils in scratch and sniff magazine inserts, persed oil droplets with a solid shell. Wall formers that are completely
which benefited from the controlled-release properties (environ- soluble in water are consequently deposited from the continuous wa-
mental decay/diffusion and mechanical shear breakage) that these ter phase onto the oil droplets and then crosslinked (see Figure 3). This
core-shell microcapsules offered. These applications paved the way mechanism is used to produce aminoplast and phenoplast microcap-
for a more widespread use of chemical microencapsulation in various sules (in situ polymerisation) [2] and to produce water-soluble hydro-
functions and different branches. Whether it be microencapsulation colloid capsules (coacervation) [3, 4]. However, the reverse case is also
of perfume oils in homecare products, additives in paints and coatings possible, for example in the case of wall formation by free-radical poly-
or one-component adhesives, the increase in patents over the years merisation of oil-soluble acrylate monomers [5]. In addition, methods
(Figure 1) highlights the great interest of industry in this technology. are used in which water-soluble and oil-soluble starting materials react
at the phase boundary of the emulsion droplets to form a solid shell.
MICROENCAPSULATION STATE OF THE ART Examples are the reaction of isocyanates and amines or alcohols to
give polyurea or polyurethanes (interfacial polymerisation) [6], but also
Microencapsulation is an umbrella term for different technologies the hydrolysis of silicate precursors with subsequent condensation to
that encapsulate liquids, gases or micronised solids with a shell, with form an inorganic capsule wall (sol-gel method) [7].
FU N C T I O N A L C O AT I N G S 33
achieved by a defined degree of crosslinking and the construction of

the polymer microcapsule shell. This diffusion-controlled delivery of
active substances by microencapsulation can be found in many tech-
nical applications such as for biocides [9], inhibitors and insecticides.
Targeted release of the core material requires a trigger, which opens
RESULTS AT A GLANCE the shell. According to the capsule structure this mechanism can be
triggered by temperature [10], UV light [11], enzymatic activity [12] or
űű A lipophilic core material is encapsulated in a solid shell and also by a change in the pH value [13]. Alternatively, mechanical forces
released on demand to provide additional functions in the form of pressure, friction and shear can also destroy the cap-
sule shell and release the contents abruptly. This release mechanism
űű Microcapsules help overcome incompatibilities within coat- is used for the sudden burst of perfume oil in fabric softeners and
ing systems, for example, biocides with binders. laundry detergents or self-healing agents in protective coatings.
űű Microencapsulating anti-corrosives and combining them MICROCAPSULES IN ACTION

with corrosion indicators produces smart, self-healing coatings
that prolong the service life of equipment The paints & coatings industry has embarked on using microencap-
sulation to increase product functionality and to offer smart coatings
űű The release mechanism is the key to functionality and anal- for different applications such as antifouling, corrosion protection and
ysis must be swift to accelerate development self-healing. The microencapsulated active ingredient within the paint
or coating matrix provides a controlled delivery system of the active
űű Microencapsulation technology offers great potential for compound via a release method anticipated by the capsule designer
more complex applications using different active compounds for the particular application.
to offer even smarter coatings
ENCAPSULATED BIOCIDES OVERCOME INCOMPATIBILITIES
The regulations for the use of biocides are becoming increasingly re-
strictive, specifying the lowest active concentration possible. Typically,
biocides should be released slowly over time to achieve the maximum
service time of the protective coating. However, controlling the bio-
logical growth of microorganisms and marine crustaceans depends
mainly on the optimal concentration of the biocide. Too low a quan-
tity of the active ingredient will not successfully prevent fouling, but if
the concentration is too high, this will have a negative impact on the
TARGETED RELEASE TRIGGERS environment and might end up in the food chain. Adding biocides
in stable core-shell microcapsules controls the leaching of the active
The choice of polymer and the degree of crosslinking makes it pos- ingredient and thus reduces the overall concentration [14].
sible to select individual capsule properties. The capsule size and the Furthermore, by using microencapsulation Rohm & Haas [15] could
wall thickness are also important control variables. In most applica- overcome incompatibilities of the biocide with the binder systems in
tions, the encapsulated core material should be released on demand the paint. Using the active compound in encapsulated form prevented
or within a defined period. In some cases, such as the encapsulation any impact on viscosity. By using a balanced mix of free and encapsu-
of phase change materials (PCM), a permanent inclusion of the core lated biocide it was possible to easily achieve the required antifouling
material is desired [8]. A prolonged release of the ingredient can be effect. 
Figure 1: Development of patents in 5-year inter vals (source:

database CAPLUS 17.01.2017; Key words; microcapsules in
paints, varnishes and coatings). Figure 2: SEM core-shell capsule.
2,093
1,555
251 322
190 210
44 58 65 118
2 6
1960 1965 1970 1975 1980 1985 1990 1995 2000 2005 2010 2015

 SMART COATINGS FOR SELF-HEALING studied in a polyurethane coating. As soon as cracks occurred in the
AND CORROSION PROTECTION paint film they could be successfully repaired by the release of the
linseed oil from the microcapsules that ruptured under simulated me-
Microcapsules, added to coatings, can fulfil additional functions and chanical action. The corrosion inhibitor played an important role in
open new perspectives in industrial applications. Microcracks and preventing corrosion in the scribed line region.
corrosion often remain undetected until severe damage becomes ap-
parent. This then proves costly, time consuming in reconditioning, and CAPSULES RELEASE ANTI-CORROSIVE
might bear significant safety risks. Smart coatings comprise corrosion COATING TO PROLONG SERVICE LIFE
indicators and self-healing agents, which make these deficiencies vis-
ible and instantly repair cracks and scratches when they arise. Further examples to increase the service time of military equipment
The key component for self-healing applications is the encapsulated include combining primers with self-healing microcapsules.
self-healing agent, which can be crosslinked using temperature, oxy- This system is called “polyfibroblast” [17], and was developed at Johns
gen or light. More reliable coatings contain both a self-healing agent Hopkins University’s (JHU) for the US Office of Naval Research for zinc-
and a crosslinking catalyst (Figure 5). Furthermore, additional function- rich military and commercial paints. Their development began in 2008
ality can be added using indicators such as colours or malodours. The to create a dry powder consisting of microscopic liquid-filled polymer
combination of the healing agent and a corrosion inhibitor is a further spheres that can be combined with standard military primers. The
extension of functionality for paints and coatings. innovative formulation allows paint scratches to heal by breaking cap-
Jadhav et al. [16] researched the encapsulation of linseed oil together sules and forming a coating over the exposed steel before corrosion
with a drying agent and corrosion inhibitor, and the protective per- takes place, while cutting maintenance costs and enabling vehicles to
formance of a coating with and without capsules. The core materials operate in the field for a longer time.
were encapsulated in phenol formaldehyde microcapsules via an in
situ polymerisation process. The self-healing properties as well as the DUAL FUNCTION – INDICATION AND INHIBITION
anti-corrosive performance of the encapsulated microcapsules were
In addition to the healing effect, NASA [18] further developed pH-
sensitive microcapsules and microparticles to incorporate the au-
Figure 3: Schematic image of microencapsulation by in tonomous corrosion indication and inhibition function into a smart
situ polymerisation or coacer vation. coating. The microcapsules and particles are designed specifically to
detect the pH changes that are associated with the onset of corro-
sion. The formulation responds autonomously to indicate early-stage
corrosion. The release of corrosion inhibitors and self-healing or film-
forming agents repairs the mechanical damage of the coating.
The use of microcapsules for self-healing applications provides many
options and inspires numerous research projects in universities and
Capsule shell in research companies. But a successful development is proven in the
Core material
practical use in industry. There are several ways to reach this goal
whether the development is carried out internally or external part-
1 Core material is 2 Condensation 3 Deposition of 4 Hardening of ners are chosen. Some approaches are crucial for developing applica-
emulsified in an and phase wall material the capsule wall
aqueous phase separation on the emulsion by increasing tion-driven solutions.
by pH reduction droplets the temperature
KEY MICROCAPSULE DESIGN CRITERIA
Microcapsules have many advantages but also certain restraints,

which must be considered during the development phase. It is there-
Figure 4: Particle size distribution – coulter particle sizer and light microscopic image.
8.0
7.0
6.0
5.0
Volume (%)
4.0
3.0
2.0
1.0
0.0
0.01 0.10 1.00 10.00 100.00 1000.00
particel size (µm)
FUN C T I O N AL C O AT I N G S 35
fore essential to provide a detailed specification of the required func- Figure 5: Schematic illustration of self-healing.
tionality.
When developing microcapsules for self-healing coatings, their design
depends on the following parameters. Coating Catalyst Selfhealing agent
Capsule size is primarily determined by the amount of active ingredi-
ent in the formulation and the substrate coating thickness. Microcap-
sules can be produced with an average diameter of between 1 and
100 µm (Figure 4). As capsules for self-healing purposes must release
enough liquid to cover the damaged surface, the capsules should be
Substrate
sized appropriately with a very narrow size distribution. Considering
the thickness of the coating layer (about 100 µm), the diameter of the t:0 Catalyst
Microcapsule
incorporated capsules should be adequate to avoid a rough surface.
The capsule size is determined during the emulsifying step and is pre-
defined basically by droplet size. As the viscosity of the core material
has a major impact on the droplet formation it is necessary to define
t:1 Catalyst
the range of acceptable viscosities during the development stage. Microcapsule
The release mechanism is the key to functionality. Application tests
can be very time consuming and therefore it is important to create a
rapid analytical method that closely reflects the capsule performance.
Modifications of the formulation and process parameters, to optimise t:2 Catalyst
Microcapsule
the functional properties, can then be quickly verified and accelerate
the development phase. The formulation of functional capsules re-
quires the following development steps to evaluate core material and
capsule performance:
 Encapsulate several oils to determine the best core material for the
application
 Ascertain the appropriate emulsifying conditions for each liquid
core material to obtain the desired narrow particle size distribution
(Figure 4). 
 Determine the optimum amount of wall material and the right reac-
tion conditions to minimise by-products.
Oversize microcapsules, agglomerations or other by-products need
to be filtered out. If the level of by-products is too high, this hinders
the final purification of the coating formulation by filtering. Fines in
the capsule slurry will cause turbidity of the coating and disturb the
rheological behaviour of the coating formulation.
Once the application tests have proven the required quality in the
coating, the next challenge is to scale up from lab scale (1–2 kg) to
pilot scale (several hundred kg). There are two factors to scale up: the
emulsifying process and the chemical wall formation. As the viscosity REFERENCES
has a great impact on droplet size it is important to determine the ad-
equate kinetics in the emulsifying step. Parameters such as the type of [1] Singh M.N., Hemant K.S.Y., Ram M., Shivakumar H.G., Res. Pharm. Sci.
stirrer, stirring speed and time must be adapted and optimised. Using 2010, 5, 65.
the right mechanical treatment results in only minor differences in the [2] Pietsch G., Schrader K.-H., DE3743427, 1989.
wall-forming reaction when changing the production scale. [3] Bungenberg de Jong H. J., Kruyt H.R., Kolloid-Zeitschrift 1930, 50, 1.
[4] Xiao Z. et al., J. Sci. Food Agric. 2014, 94, 1482.
[5] Jahns E., Freudschuh U., EP0457154, 1991.
POTENTIAL FOR MORE COMPLEX APPLICATIONS [6] Nehen U., Weisser J., EP0727251, 1996.
[7] Ciriminna R., Sciortino M., Alonzo G., de Schrijver A., Pagliaro M., Chem.
Self-healing agents and corrosion additives can be encapsulated eco- Rev. 2011, 111, 765.
nomically. However, special requirements regarding particle size dis- [8] Jamekhorshida A., Sadramelia S.M., Farid M., Renew. Sustainable
tribution, purity and polymer by-products are higher than for other Energy Rev. 2014, 31, 531.
commercial applications such as fragrance capsules for homecare [9] Nunn M. B., US5164096, 1991.
products. When encapsulating active ingredients, the most important [10] Bergueiro J., Calderón M., Macromol. Biosci. 2015, 15, 183.
factor is the evaluation of the right core material and its compatibility [11] Huang Y., Dong R., et al., Soft Matter. 2014, 10, 6121.
to the wall material. The required performance determines the cap- [12] Santinho A.J., Ueta J.M., Freitas O., Pereira N.L., J. Microencapsul.
sule size whereas the required release mechanism defines the wall 2002, 19, 549.
structure and thickness. The possibility of adding different active com- [13] Hu Y., Cheng G., et al., Colloid Poly. Sci. 2014, 292, 2611.
pounds encapsulated and separated by a stable shell opens up new [14] Nikkola J. , European Coatings Journal 2014, 4, 36.
potentials for complex applications. Microencapsulation technology [15] Reybuck S.E., Schwartz C. US7377968, 2008.
is one approach that can be used in paints and varnishes to produce [16] Jadhav R.S., Mane V., Bagle A.V. et al. Int. J. Ind. Chem. 2013, 4, 31.
smart coatings with characteristics such as self-healing and anticor- [17] Benkoski J.J., Srinivasan R., Maranchi J.P., US20130017405, 2013.
rosion properties.  [18] Li W., Buhrow J.W., Jolley S.T., Calle L.M., US 8859288, 2014.

“What is needed are not the

microcapsules, but their
desired core material.“
2 questions to Claus Jurisch Dr Claus Jurisch

Product and Process Development
The loading of microcapsules is limited in the coating film. Do you expect a technical so- TE-PVE Teamleader Carbonless Copy
lution to increase the microcapsules proportion in the future? The more microcapsules are Papers and Microencapsulation
incorporated in a coating film, the more the functionality of the film is disturbed. What is needed are Papierfabrik August Koehler SE
not the microcapsules, but their desired core material. I believe there is still some scope for reducing claus.jurisch@koehlerpaper.com
the wall material, which will automatically lead to higher contents of core material in the coating.
Another advantage of this approach is less remainder of wall material after fracture of the capsules.
The formulation of the coating, i. e. the adaptation/the tuning of the coating formulation towards a
good compatibility to the incorporated capsules is another playing field, of course in combination
with the design of the surface of the microcapsules.
Self-healing of damages in the coatings film is limited. How will the design of microcap-
sules increase the self-healing performance in the future? Cost effective methods to produce
very uniformous microcapsules with a narrow particle size distribution, which allow high release
of core material in case of rupture, have to be developed. But I think more room for improving the
self-healing systems is in searching for effective self-healing agents and trigger systems. Self-healing
coatings suffer from not satisfying efficient homogeneous catalysts, which are able to cure the spe-
cific unsaturated loading of microcapsules. The future demands for microcapsules will be less per-
meability and thinner walls by using new multi-layered shell systems.
GET TO KNOW LITTLE
HELPERS FOR PAINTS
“Additives are substances which are added to a coating
composition in small amounts to alter the properties of a liquid
paint or the resultant solid coating in a particular direction. For
example, one property of a liquid paint is its ease of applica-
tion, which can be influenced by rheological additives like
sag control agents. One property of solid coatings is their
anti-corrosion property, which can be influenced by corrosion
protection additives or adhesion promoters.“ Bodo Müller
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UNDERSTANDING ADDITIVES · This book covers
everything about the mode of action, application and
possible side effects of the most important coatings
additives. It reflects the needs of practical work – thus
enabling the reader to gain a solid grounding in these
critical, yet complex constituents of all paint formula-
tions. It provides both an overview and in-depth basic
knowledge of the main classes of additives. This indis-
pensable companion illustrates the types of damage
eliminated or prevented by additives vividly with colour
photos.
2nd Revised Edition,

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38 2 K P OLY U R E TH ANE S
Source: simonvo - stock.adobe.com
ALL-ROUND GAINS FOR

POLYURETHANES
Thiol-silane oligomer avoids limitations of amino silanes. By Nayeem Soad, Dean Kondos, Dmitry Chernyshov, Vikram
Kumar and Martin Wusik, Momentive Performance Materials (published in ECJ 03/2017).
A new low-odour oligomeric glycolic mercapto silane additive tages in these coatings. First, amino silanes react quickly with isocyanates,
for 2K PU systems eliminates disadvantages associated with which shortens the pot life of the coating formulation and may affect oth-
amino silanes, such as yellowing on exposure and shortened er coating properties (such as adhesion). Second, the addition of amine
pot life. Improvements could be obtained in pot life, surface functionality into the coating formulation can lead to yellowing upon ex-
hardness, metal substrate adhesion and corrosion resistance. posure to UV radiation, thus limiting its use in outdoor applications.
In addition to the benefits described above, this silane can be added
T his paper describes Momentive Performance Materials’ new oli-

gomeric glycolic mercapto silane known as “CoatOSil T-Cure” si-
lane (Figure 1). This oligomeric glycolic, mercapto silane has very low
to either the part A or part B of 2K polyurethane formulations, provid-
ing more formulation latitude compared to an amino silane, which
typically can only be added to the Part A side.
odour compared to standard thiol-silanes, can behave as a reactive
additive within a coating formulation, and may be used in any coat- TEST FORMULATIONS, PREPARATION AND APPLICATION
ing chemistries where thiol groups can react. The focus of this work
is, however, on 2K polyurethane coatings. The effect of the silane on Four types of 2K polyurethane coating systems were evaluated:
these coatings was studied using four types of formulation as de-
scribed below. Addition of the silane to the formulations produced ąą Basic model clear coat
coatings that developed faster surface hardness with improved adhe- ąą Formulated clear coat
sion and corrosion resistance. Colour and gloss retention were not ąą Pigmented system
affected when exposed to UVA and UVB weathering. The new silane ąą Commercial topcoat/primer system
also enhanced the pot life of a 2K PU formulation containing a high
content (wt)% of a tin catalyst, without greatly affecting cure time. In each case, these were evaluated on various metal panels that were
prepared and spray-coated following the protocol described below.
AVOIDING THE LIMITATIONS OF AMINO SILANES An alkaline metal cleaning solution was used to clean the metal panels.
The cleaning solution was stirred under slow agitation and heated to a
While other silane additives, for example amino silanes, have been used temperature between 65 °C and 70 °C. Panels were then fully immersed
to improve adhesion of urethane coatings, they have several disadvan- in this solution for two to three minutes to remove any oil contaminants.
2K P O LYU R E T HA N E S 39
life of the coating formulation. Throughout this document, product

RESULTS AT A GLANCE formulations are included as illustrative examples only. Momentive
makes no representation or warranty of any kind with regard to any
űű A coating additive based on a new oligomeric glycolic mer- such formulations. Similarly, test results relate only to these specific
capto silane structure has been developed. This is a non-HAPS formulations. Actual results may of course vary.
silane with little to no odour, a viscosity of approximately The silane was incorporated into the part A side of the clear coat for-
300 cP, and less than one percent releasable ethanol. mulation (1.45 wt% based on total formulation) in the presence of “Fo-
mrez SUL-4” (DBTDL, dibutyl tin dilaurate) and triethylamine (0.01 wt%
űű This product eliminates a number of disadvantages associ- catalyst); the part B side contained the hardener (isocyanate solution).
ated with the use of amino silanes, such as yellowing on expo- A model 2K polyurethane clear coat formulation (Table 2) with differ-
sure and shortened pot life. ent levels of silane (0.9 wt% and 2.9 wt% based on total formulation)
was developed. Coatings prepared using this model clear coat were
űű Incorporation of this silane into a two-component polyu- used to study corrosion resistance, König hardness and dry time.
rethane produced coatings with improved properties, such as The silane was also incorporated into a pigmented coating formula-
longer pot life, higher surface hardness, improved metal sub- tion (at 0.55% based on total weight) with the DBTDL and triethylamine
strate adhesion and corrosion resistance. catalysts (0.06 wt% based on total weight). The corrosion resistance of
the pigmented polyurethane coating containing silane was evaluated.
űű The gloss and colour of the coatings was also retained very The new mercapto-silane was also added into a commercial urethane
well in UV weathering studies. primer system (Table 2) to determine whether it would enhance the
performance of a standard product. Panels were coated with both the
űű The product can also bring benefits in other coating chemis- primer as purchased and the primer with silane added.
tries where reactivity with thiols can occur, making it a versatile, After the primers were cured, a topcoat (Table 1, last column) was
multi-functional, coating additive. coated onto the primed substrates. After curing for approximately
one week at ambient conditions, samples were placed in their respec-
tive testing matrices. 
These panels were then removed from the solution and immediately
rinsed with deionised water. High-pressure air was used to dry the
panels. As a quality check to determine panel cleanliness, a few pan-
els were tested for water breaks (the contact angle of water is close Figure 2: Corrosion resistance on galvanised metals, showing
to zero degrees). If the misted water did not bead on the panels, the improvement due to silane addition.
panel set was dried and stored in a desiccator for testing; otherwise,
the cleaning process was repeated. Complete delamination of coating
The coatings were applied to these cleaned metal panels cut to di-
mensions of 5 x 10 cm. Spray application was conducted using an
HVLP gravity fed siphon spray gun. Gauge pressure near the gun was
No silane
approximately 25 lb/in2 (170 kPa).
The spray application was a side-to-side sweep of the spray gun,
maintaining a gun to target distance of some 20 to 25 cm at a trav-
erse speed of around 800 inches/minute (20 m/min), indexing up and
1.45%
down the panels at approximately one inch (2.5 cm) per sweep. Wet Mercapto
film builds were measured to achieve an approximate equal dry film silane
build for further testing.
No catalyst 0.01% TEA 0.01% DBTL
DETAILS OF THE FOUR DIFFERENT TEST COATINGS catalyst tin catalyst
A basic clear coat formulation (Table 1) was used to study corrosion

resistance and adhesion to multiple substrates as well as the pot Figure 3: Adhesion test results; control vs. silane addition.
100% ‘peel off’ of 0% ‘peel off’

Figure 1: Structure of the new mercapto-silane. coating on tape of coating on
pull tape pull
HS
HS HS
Cold
0 CH 3 rolled
Si 0 0
0 0 Si steel
H 3C
0 0 Si 0
0 CH 3
CH 3 CH 3
HO
No silane 1.45% Mercapto silane

 TESTING CARRIED OUT TO STANDARD PROTOCOLS ed completely while those containing silane stayed intact even after
500 hours. The silane also significantly improved the corrosion resist-
The following tests were conducted in order to evaluate the perfor- ance of the coating.
mance of the silane. Details regarding test protocols can be found in The corrosion performance was not limited to a specific type of metal
the following ASTM methods. substrate. Similar results were observed with skin pass hot-dip, non-skin
pass hot-dip and electro-galvanised zinc. Adhesion to different types of
ąą König hardness (ASTM D4366–95) metals, such as cold rolled steel, hot-dip galvanised and bare aluminium,
ąą Dry time (ASTM D5895-03) was studied using the basic clear coat formulations (Table 1). The ad-
ąą QUV-B &QUV-A performance (ASTM G53-88) dition of the silane into the coating formulation significantly improved
ąą NSST- Corrosion resistance (ASTM D1654-92) adhesion compared to the control (Figure 3).
ąą Adhesion (ASTM D3359). Adhesion to cold rolled steel panels is illustrated in Figure 3. Similar per-
formance was also observed on hot-dip galvanised (both skin pass and
ADHESION AND CORROSION non-skin pass), electro galvanised zinc and bare aluminium substrates.
RESISTANCE MARKEDLY IMPROVED
POT LIFE EXTENDED WHEN TIN CATALYST IS USED
Model clear coat formulations (Table 1) were spray coated onto dif-
ferent types of galvanised metal (skin pass hot-dip, non-skin pass Two part polyurethane coatings are known to have very short pot
hot-dip and electro-galvanised zinc) and the neutral salt spray cor- life under certain types of catalyst system (e.g., high levels of tin-
rosion resistance of the coatings was evaluated over 500 hours. The based catalysts). Formulations (Table 1) using a high level of catalyst
results in Figure 2 indicate that the coatings without silane delaminat- (0.25 wt% based on resin solid) and silane (1.45 wt% based on total
coating weight) were prepared (Table 1) and the viscosity was moni-
tored as a function of time.
Figure 4: Corrosion resistance as a function of time and silane Table 3 shows the amount of time required for the initial viscosity to
loading. double under different catalyst system. Data from this table shows
that the addition of the silane had little to no effect on pot life for both
NSST non-catalysed and amine catalysed coating systems.
500 hours 1,200 hours However, in coatings catalysed with DBTDL tin catalyst, the addition of
silane resulted in a dramatic increase in pot life compared to the same
Control
(140 mm) formulation without it. The control, tin catalyst only system, doubled
in viscosity in less than 30 minutes, whereas the tin plus silane system
doubled in viscosity after 95 minutes.
0.9%
Mercapto
silane CORROSION RESISTANCE AND HARDNESS IMPROVED
(130 mm)
2.9% Various levels of mercapto-silane were incorporated into the formu-
Mercapto lation listed in Table 1 and coated onto cold rolled steel panels. The
silane neutral salt spray corrosion resistance, dry time, König hardness and
(120 mm) UV stability of the cured coatings were evaluated. Panels were tested
for 1,200 hours in neutral salt spray (NSST) and corrosion resistance
Figure 5: Clear coat dry times as a function of silane in formulation.
17 5
15 0
Dry tim e | min ute s
12 5
10 0
75 Dry-
through
50
Dry-hard
4
25
Tack-free
0
3
Set-to-
Control touch
2
+0.9% Mercapto
1
silane +2.9% Mercapto

silane
2 K P O LYU R E T HA N E S 41
performance was monitored as a function of time. Samples contain- for one week at ambient conditions. The corrosion resistance of the
ing the silane had better corrosion resistance when compared to a cured panels was tested in neutral salt spray for 500 hours. Coatings
control sample without (Figure 4). without silane delaminated completely while the coatings using the
Drying times were measured using a dry time recorder utilising brass silane did not show any delamination (Figure 7).
weights (5 grams). The recorder was run for six hours and thickness The silane can also enhance the performance of a commercial ure-
of the films was ca. 45 µm. Cure speed of clear coats are shown in thane primer. The primer (Table 2) with and without silane was coated
Figure 5. The addition of silane did not have a significant impact on onto cold rolled steel panels and cured for 36 hours at room tempera-
dry time. ture. The top coat (Table 1) was then coated onto the primed panels.
Figure 5 shows the dry-through time for the control was 127 minutes The cured film thickness of the primer was ~ 4 mils (100 µm) and the
and 165 minutes for the formulation with the highest loading of silane film thickness of cured top coat was ~ 4-5 mils (100-125 µm). The
(0.09 wt% on total formulation). Thus, the silane did prolong the cure panels coated with the top coat were post cured for ~10 days and the
time by approximately half an hour, but this is not significantly higher adhesion and corrosion resistance were tested. Test data are shown
than the control and is well within the acceptable range for most ap- in Figure 8. 
plications. Panels were cured at room temperature, and surface hard-
ness (Figure 6) was measured as a function of time. This data indicates
coatings containing the silane developed hardness faster and had a Table 1: Formulations for clear coats and pigmented system.
higher hardness once the coatings were fully cured.
Basic Model 2K Fully formulated
CORROSION RESISTANCE OF PIGMENTED COATINGS IMPROVED clear coat clear coat system
PART A
Pigmented coating formulations with and without the silane (Table 1) 71.8 28.52
Commercial acrylic polyol
were coated onto skin pass hot-dip galvanised metal panels and cured
Acrylic polyol 46.37
Fumed silica 0.20
Figure 6: Coating hardness as function of time and wt% mercap- TiO2 (pH ~ 6.5) 14.97
to-silane. Talc (1.2 µm) 10.29
Kaolin (pH ~ 6.0) 6.55
130 Zinc phosphate 8.42
CoatOSil 7001 silicone 0.47
120 0.09
copolymer
König Hardness
110 Tinuvin 328 UV absorber 1.14

100 Tinuvin 292 light stabiliser 0.31
90 DBTDL catalyst 0.09

N-butyl acetate 17.56 16.83
80
Methyl ethyl ketone 8.11
70
Xylene 7.48
10 100
Time l Days PART B
Isocyanate 28.2
 Control  0.9% Mercapto silane  2.9% Mercapto silane HDI trimer 18.22 6.48
N-butyl acetate 7.82
Figure 7: Corrosion resistance of pigmented coatings with and Figure 8: Adhesion and corrosion resistance data of a commer-
without the silane. cial system with and without the silane.
Skin pass hot – Dip galvansed

0% Mercapto 1% Mercapto
silane silane
No silane
500hrs-NSST
Mercapto silane
0.55%
X-hatch
adhesion
No catalyst 0.3% TEA 0.3% DBTL

tin catalyst

“Very light odour.“

3 questions to Dmitry Chernyshov
Mercapto silane interacts with the catalyst DBTL which is under environmental pressure
and will be substituted e.g. by different metal complex catalyst. How is the interaction of
this modern catalysts with the mercapto silane? In general, tin is not an exception. Other tran-
sition metals such as Ti, Bi, Zn and the like will readily complex with –SH functionality. My suggestion
will be to explore possibilities to work with tertiary amino technology. DBU or DABCO-type catalytic
systems can be very efficient even at very low application levels (ppm).
The addition of mercapto silane extends the drying time, probably in combination with
DBTL. How could the impact of alternative DBTL catalyst be described to drying times? As Dr Dmitry
far as metal type catalytic systems are concerned I should expect the similar phenomenon, namely Chernyshov
thiol-silane structures will slow down catalyst reactivity. If we are talking about thiol-urethanes or (Corresponding author)
polyurethanes in general – the maximum output with drying time kinetics can be achieved with Application Development Engineer
amino-type systems. For example, the same products as mentioned in the previous answer can be Silanes
a good match. Momentive Performance Materials
dmitry.chernyshov@momentive.com
How do the results with regard to odour compare to conventional amino silanes? “CoatOSil
T-cure” silane is a very capable product and it has very light odour which is not irritating. In addition,
it is an oligomer, which implies that the product has a relatively low volatility with respect to specific
vapor pressure. On the contrary, conventional aminosilanes are highly volatile amines with very
strong ammonia-type odor. Thus, as far as an odor perception is concerned - with the product there
are very good results for coating formulators.
 Incorporation of the silane into the primer system significantly im- In addition to improving coating properties, the silane can also in-
proved adhesion compared to the control without silane. The corro- crease the pot life of a 2K polyurethane system that contains a tin
sion resistance (500 hr neutral salt spray) of the coating formulation catalyst. This product can be added to either the part A or part B side
containing silane in the primer showed a significant improvement of a 2K polyurethane coating system.
when compared to coating formulation without silane in the primer. In addition to urethane coatings, it may be considered for use in other
coating systems (e.g. epoxy, acrylate etc.) where thiol reactivity is avail-
DIFFERENCES IN REACTIONS OF SILANES IDENTIFIED able. 
To help explain the results described above and also to highlight the
value of this new silane over other potential candidates (such as pri-
mary amino silanes), the silanes were added directly to an isocyanate Table 2: Modification of commercial primer with silane.
(HDI trimer).
Part A wt% wt%
The addition of 1 wt% of primary amino silane into HDI trimer immedi-
ately resulted in a white precipitate. However, when 1 wt% of the new Commercial primer 89.58 88.77
silane was added to HDI trimer no such precipitate formed. 1% mercapto-silane 0 0.9
The fast reaction of primary amino silanes with isocyanates can result Part B wt% wt%
in a shortened pot life for polyurethane coating formulations, which
Activator 10.42 10.33
may affect other coating properties (e.g. adhesion). Second, the addi-
tion of amine functionality can lead to yellowing upon exposure to UV Total 100.0 100.0
radiation, thus limiting their use in outdoor applications.
In addition, reaction kinetics were monitored using FTIR and it was
found that the silane can react with isocyanate groups to form thio-
urethane groups. Table 3: Pot life of coating formulations with and without silane.
WIDE RANGE OF BENEFITS FOR SEVERAL COATING TYPES Pot life (minutes) 0 wt% silane 1.45 wt% silane
A new oligomeric glycolic mercapto silane additive has been devel- No catalyst 210 220
oped. When added to 2K polyurethane coatings, this silane can en- 0.25% TEA 220 220
hance hardness, adhesion, corrosion resistance and the UV stability
0.25% DBTDL < 30 95
of the coating.
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ADDITIVES FOR COATINGS?
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44 ALK YDS
Source: Uwe - stock.adobe.com
SOLVING A VOLATILE PROBLEM

New liquid polybutadiene polymer replaces solvent and improves application. By Anne-Sophie Hesry, Stacey Syron
and Malcolm McInnes, Synthomer (UK) (published in ECJ 12/2017).
Reducing the level of volatile organic compounds (VOCs) in sol- Various alternative approaches may also be used to adjust the final
vent-based alkyd resin systems poses a huge challenge for for- coating formulation in order to lower the viscosity so that less solvent
mulators. A novel liquid hydrocarbon polymer minimises VOCs is needed to bring the paint to within the required application viscosity.
and offers improved application properties in clear coatings. A Liquid polybutadienes (LPBDs) are highly reactive, liquid hydrocarbon
newly developed liquid polybutadiene polymer provides hope polymers which can be formulated into solvent-free or low solvent coat-
for more eco-friendly binder systems. ing formulations. These polymers are similar in many respects to natural
drying oils, but due to their high level of unsaturation the cure rate of
H istorically, the majority of coatings were solvent based, but with

growing emphasis on the reduction of Volatile Organic Com-
pounds (VOCs), such systems are under significant pressure. Where
certain grades is faster than many natural oils and can be accelerated
by using metal driers. In comparison with natural oils, the LPBD films are
typically lighter in colour, harder and more chemically resistant. They
an application still demands the performance of a solvent-based coat- have proven to be particularly suited to primer coat applications, exhib-
ing, reduction of VOCs while maintaining critical application properties iting adhesion and excellent corrosion resistance on steel substrates.
such as viscosity, has become increasingly important.
The modern coatings formulator now faces the significant challenge Further research has been carried out into the range of potential prop-
of minimising solvent whilst achieving an aesthetically acceptable, de- erties delivered by incorporating LPBDs in solvent-based coatings. In
fect-free film at minimal cost. A common approach is to increase the
solids content, but this typically results in increased product viscosity
which may lead to difficulty during coating application. Figure 1: Storage stability of blends LPBD/Alkyd resin 1.
Alkyd surface coatings continue to be one of the most highly con-
sumed types of coatings globally, despite the increasing use of other
polymer film formers. The success of alkyd resin systems is a result of
their relatively low cost, versatility and familiarity of end users. They
can be tailored to meet a variety of end-use requirements through the
choice and ratio of reactants and/or modifiers. Producers continue to
develop new and improved systems for high-solids formulations to
meet increasingly stringent air pollution regulations.
ALK Y D S 45
HIGHER LOADING WITH NOVEL RESIN
Three common coating long oil alkyd-based resins were assessed; one
RESULTS AT A GLANCE based on linseed oil at 100% solid content, and two at 70% solids in white
spirit (one based on linseed oil and one on soya oil). Blends, prepared at
 Alkyd surface coatings are in high demand but the proper- specific ratios, were dispersed for 5 minutes on a high speed disperser at
ties they offer come at a cost. The emphasis on reducing VOC 2000 rpm. The blends were then transferred to glass containers to assess
levels has led to the development of a novel liquid polybutadi- their storage stability (Figure 1). One lot was left at room temperature, the
ene (LPBD). other was placed in an air oven at 40°C for 24 hours. The compatibility be-
tween LPBD polymers in alkyd binder systems was assessed and a visual
 A comparison of systems using a commercially available inspection after 24 hours and 7 days was conducted. Good compatibility
LPBD-A with those using the new LPBD-B instead of a solvent was obtained in all three alkyd resins with both LPBD products.
shows benefits, for example, in higher loading. The following study is mainly focused on work with solvent-based
Alkyd resin 1 (100% long linseed oil). Its compatibility with different
 Application properties such as substance penetration and LPBD polymers was evaluated in detail. Following this screening, a
drying time were improved by substituting solvents with high maximum load of polymer in Alkyd resin 1 was determined. To com-
levels of LPBD-B. plete the assessment, each blend was brushed on foil paper to high-
light any potential film defects.
 Reducing the quantity added may help to increase hardness. A benefit was observed from using the new LPBD-B over LPBD-A, with
greater compatibility in Alkyd resin 1. A higher loading in the resin can
 Further research will explore the benefits of LPBD in other be achieved with new LPBD-B without adverse effects on the visual
binder systems and in coatings used on different substrates.
Table 1: Typical formulations example to assess drying time.
Formulation B01 B02 B05 B06
Alkyd resin 1 71.5 68.1 68.0 58.3
LPBD-A – 3.6 – –
New LPBD-B – – 3.6 14.5

this study we focus on the benefits delivered by incorporating a newly
developed liquid polybutadiene grade (LPBD-B) in a solvent-based al- White spirit 25.7 25.5 25.6 24.4
kyd coating when compared to other commercially available liquid po- Blue pigment 0.4
lybutadiene grades. The new LPBD-B has a lower molecular weight and
higher 1,2 vinyl content than the commercial product, LPBD-A. Cobalt drier 0.5
The results demonstrate how the next generation LPBD-B delivers Zirconium drier 1.6
improved compatibility within the resin system enabling potentially
greater formulation changes and even moving closer to a solvent-free Calcium drier 0.3
system. Our study also shows that it is possible to lower viscosity whilst Total (g) 100.0 100.0 100.0 100.0
simultaneously enhancing the coating’s performance properties.
Figure 2: Rheology profile of modified alkyd blends. Figure 3: Set-up for wood penetration.
Spindle: cone an plate

Shear rate: 2s-1
100
90 Oak panel
80
Oak panel immersed
70
Viscosity in Pa.s
for 15 minutes
60
Diluent effect Cross-sectional cut
50
performed at 1.5cm
40 or 3.5cm depth
30 from bottom
20 blend
Substrate
solution Substrate
10 penetration
penetration
0
0 5 10 15 20 25 30 35 40
End grain migration
End grain migration
Temperature in °C
 Alkyd resin 1  Alkyd resin 1 + new LPBd-B (80:20)

 Alkyd resin 1 + new LPBd-B (95:5)  Alkyd resin 1 + white spirit (80:20)
 Alkyd resin 1 + LPBd-A (95:5)


46 ALK YDS
 Figure 4: 1.5 cm depth cross-section of oak panels after 15 aspect of the coatings. Brush out on foil paper showed no film defects
minutes dip. in wet or dry state.
APPLICATION PROPERTIES IN CLEAR COATINGS
Control LPBd-A (5 parts) To evaluate the application benefits, Alkyd resin 1 was formulated in a
clear coating; LPBD-A and new LPBD-B were added at different ratios.
Application properties including drying time, rheology and hardness
were assessed. Additional information was collected with a substrate
penetration assessment and a study to move towards a 100% solid
content system with lower VOC content.
RHEOLOGY
Blend rheology profile was determined on a rheometer, see Figure 2.

New LPBd-B (5 parts) New LPBd-B (20 parts)
The viscosity of Alkyd resin 1 decreased as the temperature increased.
Similar behaviour was obtained when adding either LPBD-A, New
End grain migration
LPBD-B, or solvent (i.e. white spirit). A solvent-based blend (20 parts)

had the greatest diluent effect on the alkyd resin.
DRYING TIME IMPROVED WITH HIGH ADDITION
A series of formulations was prepared to assess the effect of liquid

polybutadiene polymers on drying time. Alkyd resin 1 was partly re-
Substrate penetration placed by LPBD-A or new LPBD-B. Viscosity of each preparation was
adjusted by adding white spirit to achieve an equivalent viscosity at
room temperature (Table 1).
Figure 5: Chromatograms showing the difference in VOC content.
Control Alkyd resin 1

x10 8 x10 8
1.8 1.8
1.6 1.6
1.4 1.4
1.2 1.2
1 1
0.8 0.8
0.6 0.6
0.4 0.4
0.2 0.2
0 0
2 4 6 8 10 12 14 16 18 20 22 24 2 4 6 8 10 12 14 16 18 20 22 24
Count vs. acquisition time in min Count vs. acquisition time in min
LPBd-A New LPBd-B

x10 8 x10 8
1.8 1.8
1.6 1.6
1.4 1.4
1.2 1.2
1 1
0.8 0.8
0.6 0.6
0.4 0.4
0.2 0.2
0 0
2 4 6 8 10 12 14 16 18 20 22 24 2 4 6 8 10 12 14 16 18 20 22 24
Count vs. acquisition time in min Count vs. acquisition time in min
ALK Y D S 47
Each formulation was applied on glass panels at 75 μm wet film thick- of blends were prepared with the aim of highlighting any additional
ness. The drying time was assessed simultaneously with a linear dry- potential benefits from using LPBD.
ing time recorder. The open time and complete through cure were Each blend was transferred to a glass container. Oak panels were im-
determined by visual assessment of the scratched surfaces of each mersed for 15 minutes in the coating solution, then excess coating
dried coating (Table 2). was removed. Each oak panel was allowed to set at ambient tempera-
The open time is slightly increased by the addition of the new LPBD-B, ture prior to cutting a cross-section at 1.5 cm or 3.5 cm depth from
while LPBD-A did not show significant impact compared to the control the bottom of the panel. The test pieces were sanded, then digital mi-
sample, containing only Alkyd resin 1. croscopy was used to examine each cross-section. Both surface and
The complete cure is very slightly increased by a low addition of end grain migration were evaluated. (See Figure 3 and 4)
LPBD-A or new LPBD-B compared to the control recipe. Significant According to the digital microscopy of a cross-section at 1.5 cm depth,
differences were observed with high addition of new LPBD-B, giving a it was found that surface substrate penetration would mostly occur
shorter complete cure time (Table 3). within the control blend. Adding 5 parts of LPBD-A to the clear coating
allowed a better coverage of the wood piece and significantly, com-
SLIGHT HARDNESS INCREASE AT LOW ADDITION plete end grain migration was observed. There is some evidence that
adding 5 parts of new LPBD-B further improved the end grain migra-
To assess hardness, a series of formulations were developed by re- tion compared with the control formulation. To achieve full coverage,
placing parts of the Alkyd resin 1 and parts of white spirit with LPBDs. new LPBD-B, required 20 parts addition.
Viscosity was not adjusted to emphasise the potential benefit of LPBD. A further cross-section at 3.5 cm depth was conducted to identify how
The coating hardness was assessed using a pencil hardness method. blends behave more deeply into the grain of the wood. In the control
A wet film thickness (wft) of 100 µm was applied to glass panels with specimen, substrate penetration was observed along with some end
a flat applicator. The coatings were allowed to dry for 7 days and 14 grain migration in limited areas. Adding 5 parts of LPBD-A gave a similar
days prior to testing. profile of wood penetration to the control blend but no end grain pen-
Adding LPBD-A in the clear coating did not present any benefits in etration was noted. Despite giving a lower wood penetration at 5 parts
pencil hardness. The coating was similar or lower in hardness com- addition, new LPBD-B gave a similar end grain migration to the control.
pared to the control (no additive in Alkyd resin 1). The incorporation of It was noticed that the end grain migration was present along the speci-
new LPBD-B, allowed an increase of pencil hardness at a low-level ad- men. At 20 parts addition however, more significant wood penetration
dition. A higher addition level did not show benefit in hardness prop- was observed with new LPBD-B compared with the control, with more
erties. It was noticed that a higher addition of LPBD tended to slightly significant end grain migration visible along the specimen.
lower the pencil hardness of the clear coating.
HIGHER SOLIDS REDUCE VOCS
GREATER SUBSTANCE PENETRATION AT HIGH ADDITION
One way to reduce VOC in a solvent-based coating is to increase the
Oak panels were selected to assess substrate penetration. A series solid content. A series of formulations were developed, replacing the
amount of white spirit by LPBD-A, new LPBD-B, or Alkyd resin 1. This
moves the recipes towards higher solids content and allowed evalua-
Table 2: Drying time results. tion of 100% solid content systems.
Levels of metal driers and anti-skin agent were adjusted and calcu-
B01 B02 B05 B06 lated on %w/w on total resin weight.
Each formulation was applied on a glass panel with a flat applicator at
Formulation Alkyd resin 1 Low addition Low addition High addition 50 µm and 100 µm wet film thickness. Coatings were allowed to dry
of LPBD-A of New of new for 24 hours at room temperature prior to observation.
LPBD-B LPBD-B
To compare the different systems, a control formulation with 65% sol-
Average ids content was assessed, which showed good film-forming behaviour
Open time on glass at 50 µm and 100 µm. By increasing the total solids content
00:15 00:15 00:30 00:45
(h:min) by adding Alkyd resin 1, a good film was formed at a low thickness of
Complete cure 30:30 30:45 31:45 23:15 50 µm, whereas wrinkling defects were observed at 100 µm. The wrin-
(h:min) kling effect would be most likely due to rapid surface drying. Adjusting
the metal drier levels in the formulation should eliminate this defect. 
Table 3: Pencil hardness data.
V01 V02 V03 V06 V13

Pencil hardness
Control Low High Low High
after 14 days
addition addition addition addition
LPBD-A LPBD-A new LPBD-B new LPBD-B
100 µm wft B B <B HB B
Order of pencil hardness
6B 5B 4B 3B 2B B HB F H 2H 3H 4H 5H 6H
Very soft Very hard

48 ALK YDS
“The addition levels of LPBD have

been deliberately kept as low as prac-
tical to demonstrate the benefits but
minimise the cost impact.“
4 questions to Anne-Sophie Hesry
Applying the Liquid Polybutadienes (LPBDs), how will costs develop? An important part of
our research in this area has been to ensure it is possible to have a cost effective finished formulation
for more demanding applications. The addition levels of LPBD have been deliberately kept as low as
practical to demonstrate the benefits but minimise the cost impact. Unlike solvents, the LPBds are Anne-Sophie Hesry
permanently bound into the coating, so they perform multiple functions and can bring the formula- Synthomer
tor valuable technical benefits. Anne-Sophie.Hesry@Synthomer.com
The LPBDs are seen as similar to alkyds “in many respects”. Where do they differ the
most significantly? The compatibilities and drying behaviour are like alkyds due to the high level
of unsaturation. The LPBDs however retain their physical properties over a wide temperature range,
particularly low temperatures. LPBD films are typically lighter in colour, harder and more chemically
resistant. Their structure means they can also be cured by other routes such as sulphur or peroxide
vulcanisation.
Can you quantify the difference between LPBD-B and LPBD-A? LPBDs are highly reactive,
liquid hydrocarbon polymers, which can be designed with different chain length and microstructure
combinations. The effect of these variants on application properties, formed part of the study de-
tailed in our research paper.
Is the addition of LPBD limited with regard to compatibility? There are compatibility limits,
yes, with the most stable systems achieved with long oil alkyds. However, our development work has
identified key elements of the polymer design, which improves general compatibility and so offers
greater formulation scope.
 Introducing LPBD-A to increase the total solids content of the clear ONGOING RESEARCH TO EXPLORE
system gave film defects at both thicknesses. This result confirmed the BENEFITS IN DIFFERENT SYSTEMS
initial outcomes following the compatibility study i.e. at high loading,
LPBD-A cannot be incorporated homogenously. Benefits were clearly This study has confirmed benefits from use of liquid polybutadiene
noticed with the introduction of new LPBD-B, to achieve a higher solid polymers in solvent-based coatings with additional enhancements
content system. Clear transparent films were obtained with no visual seen from a new liquid polybutadiene. Results demonstrate that it
defects at both thicknesses (50 µm and 100 µm). is possible to reduce the VOC content of a solvent alkyd coating by
Moreover, increasing the solids content had an impact on the vis- increasing the solid content using additions of liquid polybutadiene.
cosity of the clear systems. The diluent effect of LPBD is confirmed This 100% solids content liquid polymer type, suggests a move closer
with reference to formulations V15 (LPBD-A) and V17 (new LPBD-B). to 100% solids content is achievable. It was additionally shown that
The increase was more significant with the Alkyd Resin 1 (formulation incorporating a new LPBD increased wood penetration, and end grain
V21), which could lead to application issues associated with the high penetration in particular. Other advantages noted were longer open
viscosity. time during drying of clear systems coupled with a potential for faster
To determine VOC content in those formulations, GC-MS analysis was through cure. The ability to harden the dry film was also possible by
performed according to an internal test method. selecting the appropriate addition level of liquid polybutadiene.
Results and chromatograms from GC-MS analysis clearly demon- Application properties were enhanced by using a new development
strated a drop in VOC in formulations with a higher solid content. liquid polybutadiene polymer, without adverse effects on other critical
Replacing white spirit with LPBD in Alkyd resin 1, significantly reduced properties such as gloss level, colour or outdoor exposure.
the amount of VOCs in the formulation. Limited differences were ob-
served between the resins that were added to replace the solvent We have demonstrated the benefits of a development liquid polyb-
content, i.e. in V15, V17, and V21. (Figure 5) utadiene product in one specific binder system used in solvent-based
As expected, increasing the solid content by adding polymer resins coatings. Further work is planned to explore the use in other binder
reduced the total amount of VOC. White spirit is obviously a major systems and evaluate performance on different critical substrates in-
contributor to VOC in the formulations tested. cluding oily, metal, and poorly prepared surfaces. 
Source: dimbar76 - Fotolia W O R LD O F C O L O UR 49
EARLY BEGINNINGS
One of the earliest documen-
ted usages of spray paint
with compressed air dates
back to the 1880s when a
hand pumped machine was
used to apply whitewash to
the walls of the store of the
Southern Pacific Railway.
FIRST PATENT
The first patent for an aero-
sol spray can was granted in
1926 to Erik Rotheim, a Nor-
wegian chemical engineer.
With coatings producers
Richard and Alf Bjercke, he
established a small scale pro-
duction of spray paint cans.

50 S U R FA C E
Source: Сake78 (3D & photo) - stock.adobe.com
GIVING FILMS A
SMOOTHER PROFILE
How electron beam cured varnishes improve surfaces of polymer webs. By Juliane Fichtner, Steffen Günther and
Benjamin Butschkau, Fraunhofer Institute for Organic Electronics, Electron Beam and Plasma Technology FEP (pub-
lished in ECJ 05/2017).
The film quality of electron beam (EB) curable varnish coatings The disadvantage of the water- and solvent-based systems is that the
on polymer web substrates was investigated. Properties were water or solvent has to be completely evaporated to provide a good
found to be affected by monomer level, EB dose and EB current. permeation barrier and to avoid reactions with flexible devices such
Some crosslinkable surface additives improved properties. as OLEDs through residual moisture in the film [5]. However, thermal
drying is a very time- and energy-consuming process.
P olymer webs are important substrates for all kinds of flexible ap-
plications such as food packaging, decorative products and flex-
ible electronics. If the polymer web is intended to be coated with func-
In contrast the “Barix” process is a vacuum-based technique which al-
lows good defect coverage in a multi-layer setup, but it is not able to
produce particle-free surfaces with a single acrylate layer [4]. This, how-
tional thin films, which are deposited by chemical or physical vapour ever, limits the suitability of the process for producing smoothing layers.
deposition (CVD, PVD) techniques, the surface of the polymer films Radiation curing by EB or UV has the advantage of lower energy con-
must be smooth and defect-free. sumption than thermal drying. This ensures higher productivity and a
Where defects are present, they can propagate through the thin films lower thermal impact on the polymer substrate. In comparison to UV
and interfere with their desired function: for instance with the perme- curing, EB curing has the additional advantage that no photoinitiators
ation barrier properties in regards to water vapour [1]. Several types are needed [6].
of surface smoothing layers have been reported, e.g. for permeation
barrier systems: TEST PROCEDURES SUMMARISED
ąą “ORMOCER”, a hybrid polymer dissolved in water [2],
ąą Acrylic resins dissolved in an organic solvent [3], Different formulations of EB curable coatings consisting of an aliphat-
ąą Acrylic monomer layers, which are deposited in a liquid phase and ic urethane diacrylate oligomer, 1,6 hexanediol diacrylate monomer
then UV cured (“Barix”) [4]. (HDDA, from Allnex, Netherlands), two Efka surface additives from
S U R FA C E 51
linear electron beam system. The acceleration voltage was set to 150
kV while the EB curing dose was varied between 30 kGy and 80 kGy by
adjusting the EB currents (2 mA, 6 mA and 10 mA).
In order to evaluate the morphological characteristics of the EB cured
RESULTS AT A GLANCE coatings, white light interferometry (WLI) and atomic force microscopy
(AFM) were performed. A “Smart WLI extended” by GBS unit equipped
űű The film quality of electron beam (EB) curable varnish coat- with a lens with a magnification of x 50 was used. The data obtained
ings on polymer web substrates was investigated. The formula- were filtered using a robust Gaussian filter (ISO 16610-31) with a cut-
tion consisted of an aliphatic urethane diacrylate oligomer and off wavelength of 16 µm.
1,6 hexanediol diacrylate (HDDA) in differing ratios. Different In addition, the surface was trimmed by 10% around the edges to com-
surface additives were also examined. The varnishes were also pensate for failures through the filter. The resulting surface was used
cured by EB with different parameters. to estimate the arithmetic average surface roughness (Sa) (ISO 25178-
2) and the fractional defect area. The latter is defined as an area which
űű The arithmetic average surface roughness (Sa) and the frac- is covered by defects as a proportion of the total measured area. Eve-
tional defect area increased with increasing monomer content rything which exceeds an area of 0.4 µm2 and a height or depth greater
in the formulation. than the Sa surface roughness value is defined as a defect.
AFM images of the coatings were recorded in non-contact mode by a
űű The fractional defect area rises with increasing electron Topometrix “Explorer” atomic force microscope using a silicon tip (tip
beam dose. However, a high electron beam current and hence diameter: 7 nm) and a scan speed of 4.6 µm/s. The profile roughness
a high motion speed on a line leads to a lower fractional defect parameters, arithmetic average roughness (Ra) and total height of the
area. roughness profile (Rt) were determined according to ISO 4287.
űű Certain surface additives, designed to crosslink into the HOW MONOMER LEVEL AFFECTS FILM PROPERTIES
film, could also decrease the fractional defect area.
First, a two-component formulation of oligomer and monomer was test-
ed. All samples were cured at 45 kGy using an electron beam current of 6
mA and a sample motion speed of 266 mm/s. Figure 1 shows the amount
of monomer in the formulation in relation to the arithmetic average sur-
face roughness (Sa) and the fractional defect area of the coating.
Both the arithmetic average surface roughness (Sa) and the fractional
defect area rise with increasing monomer content. The lowest surface
BASF, Germany, and three Byk-UV additives from Byk Chemie, Ger- roughness (4.9 nm) and defect area (0.4%) could be achieved at 12%
many, were prepared. monomer fraction. In comparison, the Sa value for the PET substrate
The varnish layers were applied by a wire-bar applicator with a layer is 4.8 ± 0.4 nm and the fractional defect area is 2.1 ± 0.8%. The rough-
thickness of 20 µm. The substrates used were 15 cm x 20 cm and ness of a polymer surface is thought to occur because of inhomoge-
made of “Melinex 401 CW” polyethylene terephthalate (PET). The wet neous polymer structures at a molecular level [7].
layers were cured by atmospheric pressure electron beam radiation To further analyse the surface properties, AFM measurements were
in the “REAMODE” stationary laboratory curing unit. performed. The images of a cured coating with 12% monomer and
The EB irradiation was performed in a nitrogen atmosphere (oxygen 100% monomer can be seen in Figure 2. For better comparability, the
content < 200 ppm). The system is equipped with an “EBE-150/270” same scale was used for both samples. 
Figure 1: Influence of the fraction of monomer in the formulation on the average surface roughness (a) and the fractional defect area
(b) (determined by WLI data).
a) b)
5.2 6
Average surface roughness - S a - (nm)
Fraction of defect area (%)
5.1
4
5.0
2
4.9
4.8
0 20 40 60 80 100 0 20 40 60 80 100
Fraction of monomer (%) Fraction of monomer (%)

52 S U R FA C E
Figure 2: AFM images: (a) 12% monomer, (b) 100% monomer.  It can be seen that the samples have a smooth surface with minor
defects in the diameter range of 50 to 200 nm. The images also show
that the defect-free area is smoother for the sample with 12% mono-
mer (Figure 2a) than for the sample with 100% monomer (Figure 2b).
0.0µm 0.5 1.0 1.5 0.0µm 0.5 1.0 1.5
The same trend can be seen in Table 1.
0.0 8.0 nm 0.0
a) 7.0 b) The values for Ra were determined in areas without defects and Rt
6.0 was deliberately measured in areas with defects. Ra decreases with
0.5 0.5
5.0 decreasing fraction of monomer, while Rt stays at a similar level.
1.0
4.0
1.0
This trend could be explained by the decrease of molecular weight
3.0 with increasing monomer content. In this case there are many short
2.0 polymer chains and thus more starting points for the radical poly-
1.5 1.5
1.0 merisation process. This again leads to shorter polymer chains in the
0.0
coating, which could result in a rougher surface.
Another explanation could be found in different crosslinking densities for
the different monomer contents, and also the development of different
polymer networks. The defects (white spots in Figure 2) could be explained
Figure 3: Influence of the EB dose on the fractional defect area either by the generation of polymer aggregates, during the polymerisa-
at different EB currents (2mA, 6mA and 10mA). tion process [8], by cyclisation or the generation of free polymer chain
ends [9] or by partially crystalline areas [10]. To confirm which of these
theories is correct, further research will have to be done in the future.
0.8
HIGH EB DOSES IMPAIR FILM PROPERTIES
0.7
To examine how EB process parameters influence the fractional defect

0.6
area, a varnish consisting of 49.8% monomer and 50.2% oligomer was
cured at different EB doses. The different EB doses were obtained by us-
0.5
ing different EB currents (2 mA, 6 mA and 10 mA). The results are shown
0.4 in Figure 3. The data generally shows that the EB dose has an influence
on the fractional defect area. This was expected because of the develop-
0.3 ment of different polymer networks generated by the different EB doses
[10]. Notably, the fractional defect area increases as the dose increases.
0.2
This could be due to more non-chain forming secondary reactions
0.1 such as cyclisation and the generation of free polymer chain ends [9].
20 30 40 50 60 70 80 90 A higher EB current, however, leads to a lower fractional defect area.
Dose (kGy) This could possibly support the theory that the defects are partially
crystalline areas. A high EB current requires a high speed of motion
2 mA 6 mA 10 mA
in practical curing, leading to a low EB dose. In turn quick processes
prevent the development of crystallinity.
Figure 4: Summary of the results of the influence of different surface additives on the average surface roughness (S a) (a) and the
fractional defect area (b).
0.5
5.4
Average surface roughness - S a - (nm)
5.3
0.4
5.2
0.3
5.1
5.0 0.2
4.9
0.1
4.8
0.0 0.1 0.9 1.0
0.0 0.1 0.9 1.0
Mass concentration (%) Mass concentration (%)
without additive BykUV3500 EfkaSL3259 without additive BykUV3500 EfkaSL3259

BykUV3570 EfkaFL3741 BykUV3505 BykUV3570 EfkaFL3741 BykUV3505
S U R FA C E 53
SURFACE ADDITIVES CAN ENHANCE PROPERTIES
In addition, different surface additives were added to a formulation

of 49.8% monomer and 50.2% oligomer. All of them were intended
to crosslink with the rest of the formulation via their acrylic function-
ality. Polydimethylsiloxanes (Byk additives and Efka “SL3259”) and an
acrylate copolymer (Efka “FL3741”) were used in different concentra-
tions based on the technical data sheets of the manufacturer.
The Sa values and the fractional defect area for the different ad-
ditives are shown in Figure 4. Here only the most relevant mass
concentrations of the additives are summarised. Juliane Fichtner
No matter whether additives were used or not, no change in the Fraunhofer
arithmetic average surface roughness (Sa) was recorded (Figure 4a). Institute FEP
In Figure 4b a significant decrease of the fractional defect area is dem- juliane.fichtner@
onstrated for the three additives “UV3570”, “UV3505” and “FL3741”. fep.fraunhofer.de
MAIN FACTORS AFFECTING DEFECT LEVEL SUMMARISED
The work presented in this paper has demonstrated that the val-
ues of arithmetic average surface roughness (Sa) and the fraction-
al defect area increase with increasing monomer content in an
“Reducing the
acrylic based varnish coating.
The fractional defect area also rises with increasing electron beam EB current can
dose. Moreover, a high electron beam current and therefore a high
motion speed in line production leads to a lower fractional defect increase defects.“
area. This study also showed the fractional defect area could be de-
creased by using certain surface additives. 
ACKNOWLEDGEMENTS 3 questions to Juliane Fichtner
Essential results presented in this paper were obtained in a public Can you describe the influence of a reduction of the EB current on
project, funded by the Federal State of Saxony, Germany. Funding refer- the kinetics of the polymerisation and homogenous film forming?
ence: 3000651169 By reducing the EB current, the number of electrons, which interact with the
double bonds in the varnish at the time, are reduced as well. Hence there
REFERENCES will be less starting points for the polymerization process at once. Due to the
[1] Lewis J., Materials Today, 2006, Vol. 9, No. 4, p 38. lower motion speed, electrons will react with the remaining double bonds.
[2] Fahlteich J. et al., SID Symposium Digest of Technical Papers, 2013, Thus, the polymerization is multistage and more defects could be developed.
Vol. 44, No. 1, p 354. This would lead to a more inhomogeneous film. Further investigations for
[3] Prager L. et al., Thin Solid Films, 2014, Vol. 570, Part A, p 87. deeper understanding of the polymerization kinetics are in progress.
[4] Moro L.L. et al, Process and design of a multilayer thin film encapsula-
tion of passive matrix OLED displays, Proc. of SPIE, No. 5214, Feb. 2004. Do you see the influence of the tested additives mainly as surface
[5] Mogck S. et al, Roll-to-roll OLED fabrication on transparent barrier film, active properties or as control reagents in the polymerisation? I
ICCG conference, 2014. think it is more a surface active property. If they would act as control rea-
[6] Clark E., Rochester Institute of Technology, 2009. gents, the layer would be cured irregularly due to specific distribution of
[7] Yamaguchi T., Yamazaki K., Namatsu H., Jnl. of Vacuum Sci. & Tech. B: the levelling agents in the varnish layer.
Microelectronics and Nanometer Structures Processing, Measurement,
and Phenomena, 2004, Vol. 22, No. 6, 2604. If one would use oligomers with a narrow molecular weight, would
[8] Yamaguchi T. et al., Appl. Phys. Lett., 1997, Vol. 71, No. 16, p 2388. you expect a decrease in the fraction of defect area? Yes, I would
[9] Fürst W., Heusinger H., Angew. Makromol. Chem., 1986, Vol. expect that, because of the more controlled polymerization.
143, No. 1, p 131.
[10] Harrell J.W., Ding R.S., Kispert L.D., Internat. Jnl. Radiation Applic. & In-
strumentation, Part C. Radiation Phys. Chem., 1989, Vol. 33, No. 6, p477.
Table 1: Roughness values R a and R t for different monomer

contents.
Monomer fraction [%] Ra [nm] Rt [nm]

100 1.5 110
82.4 0.9 90
49.8 0.7 110
12 0.4 70

54 B IOC I D E S
Source: archidoctor - stock.adobe.com
ECO-SHIELD FOR PAINTS

Multifunctional organoclay composition offers clean-tech protection. By Solvita Kostjukova, Julija Karasa, Karlis
Kostjukovs, Juris Kostjukovs and Davids Stebelis, Alina, Lat via (published in ECJ 09/2017).
Current and future restrictions on biocides are forcing manu- is a significant problem worldwide [2]. Alternative solutions include
facturers of building finishing materials to seek alternative encapsulating biocides into polymer systems, thus making them more
products. A novel multifunctional organoclay additive has stable and less degradable or the use of nanotechnologies, for ex-
been developed by focusing on mineral materials that control ample to obtain super-smooth non-sticking surfaces. The number of
coating degradation and which can be used in building or fin- end users that want to use biocide-free coatings has already reached
ishing materials such as plasters, mortars, primers, paints and
other protective or decorative coatings.
Figure 1: Intercalation of organic surfactant bet ween layers
of clay considerably increases the basal spacing of the lay-
N owadays one of the main focuses of the Europe legislation is

to reduce environmental pollution from toxic substances and
to improve human health and wellbeing. This trend has a direct im-
ers (d1<d2) and also changes the clay surface properties from
hydrophilic to hydrophobic.
pact on the paint and coatings industry. For example, the ECHA plans
to approve restrictions on the use of methylisothiazolinone (MIT), a
chemical compound that protects coating products during storage. quaternary salt
Use will be restricted from the currently permitted level of 1000 ppm
to 15 ppm. As the effective rate of MIT is 50 ppm, the coatings indus- d1 d2
try is forced to look for new alternatives. Significant limitations on the
Biocidal Products Regulation (BPR) list will continue until 2020 and will  
have a drastic impact on the coatings industry [1].
According to the EPA, the polluted indoor climate is one of the top 5
hazardous environments causing health problems such as asthma, al-
Na +, Ca 21 polar group carbon chain d 1< d 2
lergies and other pathologies. One of the indoor pollutants is biocidal
water
products, as 95% of their content is toxic and even carcinogenic. The
leaching of the toxic substances indoors and into the environment
BI O C I D E S 55
of potential clay mineral-organic compound reactions. Modifying the

smectite (montmorillonite) is based on exchanging naturally occurring
inorganic cations (Na+, Ca2+, etc.) in a clay mineral interlayer spacing
with organic ones without changing the structure of the clay mineral
(Figure 1).
RESULTS AT A GLANCE Organoclays are widely used in the coating industry as rheological
additives. It is also common for the concentrated organoclays to be
űű Restrictions on biocides and end user demand have forced used solely in solvent-borne coatings as their hydrophobic proper-
coating manufacturers to seek alternative products. ties make it very difficult to disperse them in water-borne coating sys-
tems [3]. The standard industrial organoclays tend to aggregate and
űű A novel multifunctional organoclay additive was developed they need special dispersants to be used in water-borne systems. The
for use in both solvent-borne and water-borne paste or powder novel multifunctional organoclay additive therefore had to avoid such
systems. limitations.
The other idea for improving standard organoclays was to choose smec-
űű It offers benefits for transparent, semi-transparent and tite clay material (smectite content ~40%) instead of bentonite clays
white wood coatings, which are either water-based or natural because of the size difference in the crystallites. It was observed that
oil-based, by improving both the lifetime and appearance of the the smectite clay has crystallites several times smaller than those of the
coating film. standard bentonite. This makes it possible to decrease the proportion of
organoclay in the composition, provide an even particle distribution, and
űű The novel multifunctional organoclay composition offers improve functionality by increasing the active surface area.
paint formulators an easy-to-use product with a cost-saving po- Organoclay stability and zero-leaching properties are key require-
tential and the added benefits of being environmentally friend- ments for the active substances used to modify the clay material. They
ly, non-toxic, non-allergic and non-carcinogenic. enable the organoclay to be classified as a sustainable material, as an
alternative that can be used to encapsulate even toxic substances,
thus reducing the indoor and environmental pollution.
CLEAN TECHNOLOGY FOR NOVEL ORGANOCLAY
Taking into account the positive and multifunctional organoclay proper-

ties and the shortages of the pure bentonite material, the state-of-the-
art organoclay composition was developed. According to the research
a critical mass. Products that can substitute biocides or support the results it was decided to use the clays that contained smectite from dif-
coating system by reducing or eliminating them are already required. ferent deposits consisting of 40% of the smectite-type clay on average.
The ideal coating product of the future would combine sustainable An active substance that is ECHA registered, non-toxic, non-allergenic
materials that are harmless to human health. A biocide-free coating and non-carcinogenic according to EU official data was chosen to modify
that does not leach toxic substances, is non-hazardous to humans, the clay [ODTMA]. Currently, raw clay material from two different de-
is durable, easy to use in manufacturing processes, and guarantees posits in the EU is used for product manufacturing. The proprietary and
surface maintenance savings. knowledge-based production technology was developed to produce
The EU’s vision is that by 2018 there should be an EU strategy for such material on an industrial scale using clean technology.
non-toxic environments, replacing dangerous substances with non- The multifunctional organoclay composition material production uses
chemical and sustainable alternatives. In 2012, research began into a proprietary one-stage mechanochemical process. The production
developing multifunctional mineral material that would support bio- technology is zero waste, saves time and 80% energy compared with
cide-free coating systems and control the coating degradation pro- alternatives that use non-deficit clay materials. The method is effec-
cess. Degradation is caused by abrasive influence, ultraviolet light, tive to organiphilise both pure (for example, Wyoming montmorillon-
moisture and microbial influence. New multifunctional materials were ite) and low-smectite saturated clays. X-ray powder diffraction analysis
developed using a combination of mineral materials as a base and is used to prove the formation of the organoclays. The basal spacing
organoclays. of the d001 for raw SWy-2 is about 12 angstroms, which increases
after organophilisation. Consequently, the characteristic d001 reflex
SMECTITE CLAY TO IMPROVE FUNCTIONALITY shifts to smaller 2Θ angles (see Figures 2 and 3).
Raw clays that are modified with the organic compounds and cationic HYDROPHOBIC AND HYDROPHILIC FUNCTIONALITY
surfactants (alkylammonium salts) are called organoclays. Numerous
studies analysing the interaction between clay minerals and organic A key improvement in the organoclay composition is the simultaneous
compounds have provided knowledge to be used for possible new or- hydrophobic and hydrophilic activity. The desired functionality of the
ganoclay applications – the most common application being rheologi- innovation was to make it possible to use the organoclay additives in
cal control agents e.g. drilling muds. Organoclays are also employed different coating systems, for example in water- and solvent-based
to absorb organic pollutants in soil, water and air, and in cosmetics, coatings, resins, mortars and binders.
refractory varnish, thixotropic fluids etc. For descriptive purposes, a multifunctional organoclay composition
Clays and clay minerals (especially smectite, montmorillonite) are suc- is used to consider hydrophilic and hydrophobic activity. 50% of the
cessfully used as carriers for surfactants because of their high ion composition is a hydrophobic organocomplex and the other 50% is a
exchange capacity, high surface area and sorptive capacity, chemi- hydrophilic part of the related minerals: illite, chlorite, quartz, carbon-
cal inertness and low or zero toxicity. The organoclays are gener- ates, hematite etc. When the coating formulation is water-based, the
ally prepared in solutions using a cation exchange technique or via hydrophilic part of the multifunctional organoclay acts as a dispersant
solid-state reaction and are synthesised based on the mechanisms for the organocomplex part. When the formulation is solvent-based, 

56 B IOC I D E S
 for example, in oil-based systems, the hydrophobic part of the addi- based on the search for [M]+ ions, using extracted ion mass chromato-
tive disperses because of its hydrophobic properties. grams and considering the data provided by the external standard. The
experimentally obtained mass spectra of QACs confirmed the calculated
UV PROTECTION values (C21H46N, (M)+ calculated – 312.3630, found – 312.3614, Δ 0.0016).
An interesting discovery was that under outdoor exposure conditions The limit of detection (LOD) and limit of quantification (LOQ) of the
the samples systematically showed UV protection. To determine the adapted method was found to be 2.18 ng/ml and 6.62 ng/ml respec-
UV protection properties of the multifunctional organoclay additive, tively. To simulate natural outdoor conditions, multifunctional organo-
a laminated resin film of a plywood was used. The additive was con- clays and wood composite materials (plywood) containing the additive
tained in the resin, which was treated with UV radiation and the col- in the binding and lamination resins were washed out with water. The
our difference with non-treated film of the plywood was calculated by plywood was leached for two weeks and the washout water was col-
using the CIELAB (or CIE L*a*b*, CIE Lab) standard test procedure. lected for tests. The multifunctional organoclay material was leached
After lamination, the 0% and 12% plywood samples were chosen to at a concentration of 15 wt% for 24 h, repeating the method for 10
determine the UV protection properties. These samples were cut in cycles. ODTMA was either not present in these washing waters or its
two parts and one part of each sample was treated with the UV line concentration was less than the LOD. We can conclude that ODTMA is
system that is used in the plywood production process: the samples not extracted from the organoclay structure by water. It was possible
were exposed 100 times to the UV exposure system. The UV protec- to completely extract QACs from multifunctional organoclay additive
tion properties were evaluated based on the calculated colour differ- structures by using isopropanol.
ence (delta) using the CIELAB procedure. The sample’s delta CIELAB Therefore, it can be concluded that materials containing multifunc-
was calculated using data taken from 20 points and the average cal- tional organoclays are completely safe to use outdoors and that they
culated (Figure 4). The obtained results show that the concentration have no environmental impact.
of 12% additive improves the UV resistance of the resin film (pigment
colour) by decreasing the delta CIELAB coefficient by 39% on average.
ZERO-LEACHING PRODUCT SAFE TO USE 
The liquid chromatography/time-of-flight/mass spectrometry (LC-ESI-

TOF) method was used to determine the occurrence and concentra- Figure 3: SEM pictures of raw and mechanochemically organ-
tion of used organic compound ODTMA in the organocomplex and ophilised SWy-2 particle aggregates.
therefore to evaluate the stability of the multifunctional organoclay
additive. LC-TOF-MS provides highly sensitive and accurate mass
analyses for a variety of applications including profiling, identifica-
tion, characterisation, and quantification of both small and large mol-
ecules based on their molecular weight. TOF mass spectrometry is
also called high resolution mass spectrometry (HRMS). LC–TOF-HRMS
methods can be used in a variety of analytical applications. The high
resolution and fast scanning speed of TOF-HRMS analysers offers par-
ticular advantages in terms of operation in scan modes over a wide
range of m/z values.
The identification of quarternary ammonium compounds (QACs) was
Figure 2: X-ray powder diffraction data for mechanochemically modified SWy-2 with different aliphatic quaternary ammonium salts
(carbon chain length varies from C8 to C18).
24000
22000
20000
18000
16000
14000
counts
12000
10000
8000
6000
4000
2000
0
3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
2Θ (coupled 2Θ/Θ)
 SWy-2 C8  SWy-2 C12  SWy-2 C14  SWy-2 raw  SWy-2 C18  SWy-2 C16
BI O C I D E S 57
Figure 4: The total colour difference of CIELAB versus the non- Figure 5: The tested compression strength of the samples.
treated part of the sample.
10
70
8 60
compressive strength, kN
50
delta cielab
40
4
30
2 20
10
0
0
re 1 -
re 2 -
re 3 -
re 4 -
re 5 -
re 6 -
n
di sa n
di sa n
n
in e
in e
in e
in e
in e
in e
si
si
si
si
si
si
0 2,5 5 10
e pl
e pl
e pl
e pl
e pl
e pl
ti v am
ti v m
ti v m
ti v m
ti v m
ti v m
di sa
di sa
di sa
s
multifunctional organoclay additive wt %

di
ad
ad
ad
ad
ad
ad
0%
0%
0%
 M10  M20
12
12
12
% of additivbe P4/C1-23 in the resin film of the samples
Figure 7: The appearance of the traditional lime paint after the 6

Figure 6: The tested tension strength of the samples. month field test exposure.
500
400
tension strength, kg
300
200
100
0
0 2,5 5 10
Multifunctional organoclay additive wt %

 M10  M20

58 B IOC I D E S
 ADDED BENEFITS INDICATE POTENTIAL FOR BROADER APPLI-

CATION
Currently the multifunctional organoclay additives are used to formu-

late water-based coatings and natural oil-based coatings, including
both simple formulations as well as other building materials, such as
mortars, plasters and binders.
To determine how the multifunctional organoclay additive influences
the physical properties of the mineral material products, mechanical
properties were tested. The additive was added to two types of mor-
tars (M10, M20) in graduations of 2.5%, from 0% (the control sample)
to 10%. The samples were tested both in compression (Figure 5) and
tension (Figure 6). The results show that the multifunctional organo-
clay additives do not substantially impact the compression or bending
strength.
Field tests were performed to determine the influence of the multi-
functional organoclay additive on the appearance and initial proper- Solvita Kostjukova
ties of the coating. Traditional lime-based paint without the additive Partner & CEO
and with the multifunctional organoclay was painted on the north side Alina
of a non-renovated building without any other treatment (Figure 7). solvita@alina-premium.com
The appearance of the traditional paint with the additive at a con-
centration of 2 wt% improved after six months. The additive not only
controlled degradation on the surface of the coating but also in the
volume. In other words, if the surface is mechanically damaged, coat-
ing volume is still protected. Surface abrasion was also reduced due “The organoclay
to a smoother application of the coating.
Current trends in exterior wood coatings are transparent, semi- composition improves the
transparent and light colours. The multifunctional organoclay additive
showed excellent results when it was used to prolong the service life durability of the
of transparent linseed oil-based primers and paints. These products
commonly degrade within 1-3 seasons and are most vulnerable to the
climate in Eastern Europe. Blue stain fungi are also becoming a com-
coating.“
mon problem for the industry, limiting the application of the trendy
transparent coatings because you can see the fungi develop. Initial
tests showed that by adding the multifunctional organoclay additive 3 questions to Solvita Kostjukova
to the linseed oil-based primer it worked as an eco-shield for the coat-
ing and the hydrophobic properties, and significantly improved the How can the improved life time of the coatings be specified?
appearance of the coated surfaces. To obtain the transparent illusion By the definition, the improvement of the product’s lifetime is either by
of the wood coating samples, the additive was grinded to 20 microns. making it more durable so that it is harder to break, or by giving the
It is also possible to grind the multifunctional organoclay additive to product a new life by enabling repair or upgrades. The multifunctional
5 microns. organoclay composition improves the durability of the coating by pro-
Intense research efforts continue to test the multifunctional or- tecting it from degradation processes as abrasive influence, ultraviolet
ganoclay additive for different applications, such as bio-composites, light, moisture and microbial influence. The field tests that are carried
packaging material, and polyurethane applications. By developing or- out in aggressive environments confirm the improvement of the dura-
ganoclay production expertise and the organoclay materials itself the bility and aesthetic look of the coating which contains the organoclay
company has developed its first eco-approved product – a multifunc- additive comparing to coating without the additive.
tional organoclay additive assessed against the criteria of the Material
Health category in the “Cradle to Cradle Certified” Product Standard What are the advantages of cationic surfactants compared to
and was awarded a Silver level Material Health Certificate by the Cra- conventional surfactants? The cationic surfactants are bounded to
dle to Cradle Products Innovation Institute [4]. the smectite clay structure (Van der Waals bonds) comparing to con-
ventional surfactants. The advantage of the cationic surfactants by us-
REFERENCES: ing the innovative technology allows to produce organoclay material
with zero-leaching cationic surfactants as they are bonded to the clay
[1] https://echa.europa.eu/documents/10162/ad13d8c6-65d3-4285- structure, thus obtaining eco-friendly and sustainable material.
ab1c-185fa3971aa2
[2] www.epa.gov/indoor-air-quality-iaq/identifying-problems-indoor- How would you explain the UV protection of the organoclay
environments additive? The clays show a potential in UV protection to absorb or
[3] Bodo Müller, Understanding Additives, European Coating Tech Files, reflect UV radiation. The UV protection of the multifunctional organo-
Vincentz Network, Germany, 2010, pp. 74-77 clay is provided by smectite, illite, hematite and silica presence in the
[4] www.c2ccertified.org/products/mhcertificate/alina-life-tm-paint-lifetime- composition. The smectite part is described with UV absorption ability
protection and illite, hematite and silica with UV reflection ability.
W O R LD O F C O L O UR 59
Source: Smile - Fotolia.com

COLOURFUL
POWDER
Basis of the colour powder
Gulal, which is used on holi
celebrations and festivals,
is usually cornmeal, corn-
starch or rice meal.
THREE HOLI FACTS

ąą Traditionally, holi is a Hindu
celebration of the begin-
ning of spring.
ąą Its is also called festival of
colour or festival of love.
ąą The date varies and is
mostly in March or February.
Source: www.bbc.co.uk/nature/
humanplanetexplorer/events_and_festivals/holi

60 M A R I N E C O AT I NG S
Source: (c) stylefoto24 - adobe.stock.com
COOLER OPTIONS
FOR SPRAY COATINGS
Diamide-based rheology modifiers offer quick activation at low temperatures. By Udo Schonhoff, Carlos Feito, Frank Abschlag and
Elke Piron, Elementis (published in ECJ 02/2018).
Many industrial, maintenance and marine spray coatings have External heating or cooling equipment is often unavailable, which
very high requirements in terms of sag stability and layer means that active temperature control during processing is either not
thickness – around 1000 µm or greater in one pass. These spe- possible or only available on a lab scale. In such cases, rheology modi-
cific needs limit the selection of suitable rheology modifiers. fiers that are suitable for use over a wider temperature range show
Novel diamide-based additives now offer processors flexibility significant benefits.
over a wide range of activation temperatures and improved Post-correction procedures currently play a minor role under real-life
viscosity at low shear forces. production conditions as most commercially available organic thixo-
trope grades require higher shear forces for proper activation than
O rganic thixotropes are typically used to fulfil the specific needs

of industrial, marine, and protective spray coatings, specifica-
tions such as high sag stability and layer thickness. However, this class
usually available in the let-down stage.
RHEOLOGY MODIFIERS FOR A WIDE RANGE OF SOLVENTS

of rheology modifiers has complex requirements in terms of incorpo-
ration and activation. These include elevated temperatures in a speci- Organic rheological additives provide exceptionally high viscosity at
fied range combined with high shear for a defined period of time in low shear combined with a strong thixotropic flow character in non-
accordance with the system. The system can be based on a manifold aqueous systems. As shown in Figure 1, the low-shear viscosity is
of binder chemistries and various solvent compositions are required much higher than for organoclays. In practical terms this means that
to achieve optimum performance. organic thixotropes potentially offer the greatest film-forming proper-
Various processing methods are used to produce coating systems. For ties. Organoclays are more beneficial in terms of levelling and this is
the most commonly used batch-by-batch processing technique, the combined with well-balanced anti-sag performance.
necessary energy to obtain and adjust the activation temperature is The first generation of organic thixotropes is based on ricinus oil de-
normally generated by friction during dispersion. The end temperature rivatives. These products are excellent organic thixotropes or “rheo-
depends on parameters such as disperser speed and pigment/extender logical additives”, performing well when incorporated and activated in
loading level and has a strong influence on the entire processing time. a specific manner.
MAR I NE C O AT I N G S 61
Figure 1: Flow characteristics provided by the various classes of

RESULTS AT A GLANCE rheological modifiers.
űű Many industrial, maintenance and marine spray coatings

100
have very high requirements in terms of sag stability and layer
thickness, which restrict the choice of rheology modifier.
Viscosity in Pas
űű Diamide-based rheology modifiers were developed to offer 10
formulators greater flexibility.
űű Compared with conventional options, the organic thixo-

1
tropes are easier to incorporate and activate with respect to
process temperature control. They also have a wider produc-
tion operating window and can even be activated at lower tem-
peratures, which reduces the equipment and energy demand. 0.1
0.1 1 10 100 1000
űű These benefits also enable faster throughput in manufac-
turing plants. Shear rate in s -1
 Organoclay  Organic thixotrope
űű The novel additives provide robust rheology control, even
under accelerated aging tests, and can be used in a variety of
applications such as high solids industrial coatings, sealants,
and adhesives. Once properly activated, the molecules orientate themselves towards
each other, forming a fibrillar structure (Figure 2) due to the nature of
the amide functionality. Intermolecular interactions such as hydrogen
bonding and van-der-Waals forces drive this formation.
The illustrated intermolecular interactions become relevant after the
additive is activated, which is similar to castor waxes. Proper activation
requires mechanical forces applied at specific temperatures in line
with the relevant solvency forces, over a defined period of time. The
Pure castor waxes are typically limited for use in aliphatic solvent- rheological structure is then built up by a redistribution of the crystal-
based and solvent-free systems. To produce a rheology modifier suit- line phases of the rheological additive and cooperative self-assembly
able for solvents of higher polarity such as aromatics, the melting point of certain molecules to produce the described microstructure.
of the castor wax needs to be shifted upwards by adding higher melt-
ing point components. This broadens the range of compatible solvents ACTIVATION AT LOW TEMPERATURES
and raises the general activation temperature. However, none of the
ricinus oil derivatives are suitable for systems formulated with high po- The melting point of the diamide waxes is generally higher than that
larity solvents, such as oxygenated solvents e.g. ketones and esters. of castor oil derivatives. This enables this class of rheology modifiers
The second class of rheology modifiers for the specified range of ap- to be used in the widest range of solvent polarities. However, the po-
plications is based on diamide waxes, which have a different general tential activation temperatures are usually higher than for ricinus oil
molecular structure. derivatives. 
Figure 2: Schematic representation of the mechanism of action of a diamide-based rheology modifier after correct activation.
O O
N—R—N
H H
O O
N—R—N
H H
O O
N—R—N
H H
O O
Fibre structure
N—R—N
H H

 Figure 3: Optimum activation temperature range. This new class of diamide rheology modifiers has been developed to
provide proper activation at markedly lower temperatures than tra-
ditional grades based on similar chemistries. This is especially impor-
200 tant in solvent-free systems which usually have high activation tem-
peratures. The main advantage of such low temperature activation is
Viscosity at 0.1 s -1 in pas
cost savings in the manufacturing process. The process can be carried

150 out without external heating and is faster.
Another major focus of the development was to generate organic
thixotropes that provide stable activation over a wider temperature
100 range. This increases the process robustness under real-life condi-
tions with frequent fluctuations in temperature, for example, the dif-
ferences between summer and winter.
50
45 50 55 60 65 70 75 80 IMPROVED VISCOSITY AT LOWER SHEAR FORCES
Activation temperature in °C Two new diamide-based rheology modifiers Thixatrol PM 8054 (in the
following graphics New RM 1) and Thixatrol PM 8056 (in the following
 New RM 1  New RM 2  Reference
graphics New RM 2) have been developed, primarily for non-aqueous
industrial, marine and protective coatings. For all organic thixotropes,
Figure 4: Rheology cur ves of a solvent-based protective and Figure 5: Viscoelastic behaviour of test systems. The yellow line
marine coating equipped with 1% of the relevant rheology modi- indicates the point at which shear was stopped after application.
fier activated at 63 °C.
1000 Rotation Oscillation
tan delta > 1

1.5
Shear rate Strain = Ɣ 0.1%
= G“ > G`
Damping factor/tan delta
.
= Ɣ1000 s-1 ω = 10 s-1
100
Viscosity in pas
1.0
10
tan delta < 1

= G` > G“
1 0.5
0.1
0
0.1 1 10 100 1000
1.5 2.0 2.5 3.0 3.5 4.0
Shear rate in s -1
Time in min
 New RM 1  New RM 2  Reference
 1% New RM 1  1% New RM 2  1% Reference
Figure 6: Intercoat adhesion testing.
New rheology modifier 1 New rheology modifier 2 Negative reference
MAR I NE C O AT I N G S 63
these novel rheology modifiers need specific process temperatures after removing shear. However, both samples with the novel rheology
and mixing times to achieve their maximum performance. However, modifiers rebuild their structure noticeably quicker than the material
in comparison to currently available organic thixotrope grades, both containing the reference grade. This is shown by the first measuring
products are less temperature sensitive and offer broader solvent points of lower tan delta values, which indicate a stronger structure.
compatibility. For the reference modifier (Pro), structural recovery occurs with a
The following study identifies the ideal activation conditions to achieve slight time delay. When comparing the samples with the novel grades,
optimum performance and was carried out in an epoxy-based marine the results show slight benefits for the second modifier. These results
primer. As presented in Figure 3, the newly developed additives give correlate strongly with the sag stability data.
excellent low shear viscosity built over a wide range of activation tem-
peratures. ROBUST INTERCOAT ADHESION
These results suggest that one of the novel additives achieves the
best results within a temperature range of 50–70 °C. The second addi- As the tested coating type is typically applied in a multi-layer build-up,
tive has a much wider temperature window of 45–70 °C for activation. intercoat adhesion is of great significance. Therefore, the influence of
In comparison to the application temperature range of 50–60 °C for rheological additives on the intercoat adhesion is usually tested. In
the reference product Thixatrol Pro (in the following graphics called this assessment the epoxy primers equipped with the individual or-
reference), the results indicate that the newly developed grades are ganic thixotropes were applied on a metal substrate and cured. After
much more flexible. re-coating, a cross-cut test with an associated tape-peel test based on
The rheological activity of the new grades after activation at the same DIN EN ISO 2409 was performed and the intercoat adhesion evalu-
temperature of 63 °C, display only minor differences (Figure 4). How- ated.
ever, the resulting viscosities at low and mid shear rates are markedly In accordance with our experience, high temperature and humidity
higher than with the reference grade. Furthermore, the new organic when curing the primer could be critical for the intercoat adhesion.
thixotropes provide clear advantages in terms of the maximum layer Therefore, a temperature of 40 °C and 100% humidity was chosen.
thickness after spray application. A layer thickness of up to 1200 µm As it can be seen in Figure 6, neither of the new products indicated any
can be achieved in one spray pass. intercoat adhesion failure. This was only the case with the reference,
Figure 5 shows the viscoelastic characteristics of the tested coating, another rheology modifier also based on a diamide technology, which
generated in a structure recovery test. This test simulates the behav- shows a total loss of the topcoat adhesion after the tape-peel test.
iour of the system after application at the high shear forces relevant
to spray application. HIGHEST VISCOSITY AND LAYER
In the first rotational measuring step the structure of the coating THICKNESS WITH MILLBASE ADDITION
was disrupted by high shear forces. In a second oscillatory step, the
behaviour after removing shear was analysed. This step represents As the incorporation method also influences the resulting viscosity of
the performance of the coating after substrate impact. When the dis- the final system, two different activation procedures were performed.
played damping factor (tan delta) is below 1, the elastic behaviour of In the first case, the additive portion was added before the pigments
the sample is dominant. The smaller this value, the stronger the sam- and filler, and was dispersed with the entire system until the activa-
ple structure. A strong structure indicates excellent sag stability and tion temperature of 66 °C was reached. Here, the energy to obtain the
should consequently correlate with the results achieved in practice. relevant temperature was generated only by shear. Two batches were
As Figure 5 shows, all samples display strong elastic behaviour soon manufactured using this method and two different tip speed values. 
Figure 7: Low-shear viscosity data at 0.1 s-1 and the maximum applicable layer thickness by blade application in accordance with
the specified incorporation and activation method.
Viscosity at Max layer thickness

Point of addition Dispersion speed Temperature control Process
0.1 s-1 in Pas with blade in µm
21 m/s No, up to 66°C

millbase 141 1200
Temp
18 m/s No, up to 66°C 157

millbase 1200
Time
12 m/s Yes, 63°C

post-addition 128 1200
Temp
post-addition 12 m/s Yes, 66°C

131 1000
Time
 Addition of diamide

 4 questions to Udo Schonhoff
To what extent is the minimisation of potential side-effects related to the higher melting
point of the diamide waxes? Side effects such as classical seeding and false bodies are heavily
dependent on the melting point of the diamide wax. Increasing the melting points will minimize these
effects. The effect of “latent seeding” on the other hand means particle formation over longer storage
periods and is caused by under-activation due to excessively low temperatures during processing.
This effect is counteracted by the low temperature at which the new diamide waxes can be activated.
Dispersing of the diamide waxes, i.e. achieving the finest-possible distribution in the mill-
base, requires the most effective decomposition possible. How is this achieved and under
what conditions? How can this be verified? Diamides are typically agglomerated in their powder
delivery form. During activation they are converted into a rheologically active fiber structure. This
process depends heavily on the solvating power and polarity of the system as well as the shear forces
applied during processing. For optimum performance, all parameters have to be correctly preset for
each individual system. Our main objective in developing the new product class was to achieve the
widest possible activation window.Optimum activation can be verified by measuring rheological data Udo Schonhoff
and their correlation with practical properties, such as sag resistance. Elementis GmbH
udo.schonhoff@elementis.com
The particle size distribution is important for the application. What is the particle size
distribution of the diamide waxes described here? The swelling process to activate organic
thixotropes is related to the particle size distribution of the product in its delivery form. We typically
endeavour to keep the particle size in a very narrow range of 6 µm. “Achieve the
The melting behaviour is just as enlightening when it comes to decomposition. Are there widest possible acti-
any descriptions about this behaviour available, e.g. in the form of DSC? The melting point
is one of the main quality criteria for these products and is always reviewed in production. Further
vation window.“
analytical procedures, such as DSC, are mainly used in R&D.
In another process, the first novel modifier was post-added to a dis- Suzuki M., Abe T., Hanabusa K., J. Colloid Interface Sci., 2010
persed system. Due to the markedly lower system viscosity, the dis- De Loos M., van Esch J., Kellogg R. M., Feringa B. L., Angew. Chem. Int. Ed., 2001, 40
persion tip speed needed to be much lower than in the first instance. van Esch J., de Feyter S., Kellogg R. M., de Schryver F., Feringa B. L., Chem. Eur. J.,
This also resulted in lower friction which meant an external heat 1997, 3(8)
source was necessary to control the temperature during the activa- van Esch J. H., Schoonbeek F., de Loos M., Kooijman H., Spek A. L., Kellogg R. M.,
tion process. Feringa B. L., Chem. Eur. J., 1999, 5(3)
Comparing the results in terms of viscosity at low shear rates and
sag stability of material generated by both methods, there were only
minor differences (see Figure 7). The highest viscosity values and the
highest achievable layer thicknesses are obtained after millbase addi-
tion of the organic thixotrope. However, the results of the post-added
activated rheology modifier are also surprisingly good. Viscosity values
and the maximum applicable layer thicknesses are only slightly lower Find out more!
than for the millbase addition. Consequently, this method is deemed
suitable for screening organic thixotropes or, if equipment allows, on
a production scale. As such, the activation of the organic thixotrope
and the pigment dispersion could be performed separately.
Furthermore, the new organic thixotropes can be used in processes
where only lower shear can be applied 
Marine coatings
ACKNOWLEDGEMENTS
We would like to thank the Cologne lab team Anja Wingerath, Wolfgang Fuchs,
Jörg Bungarten, Parwis Adli, Vimal Saimi and Sebastian Heinz.
LITERATURE
184 search results for marine coatings!
Rheology Handbook, 2013, Elementis Specialties, Inc., East Windsor, NJ
Find out more: www.european-coatings.com/360
Maity G. C., J. Phys.Sci., 2007
W O R LD O F C O L O UR 65
Source: phanuwatnandee - Fotolia.com

LIKE CLOCKWORK
Big factories can coat up to
100,000 pencils a day. The
pencils are pushed in a pipe-
like case with paint. Surplus
coating is then wiped off
when they are extruded from
the container. The process is
repeated up to seven times.
LESS IS MORE
Only small amounts of coa-
ting are needed to coat a
pencil – less than one gram
is used apiece. The pencil
has a long history – its first
precusors were produced in
1565 in England.
Source: Deutsches Lackinstitut

66 P IG M E N T E F F ICIENCY
Source: dja65 - stock.adobe.com
WHY SMALL IS BEAUTIFUL

Benefits of finer particle size in UV inks and coatings quantified. By Mark Ortalano, Sun Chemical (published in ECJ
04/2017).
vent re-aggregation, as the benefits of small particles vanish if floccula-

The benefits that very small particle size pigments provide in tion occurs. It is extremely difficult to find proper dispersants or additives
a variety of graphics and design applications are considered. to stabilise the small particles and simultaneously yield a low viscosity.
Gloss, chroma, transparency and strength can all be increased. By providing a variety of examples, this article reviews the benefits
Strategies to stabilise the small particles with improved dis- that very small particle size pigments provide in a variety of graphics
persability and low viscosity are presented. and design applications. Also, strategies to stabilise the small particles
with improved dispersability and low viscosity are presented.
I t is well known in the industry that in order to achieve optimum

pigment dispersion, the pigment surface must be compatible with
the medium of the dispersion. This is often difficult, due to the fact
ORGANIC PIGMENT PRODUCTION AND DISPERSION
that pigmentary properties are inherent in the chemical nature of the Organic pigments are manufactured by processes dependent upon
pigment as well as being driven by its physical characteristics. the pigment type, but almost all pigments can end up in a ‘presscake’
In order to formulate with a given pigment chemistry, dispersant tech- form with water or then be dried further into a powder. Azo pigments
nology must be employed. This is especially true in the case of trans- are made in a strike tank with non-coloured and water soluble inter-
parent particles, where the small size of the particles results in an mediates that react in the water under controlled reaction conditions
effectively high surface energy, leading to aggregation. to form highly coloured but insoluble molecules.
For pigmented UV systems, inks including flexo, sheetfed and inkjet The molecules form into crystalline particles of various sizes (Figure 1)
have the greatest commercial usage. The properties desired of these which are determined by the process conditions and the use of ad-
inks are transparency, colour strength and stability. ditives, such as crystal growth inhibitors or surface modification. This
These parameters are driven by particle size, shape and chemis- primary particle size can be tens to hundreds of nanometres.
try, where small particles offer the highest transparency and colour These crystals then associate after drying into aggregates or agglom-
strength due to lower scattering of visible light. However, these small- erates, which have to be dispersed and stabilised in order to achieve
er particles tend to be more difficult to effectively disperse and sta- the lowest particle size, highest colour value and other key properties.
bilise due to their higher surface area and effective surface energy. Organic pigments, being highly aggregated and agglomerated, have
Proper stabilisation of small pigment particles is very important to pre- composite particles in the tens to hundreds of micrometres range that
P I G MEN T EFFI CI EN C Y 67
was checked on a “Brookfield DV-II-Pro” viscometer. Prints were made

using an RK PrintCoat Instruments’ “K Control Coater” on various Len-
eta charts. TEM measurements were made using a “JEOL 100CX-II”.
RESULTS AT A GLANCE BENEFITS OF FINER PARTICLE SIZE ILLUSTRATED
 The benefits that very small particle size pigments provide Quinacridone pigments are used in applications requiring high per-
in a variety of graphics and design applications are considered. formance properties, with shades that range in from the very yellow
Strategies to stabilise the small particles with improved dispers- gamma quinacridone form of V19 to the deep violet shade of C.I. Pig-
ability and low viscosity are presented. ment Red 55. Due to the differing surface energies of each crystal
face of the pigment, it becomes difficult to stabilise – particularly at
 Organic pigments in particular form crystalline particles small particle sizes where proper surface treatment and dispersants
which aggregate after drying into much larger particles. These are required for optimal stability [1].
must be effectively dispersed to obtain maximum efficiency. In Figure 3, the red line demonstrates the particle size of a conven-
For applications such as UV inkjet printing, very fine and stable tional dispersion of quinacridone magenta pigment in a monomer for
particles are essential to avoid clogging the print nozzles. energy-curable application. This is in the range of acceptability for UV
flexo or similar applications. For UV inkjet, however, smaller particle
 Tests on two quinacridone pigments and a monoarylide size is essential.
yellow showed that reductions of 40-50% in particle size led Using processing techniques, the particle size was reduced further as
to substantial increases in tinting strength. Improved chroma, demonstrated by the green line on the graph. This dispersion is prop-
gloss and transparency can also be obtained. erly formulated to maintain stability at the smaller particle size levels.
A UV ink formulated with C.I. Pigment Red 122 with a mass median
 Careful choice of dispersant is essential to maintain the sta- diameter (d50) of 125 nm exhibits a clear increase in colour strength
bility of fine particle size dispersions. compared with a UV ink having a d50 of 228 nm, as seen in Figure 4.
Reducing the median particle size of the C. I. Pigment Red 122 grade
studied here by approximately 50 percent results in an increase of
approximately 37 percent strength.
Similarly, there is also a significant effect on the colour strength when
the particle size of C.I. Pigment Violet 19 is reduced. Again, reducing
the particle size of C.I. Pigment Violet 19 by 44 percent results in ap- 
need to be dispersed down to the primary particles sizes of tens to Figure 1: TEM images of primary pigment particles (identified by
hundreds of nanometres. This means a reduction of about 1000 X, and C.I. numbers) and associations of pigments.
can be accomplished by various milling and processing techniques.
As Figure 2 demonstrates, energy is used to de-aggregate the pig-
ments, while a dispersant/surfactant is used to stabilise the resulting 0,1 µm 0,1 µm
particles. In the schematic, a surfactant is used as the dispersant, and
this is appropriate for a waterborne system.
Other dispersants can be used, including resins and other polymers,
or combinations with surfactants. Mechanisms of stabilisation can be
steric, electrostatic or electro-steric, depending upon the vehicle (UV Pigment Blue 15:4 (150,000X) Pigment Red 122 (120,000X)
monomer, polar solvent, non-polar solvent, hydrocarbon or other). 0,1 µm 0,5 µm
Surface modification with additives can improve dispersability and

stability.
Among the useful approaches to stabilising the pigment in a continu-
ous solvent, a pigment residue reacted with a polyalkylene oxide moi-
Pigment Green 7 (150,000X) Pigment Yellow 74 (30,000X)
ety may be used as the additive. The pigment residue has affinity for
the pigment surface, while the polyalkylene oxide moiety has solubility
in the liquid phase. This pigment-specific formulation approach has
particular value in stabilising difficult pigment particles, such as phth- Figure 2: Basic concept of the dispersing mechanism.
alocyanines, in semi-polar systems such as UV monomers.
PIGMENT AND COATING TEST PROCEDURES SUMMARISED
Various processing techniques known in the art were employed to

make the test pigment dispersions, with the goal of achieving the
E
lowest primary particle sizes. Particle size was measured on the “Na-
notrac 250” particle size analyser from Microtrac with settings (i.e.,
viscosity, refractive index) specific to the liquid carrier (e.g., monomer, Pigment Energy Surfactant Dispersion
solvent or water) and that of the particle. aggregate input
Colour testing was performed on an X-Rite “Color i7” spectrophotome- (milling)
ter and gloss on a BYK Gardner “micro-TRI-gloss” glossmeter. Viscosity

68 P IG M E N T E F F ICIENCY
 Figure 3: Representative reduction in particle size for a quina- proximately a 19 percent increase in strength.
cridone pigment, where the red line shows a conventional size
pigment dispersion, and the green line the much smaller particle MONOARYLIDE YELLOW SHOWS SIMILAR GAINS
dispersion.
In digital printing ink applications, maintaining a low and stable vis-
cosity is very important. Typically, inks are jetted at high temperature
Comparison plot for UV inkjet in order to be at around 7–15 cP. In order to achieve
20
19 higher chroma, additional pigment can be added but at the expense
18 of higher viscosity. Reducing particle size at similar viscosity results in
17 a higher chroma, as Figure 5 illustrates.
16
15 C.I. Pigment Yellow 74, a monoarylide pigment, is also commonly used
14
13
12
% Channel
11 Table 1: Increased gloss and colour strength of C.I. Pigment Yel-

10 low 74 in aqueous system relative to reduction in particle size.
9
8
7
6 Parameter C.I. PY 74 standard C.I. PY 74 smaller particles
5
4
Tint strength Standard 114%
3
2 Gloss 60° 46.4 62.1
1
0 Particle size d50 213nm 121nm
Particle size d90 426nm 294nm
0.01 0.1 1
Size (micrometres)
Figure 5: Chroma achieved relative to particle size reduction as a

function of the amount of C.I. Pigment Red 122 in a UV inkjet ink.
Figure 4: Colour improvement due to finer grinding with C.I. Pig-
ment Red 122 in a UV curable application.
80
78
76
Chroma
74
72
70
68
2 3 4 5 6 7 8
% Pigment level in ink
D50=228nm D50=125nm
 d50=125nm  d50=228nm
Figure 6: Inks made and printed over foil and coated paper Figure 7: TEM of C.I. Pigment Yellow 74 with and without additive
demonstrates the high degree of transparency achieved by the technology.
smaller particles.
0,25 µm 0,25 µm
C.I. Pigment Yellow 74 ink C.I. Pigment Yellow 74 ink

printed over foil printed over coated paper
D50=213nm D50=121nm D50=213nm D50=121nm

C.I. Pigment Yellow 74 C.I. Pigment Yellow 74
without additive with additive
P I G MEN T EFFI CI EN C Y 69
in a variety of applications, including architectural paints, water-

based inkjet and water-based flexo inks.
Opacity and gloss vary dramatically with particle size with some
monoarylide and diarylide yellow pigments. In this example, a medi-
um opacity C.I. Pigment Yellow 74 was reduced in particle size from
a d50 of 213 nm to 121 nm in a water-based dispersion stabilised
with styrene-acrylic resin and surfactant.
Inks were prepared from the dispersions and compared for gloss and Mark Ortalano
transparency, and a tint in a white paint base was made to compare for Dispersions
colour strength. Table 1 demonstrates the particle size reduction, tint Group Leader
strength and gloss while Figure 6 demonstrates the inks made and print- Sun Chemical
ed to achieve a high degree of transparency by using smaller particles. Performance
Pigments
IMPORTANCE OF DISPERSANTS AND SURFACE TREATMENTS mark.ortalano@
sunchemical.com
When reducing particle size, it cannot be overemphasised that sta-
bility must still be maintained. Small particle size leads to higher sur-
face energy which tends to poorer stability.
For energy-curable systems, poor stability can result in higher vis-
cosity and growth in particle size over time. Synergists and pigment
surface treatments can help, along with proper choice of disper-
sant. Without surface treatment, C.I. Pigment Red 122 and C.I. Pig-
ment Violet 19 show a steep increase in viscosity with increasing
pigment loading in a UV inkjet ink.
Higher pigment loading can be achieved within the print viscosity “Prints on non-
range with surface treated pigment technology [1]. Additives or pig-
ment treatments allow for smaller primary particles and improved absorbent substrates
compatibility and stability, and result in higher transparency, gloss
and strength. An example is the phthalocyanine derivatives from
companies such as Lubrizol that are well-known in the industry and
benefit most.“
give excellent stabilisation of phthalocyanine blue and other similar
pigment chemistries [1].
The TEM images in Figure 7 demonstrate the effect of the additive
technology upon the primary particle size of the pigment for C.I.
Pigment Yellow 74. During pigment manufacture, the additive is in-
corporated and reduces crystal growth. The head group remains in
the pigment while the polymeric tail portion is soluble in the carrier,
which then allows for improved stability due to steric hindrance.
3 questions to Mark Ortalano
OPTIMISING PIGMENT EFFICIENCY
The film building process in UV-curable waterborne dispersion
The benefits of small particle size dispersions for UV inkjet in par- and 100% UV-systems show a difference. What measures are
ticular and for UV inks and coatings in general include increased necessary to transfer the positive properties of finer particle
chroma, gloss and transparency. Advanced processing technology, size to both systems? The dispersion for 100% UV-systems will contain
along with pigment specific additives, allow for improved stabilisa- pigment dispersed in acrylated monomers, while those for UV-curable
tion of the energy-curable inks and coatings. waterborne will be dispersed in water. The choice of dispersants and
This allows the UV inkjet ink maker to produce inks that jet at print- additives will be optimized for the proper vehicle.
able viscosities and simultaneously allow for high colour value. High
chroma and colour strength are very important for graphics and sig- As well the printing process of absorbent substrates and non-
nage applications, where high performance pigments are also used. absorbent substrates might require a different processing of
As the UV market shifts to unique technology to improve the quality stabilizing finer particles. How could one achieve the best per-
of prints and coatings, pigment dispersion formulations and prod- formance on varying substrates? Some of the key benefits of smaller
ucts must adapt to optimise the performance. In some cases, ink particle size pigment dispersions are gloss and transparency. Prints on
formulations have shifted to hybrid ink systems that allow for lower non-absorbent substrates benefit most from these attributes.
film thicknesses. Though energy curable inks, and particularly UV
inkjet inks, have been emphasised here, the technology has applica- Would you recommend suitable dispersion and wetting addi-
tion to other energy-curable coatings and ink technologies.  tives in regard to the different applications of finer particles?
If so, which ones would that be? Dispersant and synergists are specific
to the pigment type and will differ according to the system (aqueous or
REFERENCE monomer). Pigment affinic headgroups will connect to the surface of
the pigment, but the remainder of the molecule will be designed to be
[1] Pigments & Dispersions for Energy Curable Inkjet Inks, NIP23: Interna- soluble in the vehicle.
tional Conference on Digital Printing Technology and Digital Fabrication,
February, 2007, pages 126 – 128.

70 WAT E R - B OR N E
Source: Peter Geithe - Stock.Adobe.com
KEEPING UP THE SUSPENSION

Novel bio-based neutralising agent for fumed silica dispersions. By Peter Klug, Jörg Rüger, Clariant Germany and Silvia
Ziebold, Clariant Switzerland (published in ECJ 05/2018).
Dispersions of fumed silica must be neutralised in order to cal substances in paints, consumers must rely on ecolabels in their
maintain stability in water-based coatings. Common stabilis- buying decisions. With currently available raw materials and additives,
ers fail to comply with several eco-labels. Dimethyl glucamine formulators must therefore consider not only function but also the
offers a completely safe and largely bio-based alternative. environmental profile when it comes to selecting paint ingredients.
Rheology studies showed that it performs at least as well as From their perspective, additives should be multifunctional and uni-
DMEA. versally applicable in order to reduce formulation complexity, raw ma-
terial handling and logistics costs. In addition, they need to comply
T oday, indoor home environments are polluted by an accumu-

lation of molecules generated by outside air, solvents, tobacco
smoke, biological pollutants such as mites, allergens and moulds, and
with increasing safety and environmental regulatory requirements.
THE VALUE AND PROBLEMS OF FUMED SILICA DISPERSIONS

building materials. People are subjected to two to five times more
contaminants indoors than outdoors [1]. Fumed silica dispersions are primarily added to control the rheology
Experience and measurements show that the levels of indoor pol- of liquid paint systems such as low PVC water-based paints, especially
lution, and specifically levels of heavy metals and particulate matter lacquers and varnishes. In addition to generating structural viscosity
(PM), are higher than the average allowed by the World Health Organi- and behaving as an anti-settling agent for pigments, highly dispersed
sation, all over the world. This is particularly concerning given that we silica has been repeatedly shown to positively influence the mechanial
now spend up to 90% of our time indoors [2]. properties of paint and coating films [4].
For the coatings industry, an increasing consumer focus on creating For example, it can improve mechanical strength and scratch resist-
healthier indoor surroundings means that high-quality water-based ance and increase hydrophobicity, which assists in improving corro-
paints with a low VOC content are in demand. More broadly, a World sion resistance. Typically, the higher the loading level used, the more
Paint & Coatings Industry Study [3] forecasts water-based coat- noticeably these attributes can be improved [5].
ings gaining share over solvent-borne products in virtually all world Dispersions are preferred by the industry because of their easy han-
markets. dling. They are easily pumpable and are dust-free. In order to create
Growing regulatory attention surrounding paint ingredients adds to storage-stable fumed silica dispersions, a suitable neutralising agent
concern. Because it can be difficult to understand the different criti- is necessary.
WAT ER -BO RN E 71
Figure 1a: Particle size distribution of the fumed silica slurry Figure 1b: Particle size distribution of the fumed silica slurry
dispersions stabilised with dimethyl glucamine. dispersions stabilised with DMEA.
12 120 9 120
8
10 100 100
7
Cumulative volume in %
Cumulative volume in %
8 80 6 80
Relative volume in %
Relative volume in %
5
6 60 60
4
4 40 3 40
2
2 20 20
1
0 0 0 0
Particle distribution in µm Particle distribution in µm
 Relative volume %  Cumulative volume %  Relative volume %  Cumulative volume %
Usually, amine neutralising agents such as the aminoalcohol dimethyl

aminethanol (DMEA) are used for this purpose. Due to its hazardous sub-
stance labelling and VOC content, this neutralising agent has limitations
when used in a modern and environmentally conscious formulation.
A NEUTRALISER THAT MEETS ALL ECOLABEL REQUIREMENTS
Based on the general need for sustainable neutralising agents [6],

RESULTS AT A GLANCE Clariant has developed a sugar-based speciality amine that is new to
the market [7]. The product is a dimethyl glucamine marketed under
űű Dispersions of fumed silica must be neutralised in order to the name “Genamin Gluco 50”.
maintain a stable form suitable for use in water-based coatings. The potential now available to improve environmental profiles follow-
Commonly used stabilisers such as dimethyl ethanolamine ing the introduction of this new sugar-based neutralising amine for
(DMEA) have a poor hazard profile and fail to meet the require- the neutralisation and stabilisation of fumed silica dispersions is con-
ments of several eco-labels. sidered below. Its application and performance profile is discussed in
detail in comparison to common neutralising agents on the market.
űű Dimethyl glucamine has been developed as a largely bio- In order to create a comprehensive assessment of these neutralising
based alternative with up to 75% renewable content which is agents, environmental, health and safety aspects have been consid-
completely safe (it is approved for use in unlimited amounts ered in addition to performance characteristics. To support perfor-
under various eco-labels). mance evaluation, comparative tests are based on fumed silica slur-
ries of the “Aerosil” types developed by Evonik.
űű A study of rheology curves for two different coating formu- Matters such as labelling or VOCs play an important role, especially in
lations thickened with fumed silica showed that the new sta- relation to eco-labels. It is no easy task for a paint formulator to de-
biliser performs at least as well as DMEA. In some cases, bet- velop a high-quality paint that fulfils stringent ecolabel criteria.
ter stability and efficiency were obtained when using dimethyl Dimethyl ethanolamine (DMEA), however, is not suitable for paints
glucamine. and varnishes with the German Blue Angel RAL UZ12a, Nordic Swan
for indoor paints and varnishes or the French Décret NF Environment
because of its VOC content and its hazardous labelling, especially the
hazard phrase H331 (toxic if inhaled).
In the evaluation of neutralising agents’ suitability for ecolabels, di-
methyl glucamine stands out as a multifunctional neutralising agent
as it is the only one that can be used in unlimited amounts in paints
which are certified according to the German Blue Angel, Nordic Swan
or French Décret NF Environment. This is because the additive has no
hazardous labelling and is VOC/SVOC-free. 

 Although the renewable content is not yet a criterion for ecolabels, Dispersions were produced using an “Ultra Turrax” (UTE) dissolver,
another advantage of dimethyl glucamine is that it consists of up to Skandex shaker or a Hilscher ultrasonic disperser. The starting formu-
75% glucose and is therefore very much in line with the trend of re- lations for the fumed silica slurry dispersions are described in Table 2.
newable raw materials.
A selection of important sustainability aspects comparing dimethyl- INITIAL FLOW CURVE EVALUATION SUMMARISED
glucamine to DMEA is listed in Table 1.
In Figures 1a and 1b, the results for the particle size distribution of
HOW NEUTRALISING AGENT PERFORMANCE WAS EVALUATED the fumed silica slurry formulations are shown after dispersing the
fumed silica with the UTE disperser (circumferential or peripheral
In addition to the environmental, health and safety aspects, the per- speed 13 m/s).
formance of both neutralising agents was also evaluated. The neu- The particle size distribution of the dispersions with DMEA and di-
tralising amines were first formulated into fumed silica slurry disper- methylglucamine show equivalent behaviour. This means that the dis-
sions and then 10% of these dispersions were incorporated into a persing and wetting time of both formulations are comparable and a
PU-acrylic as well as into a styrene-acrylic clear coat. switch from one neutralising system to the other would not affect the
The formulations were tested on the following criteria: overall processing time.
ąą Particle size distribution Based on these results, flow curves of the fumed silica slurry disper-
ąą Flow curves sions were measured. When comparing the flow curves in Figure 2,
ąą Shear recovery dispersions prepared with the UTE disperser show slightly higher vis-
Table 1: Over view of the sustainability profiles of dimethylglucamine versus DMEA.
GHS
Neutralising agent Hazard statements Flash point VOC* SVOC* Biodegradation
labelling
H226 Flammable
H312 Harmful on contact with skin
H331 Toxic if inhaled
Dimethylethanolamine
H302 Harmful if swallowed 39 °C Yes No Readily biodegradable
(DMEA)
H335 May cause respiratory irritation
H314 Causes severe skin burns and eye damage
H402 Harmful to aquatic life
Dimethyl glucamine none none > 100 °C No No Readily biodegradable
* according to ISO 11890-2 and ISO 16000-9
Figure 2: Flow cur ves of the fumed silica slurry dispersions. Figure 3: Shear recovery of the fumed silica slurry dispersions.
0.16 0.16
0.14 0.14
0.12 0.12
0.10 0.10
Viscosity in Pa.s
Viscosity in Pa.s
0.08 0.08
0.06 0.06
0.04 0.04
0.02 0.02
0 0
-0.02 -0.02
-0.04 -0.04
0.1 1 10 100 1000 0 50 100 150 200 250 300 350 400 450 500
Shear rate in 1/s Shear rate in 1/s

 Demineralised water  Demineralised water
 “Aerosil” dispersion with 7.2% Genamin Gluco 50 (UTE)  “Aerosil” dispersion with 7.2% Genamin Gluco 50 (UTE)
 “Aerosil” dispersion with 3.0% DMEA (UTE)  “Aerosil” dispersion with 3.0% DMEA (UTE)
WAT ER -BO RN E 73
cosity for dimethylglucamine compared to DMEA. One advantage of less well than non-renewable alternatives. The advantage of the con-
a higher viscosity can be that less rheology modifier is required in the stant levelling behaviour is that there is no need to change the paint
paint formulation in which the fumed silica slurry dispersion is used. recipe and/or use other additives to adjust the levelling behaviour.
If the fumed silica slurry dispersions are required to have comparable
flow curves and viscosity profiles over the complete shear range, ad- RHEOLOGY CONTROL EVALUATED IN CLEAR COATS
ditional dispersion using the Hilscher ultrasonic disperser is recom-
mended. All dispersions tested were then water-thin. 10% of the fumed silica slurry dispersions were next formulated into
In the next test, the dispersions were evaluated in relation to their clear coats. The main function of the dispersion in this application is
shear recovery after high shear treatment. Dispersions with both sta- rheology control. For this purpose, two water-based clear coat formu-
bilising agents had similar low shear thickening behaviour as shown in lations based on the following binders were used:
Figure 3. Under dispersion with the Hilscher ultrasonic disperser, an ąą PU-acrylic hybrid dispersion: Solids content 35%; neutralisation:
almost perfect Newtonian rheology was achieved. triethanolamine (TEA); pH value: 8.0.
This means that the levelling behaviour of both fumed silica slurry ąą Styrene-acrylic copolymer: Solids content: 40%; neutralisation: am-
dispersions remains constantly at the same level. This is of particular monia; pH value: 9.0.
interest as dimethylglucamine is a renewable-based additive and re- As can be seen in Figure 4, the PU-acrylic clear coat containing the
newable ingredients are often considered by the industry to perform fumed silica slurry dispersion which has been neutralised with DMEA
Figure 5: Rheology cur ves of of the aqueous styrene-acrylic

Figure 4: Rheology cur ves of the aqueous PU-acrylic clear coat. clear coat.
750 6,000
650
5,000
550
4,000
Viscosity in Pa.s
Viscosity in Pa.s
450
3,000
350
2,000
250
1,000
150
0 50 100 150 200 250 300 350 400 450
0
Time in s 0 50 100 150 200 250 300 350 400 450
 PU-acrylic clear coat without “Aerosil” dispersion Time in s

 P
U-acrylic clear coat containing 10% “Aerosil”
 Styrene-acrylic clear coat without “Aerosil” dispersion
dispersion neutralized with DMEA after 24 hours storage
 S
tyrene-acrylic clear coat coating10% “Aerosil” dispersion
 P
U-acrylic clear coat containing 10% “Aerosil”
neutralized with DMEA after 28 days storage
dispersion neutralized with DMEA after 28 days storage
 S
tyrene-acrylic clear coat coating10% “Aerosil” dispersion
 P
U-acrylic clear coat containing 10% “Aerosil” dispersion
neutralized with Genamin Gluco 50 after 28 days storage
neutralized with Genamin Gluco 50 after 24 hours storage
 P
U-acrylic clear coat containing 10% “Aerosil” dispersion
neutralized with Genamin Gluco 50 after 28 days storage
Table 2: Fumed silica slurry formulations with dimethylglucamine versus DMEA.
Ingredient Fumed silica slurry formulation with dimethylglucamine Formulation with dimethylethanolamine
(active content 50%) (active content 98%)
“Aerosil” R 972 20% 20%
Wetting agent 10-20% 10-20%
Neutralising agent 4-8% 2-4%
Cosolvent 1-4% 1-4%
Defoamer 1% 1%
Demineralised water Add up to 100% Add up to 100%


 shows a more pronounced rheology response, with a change of the to be produced. In addition, clear coat formulations containing fumed
viscosity behaviour during storage at room temperature between 24 silica slurry dispersions that have been previously neutralised with
hours and 28 days. dimethylglucamine show excellent rheology performance. This offers
The analogous clear coat based on the fumed silica slurry dispersion the possibility of improving the cost/performance of the paint as the
with dimethylglucamine shows a very good, unchanged viscosity pro- overall amount of fumed silica slurry dispersion can be adjusted in
file behaviour during the complete storage time, indicating improved the formulation.
wetting behavior with dimethylglucamine. The ingredient combines multi-functionality with an excellent eco-pro-
Dimethylglucamine shows excellent shear thinning behaviour and also file and is therefore a new, highly valuable ingredient for the paints
good storage stability at low shear rates in comparison to the DMEA and coatings industry as it seeks to address increasing requirements
system. This means that the levelling behaviour of the PU-acrylic coat- from end-users and the industry’s own priorities. 
ing is excellent. Also, the absence of any significant change in the rhe-
ology behaviour between 24 hours and 28 days is especially valuable
for the quality department of the paint manufacturer, as it is possible REFERENCES
to test and evaluate the paint quality very shortly after its production.
This helps to save valuable time and internal storage costs. [1] http://articles.mercola.com/sites/articles/archive/2011/07/25/poor-
As can be seen in Figure 5, the styrene-acrylic clear coat containing indoor-air-quality-could-be-jeopardizing-your-health.aspx
the fumed silica slurry dispersion which has been neutralised with di- [2] https://www.epa.gov/indoor-air-quality-iaq
methylglucamine shows a more pronounced rheology response, with [3] Freedonia Group World Paint & Coatings Study, with Forecasts for 2017
a higher viscosity at low shear rates compared to the corresponding and 2022, March 2014.
formulation with DMEA. Achieving higher viscosities would allow the [4] Evonik: AEROSIL R 9200 to improve the scratch resistance of paint and
amount of fumed silica slurry dispersions and/or the rheology modi- coating systems, Technical Information 1284.
fier in the clear coat formulation to be reduced. [5] Evonik: AEROSIL specialized fumed silica to enhance coatings perfor-
mance, AEROSIL 03-16.
HIGH PERFORMANCE IS COMBINED [6] Jessop P.G. et al, Opportunities for greener alternatives in chemical formu-
WITH A GOOD ECO-PROFILE lations, Green Chem., 2015, Vol. 17, pp 2664-2678.
[7] Ziebold S., Rüger J., Novel sugar-based additive for ecolabel-certified
The most important applications of fumed silica slurry are rheology paints, ECJ, 03-2017
control, thickening, thixotropy, anti-settling of pigments and fillers and
anti-sagging of coatings on vertical substrates.
Neutralising agents are only used in small quantities in water-based
formulations. However, their effect is of significant importance in
paints and in fumed silica slurry dispersions. Neutralising agents not
only regulate the pH value, but also influence the dispersibility and
storage stability as well as the rheology behaviour of the formulation.
Dimethylglucamine is new to the market and was developed specifi-
cally for use as a multifunctional perfomance additive in ecologically-
compatible, water-based paints. It contains up to 75% renewable raw
materials, does not require labeling, is VOC/SVOC free and is there-
fore especially suitable for eco-label certified lacquers and varnishes.
From a performance point of view, this is a multifunctional additive
that allows stable, pumpable and label-free fumed silica dispersions
Find out more!
Additives
437 search results for additives!

WAT ER -BO RN E 75
“Formulators have the oppor-

tunity to reduce the levels of
high-cost raw materials.“
3 questions to Jörg Rüger Jörg Rüger

Clariant Germany
You repeatably claim that your additive is multi-functional. Which other functionalities be- joerg.rueger@clariant.com
side neutralising does the new additive have? Dimethylglucamine has a functionality as neutralis-
ing agent, stabiliser, wetting agent and rheology enhancer. The additive is not only used to adjust the
pH-value of the fumed silica dispersion from a value of 10.0 to 10.5, but also to improve its storage
stability, by avoiding syneresis or sedimentation and by maintaining a stable viscosity and pH-value
of the formulation during long-term storage. This can be explained by the product’s improved wetting
behavior on the other ingredients of the slurry. Dimethylglucamine is also beneficial in influencing the
rheology behavior of paints when prior used in the fumed silica dispersion. It increases the viscosity of
the paint formulation and in consequence less amount of rheology modifier is required.
Your tests with the acrylic test system indicated an improved wetting behavior of the di-
methylglucamine. Did you saw similar results for the styrene-acrlic copolymer system?
We saw different results from different systems. In the styrene-acrylic clear coat system, we observed
the same initial rheology curve as the acrylic system. After 28 days, we observed an increase in the
viscosity of the styrene-acrylic system that did not occur in the acrylic system. Due to the increase in
viscosity over time of the styrene-acrylic system, formulators have the opportunity to reduce the levels
of high-cost raw materials in styrene-acrylic formulations, including rheology modifiers or the amount
of fumed silica slurry.
What is the source of your bio-based content. Is it in competition to the food supply chain?
Dimethylglucamine is based on glucose, extracted from European non-gene-modified corn. The prod-
uct’s renewable content is 75% according to the renewable carbon index RCI. (Dimethylglucamine
consists of 8 carbon atoms, thereof 6 atoms are sugar-based. The other 2 are of synthetic origin.) As
glucose can be used in the food production, there is a certain competition with the food supply chain.
But in comparison to other raw materials such as palm oil where there is a valid discussion ongo-
ing on how to improve the impact on people and planet, sugar or glucose is abundantly available
on the world market. We therefore did not consider this aspect as a major risk in the sustainability
assessment of our product. Dimethylglucamine underwent a thorough screening against 36 criteria
covering the entire product lifecycle and was also benchmarked against market standards. Due to the
product’s outstanding sustainability profile, dimethylglucamine has therefore been awarded Clariant’s
EcoTain label.

76 P IG M E N T D I S P E R S ION
Source: (c) Leigh Prather - stock.adobe.com
PAINTING A MORE STABLE PICTURE

Improving pigment dispersion and paint performance with versatile amino alcohols. By Dr Romain Severac and Yoann
Fernandes, Angus Chemical (published in ECJ 06/2018),
Alkanolamines, such as 2-amino-2-methyl-1-propanol (AMP) and AMP ADSORPTION LINKED TO PARTICLE SURFACE
2-amino-2-ethyl-1,3-propanediol (AEPD), are commonly used as
key stabilising agents in a wide range of water-borne paint formu- As shown in Figure 1, the adsorption ratio of AMP at the surface of sev-
lations. Not all alkanolamines are equivalent but AMP and AEPD eral pigments was measured. The protocol used in this investigation is
can be used to improve the pigment particle size distribution and based on the preparation of slurries of each individual pigment at about
exploit synergistic effects with common dispersing agents. Opti- 60 wt% solids content, with a disperser at high shear (20 min at 1700
mising the formulation in this way has the potential to reduce rpm) in the presence of several concentrations of AMP. After this dis-
raw material costs while improving paint performance. persing step, slurries are centrifuged (min. 2h30 at 4500 rpm) until the
dispersed pigments are fully settled, and the unabsorbed amount of
O ne the most crucial steps in paint manufacturing is the disper-

sion of pigments, which drastically impacts almost all perfor-
mance aspects of both the coating and dry film. The selection of a reg-
AMP, free in the filtrate, is determined by a straightforward titration
with a strong acid. All raw materials were used as supplied.
The adsorption of AMP is significant in all cases (Figure 1) and this is
ular dispersing agent mixture usually depends on the composition of important evidence of the strong affinity driving this phenomenon.
the pigment blend [1]. This is due to the variety of pigments and their The adsorption reaches a plateau that corresponds to the saturation
chemical compositions, as well as the development of a wide range of of the surface.
surface treatments [2]. With the presence of the amine function and The quantity of adsorbed products appears to be linked to the par-
the alcohol group, alkanolamines can form both ionic and hydrogen ticle diameter. Given equivalent porosity, smaller particles have a
bonds with the surface of pigments [3], which drives both the wetta- higher surface area that can adsorb a higher concentration of AMP.
bility of pigment agglomerates and the reduction of attractive forces By using the same protocol, five slurries of titanium dioxides were
between the particles resulting in the breakdown of pigment agglom- prepared with a wide range of surface treatments (0.1% to 10.3% of
erates. In addition, AMP or AEPD interacts with conventional anionic SiO2, 2.1% to 4.0% Al2O3, 0.0% to 0.5% ZrO2, and up to 0.25% organic
dispersing agents such as polyacrylic surfactants or polyphosphates. treatment). The adsorption of amino alcohols was standardised by
Modifying the nature of the counter ion of these polymeric species ad- dividing the molar adsorption by the TiO2 surface areas. The versatil-
justs affinities with pigment surface. The combination of these specific ity of the adsorption is confirmed as adsorption occurs whatever the
synergies leads to an improved particle size distribution of pigments. TiO2 treatment (Figure 2). The differences shown between the level of
P I G MENT DI SP ER S IO N 77
the saturation plateau are close to the accuracy of the methodology

and are insignificant.
IMPROVING TIO2 DISPERSION FOR BEST

LIGHT SCATTERING EFFICIENCY
RESULTS AT A GLANCE In parallel, means of particle size (PS) have been determined using a
laser scattering technique. The evolution of the PS means as a func-
 Alkanolamines, such as 2-amino-2-methyl-1-propanol (AMP) and tion of both AMP and AEPD concentrations is shown in Figure 3. The
2-amino-2-ethyl-1,3-propanediol (AEPD), are commonly used as sta- correlation between the concentration of both amino alcohols and the
bilisers in water-borne paint formulations. improvement in the TiO2 dispersion applies to almost all TiO2 types.
This correlation is not visible with TiO2 “Kronos 2043” or TiO2 “Ti-Pure
 Depending on the chemical structure, agglomerates and particle 706” as even at the lowest dosage (0.25 wt% of alkanolamines per pig-
size distribution can be optimised by exploiting specific amino alco- ment weight), the particle size is at the plateau. Further investigation
hols and their interaction with pigments and dispersing agents. will be performed at lower concentrations of these dispersing agents.
In Figure 2, these two examples correspond to pigments with the high-
 Formulators can use amino alcohols to minimise undesirable side est affinity with AMP and AEPD (the adsorbed amount is the highest).
effects and improve overall pigment efficiency and potentially reduce Confirmation of the fundamental difference between a neutraliser,
costs. such as sodium hydroxide, and stabilisers, such as AMP or AEPD, may
be seen in Figure 4. According to this experiment, showing the evolu-
 Wet abrasion resistance is one example where amino alcohols tion of the TiO2 particle size, shown as a function of dispersion time
and their synergy with common dispersing agents can improve paint (66 wt% TiO2, 1.5% of neutraliser, disc diameter 4 cm, can diameter 7
performance. cm, speed 1600 rpm), either AMP or AEPD are able to wet and support
the dispersion of TiO2 which makes it possible to recover the expected
optimum particle size and results in the best light scattering efficiency.
At the opposite end of the spectrum, a simple neutraliser such as
sodium hydroxide, even after a long dispersion time, is not able to
significantly support this process.
AEPD REDUCES THE NEED FOR DISPERSING AGENTS
In addition to the natural dispersing property of both AMP and AEPD,

the interaction with regular dispersing agents commonly used in the
industry was evaluated [4]. Table 1 presents a select list of dispersing
agents containing polyphosphate and either a hydrophilic or hydro-
Figure 1: Adsorption of AMP at the surface of several pigments. phobic, neutralised copolymer of maleic anhydride. Samples of co-
polymers were classified from the most hydrophilic (Sample 1) to the
most hydrophobic (Sample 5). Dispersing agents have been engaged
in dispersing agent demand curves (evolution of Krebs viscosities with
0,4 dispersant concentrations) either alone or combined with AEPD. This
common procedure consists of determining the minimum concentra- 
0,35
Concentration of adsorbed AMP
0,3 Figure 2: Adsorption average of AMP and AEPD at the surface of

0,25 several TiO 2 particles.
0,2
0,15
n absorbed (stabiliser)/TiO2 surface
0,1 0,00000035
0,0000003
0,05
0,00000025
0 0,0000002
0,03 0,53 1,03 1,53 2,03 2,53 3,03 3,53 0,00000015
0,0000001
Concentration of loaded AMP in %wt per pigment weight 0,0000005
0
0,0% 0,5% 1,0% 1,5%
% Stabiliser
 Ground calcium carbonate  Rutile TiO 2  Delaminated clay
 Kaolin clay, medium particle size  “Kronos 2043”  “Kronos 2056”
 Kaolin clay, ultra-fine particle size  “Kronos 2160”  “Kronos 2190“
 “Ti-Pure 706“

 tion of dispersing agent required to produce the optimum wetting In addition to the ability of minimising the overall dispersing agent
point. This point corresponds to the concentration at which the vis- concentrations to reduce the dry-film hydrophilicity, the strong inter-
cosity no longer decreases. action between AMP and AEPD with an acrylic dispersing agent can
Figure 5 sums up all comparative examples, and the impact of the pres- improve its intrinsic property. A set of satin water-based coatings with
ence of 0.3 wt% AEPD on these dispersing agents is significant. The sys- low volatile organic compounds, were taken through a design of ex-
tematic improvement of the dispersing agent shows the universality and periment methodology (4 concentrations of TiO2 from 12% to 18%;
versatility of AEPD. It means that the use of AEPD enables the reduction three neutralisers including AMP, AEPD and NaOH; and three concen-
in primary dispersing agents in water-based formulated products, mini- trations of polyacrylic dispersing agents). Wet scrub resistance tests,
mising drawbacks of these hydrophilic anionic species [5, 6]. based on the ISO 11998:2006 standard, were performed under harsh
conditions (1500 cycles, 4 weeks of dry film drying, 200 µm applied
LOW CONCENTRATIONS MINIMISE COMMON SIDE EFFECTS on a panel, 4 repeated tests). Figure 6 shows the statistical analysis in
Figure 3: Evolution of the particle size means of TiO 2 slurries Figure 4: Evolution of particle size of TiO 2 Kronos 2190 slurries
containing AMP and AEPD. as a function of the dispersing time with difference neutralisers.
Particle size in nm of slurry vs. % stabiliser

2000
1100 1800
1600
Mean of particle size in nm
1000
particle size in nm of slurry
900 1400
800 1200
700 1000
600 800
500 600
400 400
300 200
200 0
0.0% 0.5% 1.0% 1.5% 0 10 20 30 40 50 60 70
% Stabiliser per TiO2 weight Dispersing time in min

 “Kronos 2043”  “Kronos 2056”  NaOH  AMP  AEPD
 “Kronos 2190”  “Kronos 2310”
 “Ti-Pure 706”
Figure 5: Dispersant demand cur ves with several dispersing agents and TiO 2 D with and without 0.3 wt% AEPD.
130
120
110
100
90
Krebs viscosity in KU
80
70
60
50
40
0.05%
0.10%
0.15%
0.20%
0.25%
0.30%
0.35%
0.40%
0.45%
0.50%
0.55%
0.60%
0.65%
0.70%
0.75%
0.80%
0.85%
0.90%
0.95%
1.00%
%wt of dispersing agent per TiO2 weight
 “Calgon N new” (sol 25%) with 0.3% AEPD 1000/tit  “Calgon N new” (sol 25%)  “Orotan CA2500” with 0.3% AEPD 1000/tit
 “Orotan CA2500”  “Orotan 681” with 0.3% AEPD 1000/tit  “Orotan 681”  “Orotan QR1124” with 0.3% AEPD 1000/tit
 “Orotan QR1124”  “Orotan 731” with 0.3% AEPD 1000/tit  “Orotan 731”
P I G MENT DI SP ER S IO N 79
a box plot representation. Despite the lower concentrations of these material costs while improving paint performance. Formulators are able
additives, in the range of 0.1 wt% to 0.3 wt% loaded at the dispersion to unleash the potential boosting effect of amino alcohols to significantly
step, this experiment provides a good illustration of the result of the minimise the undesirable “side effects” of regular additives, and improve
interaction provided by these amino alcohols. This effect could be also the overall pigment efficiency. In particular, the improvement of wet
linked to the initial adsorption mechanism disclosed in this paper. As abrasion resistance can be enhanced by the presence of amino alcohols
amino alcohols such as AMP or AEPD are adsorbed to a large extent and thanks to synergistic effects with common dispersing agents. 
on both pigments and fillers surface, and linked to dispersing agents,
this reduces the remaining free amino alcohols in the binder matrix, ACKNOWLEDGEMENTS
minimising the well-known usual effect of highly polar compounds in a
dry paint film. This effect becomes especially significant when consid- The authors would like to thank Kronos and Chemours for providing both
ering the current reformulation trends for titanium dioxide optimisa- materials and valuable feedback throughout this investigation. In addition,
tion, which leads to an increase of filler concentration that negatively thanks go to Farah Shaik Dawood and Marianne Riffault who performed
affects this parameter if not properly adjusted. laboratory work during their student internship at ANGUS Chemical Company.
AMINO ALCOHOLS BOOST PIGMENT EFFICIENCY REFERENCES
Alkanolamines such as 2-amino-2-methyl-1-propanol (AMP) and 2-ami- [1] T iarks F., Frechen T., Kirsch S., Leuninger J., Melan M., Pfau A., Richter F.,
no-2-ethyl-1,3-propanediol (AEPD), are commonly used as key stabilising Schuler B., Zhao C.-L., Formulation effects on the distribution of pigment
agents in a wide range of water-borne paint formulations. Due to the particles in paints, Progress in Organic Coatings 48 (2003) pp 140–152
strong interaction between specific amino alcohols and both pigments [2] W inkler J., Dispersing Pigments and Fillers, (Hanover: Vincentz Network,
and dispersing agents, the level of agglomerates and the overall particle 2012), p. 35.
size distribution of pigments can be improved in paint formulations. Not [3] M üller B., Poth U., Coatings Formulation, 2nd revised Edition (Hanover: Vin-
all alkanolamines are equivalent, and these effects strongly depend on centz Network, 2011), p. 172.
the chemical structure of the product. In addition to the natural dispers- [4] C layton J., Pigment/Dispersant Interactions in Water-based coatings,
ing ability of these molecules, synergistic effects have been identified Surface Coatings International 9 (1997) pp 414-420
with regular dispersing agents, such as polyphosphates and neutralised [5] V erkholantsev V. V., Multifunctional aids, European Coatings Journal, 5
copolymers of maleic anhydride. The versatility of 2-amino-2-methyl- (2000) pp 42–50
1-propanol and 2-amino-2-ethyl-1,3-propanediol can be used to re- [6] M uth M., Freytag A., Conrad M., Maintaining protection: how dispersants
duce both numbers and levels of some commonly used paint additives affect corrosion resistance of waterborne paints, European Coatings
through the optimisation of paint formulations, potentially lowering raw Journal, 1 (2016) pp 30-33
Table 1: Selected dispersing agents.
Dispersing agents Technology Neutralisation
“Calgon N*” polyphosphate sodium salt

Find out more!
hydrophobic copolymer of
“Orotan QR 1124*” ammonium salt
anhydride maleic
“Orotan 731*”
anhydride maleic
sodium salt
Additives
“Orotan 681*” ammonium salt
anhydride maleic
“Orotan CA2500*”
anhydride maleic
sodium salt
449 search results for additives!
* Registered trademark of a third party
“Formulators can minimise

several negative side effects.“
3 questions to Dr Romain Severac Dr Romain Severac

ANGUS Chemical Company
Concerning the cost reduction: what would be your estimate in a standard formulation RSeverac@angus.com
for a premium indoor paint? We’ve seen in a number of formulations how the functional versatili-
ty of our amino alcohols can help formulators reduce both the number and levels of commonly used
paint additives. For example, as demonstrated in this investigation, the highly effective co-dispersion
properties of AMP or AEPD can enable the reduction of primary dispersing agents used in the grind
phase. At the same time, the hiding and gloss performance of AMP and AEPD also imply a potential
for reducing the use of both pigments and binders. The unique nature of our amino alcohols can
enhance the long-term stabilisation of the coating system, which is primarily based on the pH buff-
ering effect combined with the enhancement of regular dispersing agents (such as polyacrylates),
improving the robustness, the reproducibility, and the shelf life of the formulated product. In addi-
tion, numerous studies demonstrate a potential synergistic effect between both AMP and AEPD and
certain approved biocides in many formulation types across multiple applications. This synergistic
effect can provide enhanced syneresis control and improved in-can stability, while helping formula-
tors optimise their use of approved biocides, depending on the individual formulation.
Which side-effect is minimised the best by using AMP and AEPD? Because the versatility of
AMP and AEPD may enable the significant reduction of commonly used primary dispersing agents,
formulators can also minimise several negative side effects of these additives, such as water resist-
ance or wet scrub resistance. In the case of reducing polyphosphates concentrations, the optimisa-
tion of these wetting agents helps to improve the overall rheology profile of the formulation. It is also
important to stress that, as is with all dispersing agents, the optimum performance can be achieved
by finding the right balance between the use of different dispersing agents.
How can AMP and AEPD be implemented into an established formulation? This is strongly
driven by what individual performance improvements or attributes are being targeted with the for-
mulation. To start, AMP or AEPD can be loaded, even partially, to enhance dispersion during the
grind phase, especially when prepared as a solution of pre-neutralised blend of dispersing agents.
This will enable AMP or AEPD to interact with the dispersing agent and, as a result, enhance the
synergistic effect. Then, step by step, dispersing agents can be reduced until all desired critical perfor-
mance properties are maintained.
Source: platongkoh55 - Fotolia.com W O R LD O F C O L O UR 81
COLOURED TREES
50,000 litres of protecti-
ve coatings were used on
Singapore‘s Gardens by the
Bay. This attraction consists
of the world‘s largest clima-
te-controlled glass houses
as well as 18 of the pictured
supertrees.
MIMICKING NATURE
Not only the consevatories
of Gardens by the Bay but
also the trees are home to
many tropical plants. They
provide air intake and mimic
the ecological functions of
real trees.

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EUROPEAN

Testing and measuring instruments from BYK

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I trust you will find this an exciting and informative read!

E U R OP E AN COAT I NGS JO UR N A L 2019

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EUROPEAN COATINGS JOURNAL 2019

6 MARKET REPORT 20 WETTING AGENTS

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54 BIOCIDES 76 PIGMENT DISPERSION

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E U R OP E AN COAT I NGS JO UR N A L 2019

THE DEMAND FOR COATINGS

R aw materials used in the manufacturing of paints and coatings rep-

Figure 1: Coatings raw materials value by type (2017).

E U R OP E AN COAT I NGS JO UR N A L 2019

 Resins  Solvents  Resins  Solvents

tives at 15%. ąą Silberline Synthopol

As is the case with multinational chemical companies, mergers and ac-

E U R OP E AN COAT I NGS JO UR N A L 2019

THE BIG FIVE IN THE SCOPE

C onsumption of these five additives was 1.15 million tonnes in 2017

Rheology 439 16 455 1,580

Foam 182 7 189 717

Slip/rub 97 46 142 683

Wetting 129 7 136 623

E U R OP E AN COAT I NGS JO UR N A L 2019

It’s not so welcome in paints and coatings, though. In this

R educed gloss, less transparency and imperfections that can even

Foamstar ED Polymer emulsion with small 1.00 g/ml 2,000 mPa.s

Foamstar SI Compound of modified polydi- 1.00 g/ml 600 mPa.s

silicone-free polyamide particles 1.00 g/ml 62 %

Additive 108F Silicone - 1,600 mm²/s - 25.5%

Blend of hydrophobic silica, 0.90 450 mPa.s

Blend of organic modified poly- 0.98 g/cm³

with a high-class finish and, above all, are properly protected.

VOC-free according to EU Directive 2004/42/EC and EPA

Pigment concentrates, pigmented aqueous coatings, Broad food contact compliance

Suitable for food contact applications Stable to acids and

Does not impact the transparency Little or none reduction

Water-based paints, coating and inks APEO free

Particularly useful for gloss paints and clear acrylic coat-

Alkali and acid resistant (can be used in a pH-range

E U R OP E AN COAT I NGS JO UR N A L 2019

DRY AND DURABLE

­ e humans can make ourselves comfortable in our own

A good architectural paint has to meet many requirements. As a

Apperi- Wax melt- Recommend-

Emulsion of amino 200 mPa.s 0.98 g/cm³

Paraffin wax emul- White

Modified paraffin White 0.95 g/cm³

Lanco Glidd Blend of waxes and Smooth

Nanoscale wax Semi- < 1,000 mPa.s

Anionic paraffin/ Semi- < 100 mPa.s

“The global architectural

Understanding Additives, 160 pages, Bodo Müller

e humans can make ourselves comfortable in our own