A Safe and Effective Anti-skinning Agent

for Replacing MEKO

Edward Asirvatham, AdvanSix Inc., USA
and Cèline de Lame§,
Coatings Research Institute, Belgium
A Safe and Effective Anti-skinning Agent
for Replacing MEKO

Air-drying, solvent-borne alkyd paints represent a significant share of decorative paints. Typically, such paint
formulations contain alkyd resins, fillers, pigments, solvents, and other additives tailored to applications.
Additionally, metal catalysts (driers) are used in the formulations to facilitate air-drying of such paints.

Formulators add anti-skinning agents to alkyd paint cans to prevent oxidative drying of the paint, which is the
result of resin crosslinking, while it is in the can. Anti-skinning agents form a complex with the drier salts, thereby
preventing premature crosslinking of the alkyd resin which would otherwise lead to drying of the paint. When the
paint is applied, however, the anti-skinning agent must timely evaporate so that the metal ion of the drier salt can
be released to promote oxidative crosslinking and drying of the alkyd resin on the intended surface.

Methyl Ethyl Ketoxime

Until recently, the most widely used anti-skinning
agent is 2-butanone oxime, also known as MEKO
(methyl ethyl ketoxime). Although the mechanism
associated with the anti-skinning effect of MEKO is
not well understood, a study by S. Tanase et al.1
provided some insight into the MEKO-cobalt
complex and an alternative theory that MEKO acts
as a radical trap to inhibit drying in the can.
The advantages of MEKO include its high efficiency
for a wide variety of coatings for different substrates,
its ability to leave no residue in the dried film, its
resistance to yellowing or discoloration of paints, no
or low impact on the drying profile of the paints, and
no influence on the other aspects of paints such as
viscosity, gloss, adhesion, and solvent resistance.
Also, the amount of MEKO does not have to be
exact, as excess MEKO in the paint formulation
does not appear to negatively impact the overall
performance of the paint.
The use of MEKO as an anti-skinning agent
has been under regulatory threat for some
time, especially in Europe, for its suspected
carcinogenicity. For many years it was anticipated
that such a suspected toxicity would likely make it
necessary to label MEKO as a carcinogen, leading
to restrictions on its use in paints and coatings. In
fact, starting March 1, 2022, the European Union will
reclassify MEKO as a Carcinogen 1B.
To prepare for this, the alkyd paints and coatings
industry has been looking for an alternative anti-
skinning agent to MEKO – one that can confer
the same or similar performance benefits and
become a simple “drop in” replacement. One option
extensively researched and tested for feasibility was
for oxime-free anti-skinning agents including, for
example, N-substituted hydroxyl amines, substituted
phenols, hydroquinone and ureas, phosphates, and
carboxylic esters.
From these extended efforts, conclusions have been
drawn that a true, drop-in replacement of MEKO
would only be found in another oxime derivative2.
Oxime-free anti-skinning agents tend not to meet
the need, since they do not reliably confer good
performance in use.
Several aliphatic oximes have been evaluated as
anti-skinning agents. Notable options include,
without limitation, acetone oxime, cyclohexanone
oxime, methyl isobutyl ketoxime (MIBKO),
acetaldehyde oxime, and butyraldehyde oxime.
Although some were found suitable for special
purposes (e.g., cyclohexanone oxime was found
to be a potentially useful anti-skinning agent for
offset-inks), none has been proven to be an ideal
replacement for MEKO for either functional or
safety reasons2-3.

1
2-Pentanone Oxime (2-PO)
A. Comparable If Not Better Performance
than MEKO
An aliphatic ketoxime not mentioned above,
2-pentanone oxime (2-PO), has been developed
as an alternative to MEKO. Although 2-PO bears
structural similarity to MEKO, its physical properties
are different in several important aspects.
Vapor pressure is a key property for determining
viability of a material to serve as an additive for
coatings. The vapor pressure of 2-PO, 1.6 mm
Hg @ 20ºC, is significantly lower than that of
MEKO (8.0 mm Hg @ 20ºC). Based on this, one
might expect to see a negative impact on the
drying profile of the paints formulated with 2-PO.
However, and surprisingly, in standard drying tests
(ASTM D 5895-03) the overall drying time for paints
including equivalent amounts of 2-PO is similar to
that of MEKO-based paints. J. Flapper and F. L.
Duivenvoorde demonstrated that the performance of
2-PO in paints shows no discernable differences to
that of MEKO2. Just like MEKO, 2-PO confers similar
anti-skinning effectiveness and does not negatively
impact other key properties.
In high-gloss white paints (Table 1) with cobalt drier
salts (A) and non-cobalt drier salts (B)3 formulations,
the anti-skinning performance (Table 2) and drying
profile at 0.25 wt. %, 0.35 wt. % and 0.5 wt. %
levels of 2-PO showed similar results to that of
MEKO (Figures 1 and 2). Note that although there
might have been some earlier reservations about the
efficacy of 2-PO as compared to the tried-and-true
MEKO1 when used with cobalt-free formulations,
no doubt due to natural hesitations associated with
the new and unfamiliar, the data clearly indicate that
rather than being inferior in the presence of non-
cobalt driers, 2-PO in fact performs better in such
driers than it does in the presence of cobalt-based
driers, at least when it comes to paint drying times
across all formulations tested.
In alkyd urethane satin- and clear-gloss formulations
(Table 3), the satin-clear formulations with a cobalt
drier (Figure 3) and clear-gloss formulations with
a cobalt drier (Figure 4), 2-PO performed on par
2
with MEKO at 0.35 wt. % and 0.5 wt. % levels.
These clear high-solid formulations contain an alkyd
urethane resin (85-90 wt. %), a siccative agent
(3.8-4.0 wt. %), white spirit (~6%), and anti-skinning
agents MEKO or 2-PO. Satin clear formulations
also include a thickener and a matting agent. (Paint
samples were provided by RD Coatings - DOTHEE
SA, Assesse, Belgium.)
B. Tests and Methods
• Storage Stability and Skinning Tests
Storage at elevated temperature was conducted
in closed containers where the head air volume
above the liquid paint was higher compared to
the liquid paint volume itself to accelerate the
aging process. Visual observation was made
of the aged liquid paints for skin formation
(or thickening) of the samples stored at
room temperature.
• Drying Time
The drying time of each raw material was
evaluated both manually and with a drying time
recorder used in accordance with ASTM D
5895-96, “Measuring Times of Drying or Curing
During Film Formation of Organic Coatings
Using Mechanical Recorders”.
Drying time measurements using a straight-line
drying time recorder were performed using the
following approach. The samples are applied on
glass plates in a well-defined film thickness. The
stylus of the drying time recorder is immediately
after application lowered into the wet film. The
stylus then moves across the sample on the
glass plate with a constant and well-defined
velocity. The measurements are performed at
23 ± 2°C and at a relative humidity of 50 ± 5%.
Afterward, the track left of the stylus on the film
is evaluated. The drying of the film is divided into
four stages: Stage 1: Set-To-Touch Time, Stage
2: Tack-Free Time, Stage 3: Dry-Hard Time, and
Stage-4: Dry-Through Time.
Table 1: High-Gloss White Paint Formulations

High-Gloss White A B

Components Wt. % Wt. %

1 SETAL AF 681 TB 30.00 30.00

2 White Spirit D60 10.00 10.00
Mill-base Formulation
3 Borchi® Gen 911 2.60 2.60
(Grinding on balls / 3500 rpm
4 Kronos 2310 26.00 26.00
45 minutes under cooling)
5 Borchi® Gol E, 50% in Solvesso 100 1.00 1.00
6 Octa-Soligen® Calcium 10, Basic 0.50 0.50

7 SETAL AF 681 TB 20.00 20.00

Let Down 8 White Spirit D60* 7.85 8.37
(Incorporation with slow 9 Borchi® Gol OL 17, 10% in Xylene 1.00 1.00
stirring and homogenization 10 Octa-Soligen® Zirconium 12 0.50 -
for 5 minutes) 11 Octa-Soligen® 69 0.30 -
12 Borchi® OXY - Coat - 0.28

Post-addition with Stirring 13 Anti-skinning Agent (MEKO or 2-PO) 0.35 - 0.50 0.35 - 0.50

TOTAL 100 100

*Adjusted per wt. % of MEKO or 2-PO

Table 2: Anti-Skinning Performance of 2-PO vs. MEKO

Anti-skinning Agent 8 weeks @ Room Temperature 4 weeks @ 50oC

0.5% MEKO No Skin No Skin

0.5% 2-PO (EZ-Blox®) No Skin No Skin

None Skin Skin

Figure 1: Drying Performance of Cobalt-based Figure 2: Drying Performance of Cobalt-free

High-Gloss White High-Gloss White

Drying
Drying Time
Time (Hrs)
(Hrs) Drying
Drying Time
Time (Hrs)
(Hrs)
0 0 1 1 2 2 3 3 4 4 5 5 0 0 1 1 2 2 3 3 4 4 5 5

2-PO
2-PO @ 0.5
@ 0.5 Wt.%
Wt.% 2-PO @ 0.5 Wt.%
2-PO @ 0.5 Wt.%

MEKO @ 0.5 Wt.% MEKO @ 0.5 Wt.%

MEKO @ 0.5 Wt.% MEKO @ 0.5 Wt.%

2-PO @ 0.35 Wt.% 2-PO @ 0.35 Wt.%

2-PO @ 0.35 Wt.% 2-PO @ 0.35 Wt.%

MEKO @ 0.35 Wt.% MEKO @ 0.35 Wt.%

MEKO @ 0.35 Wt.% MEKO @ 0.35 Wt.%
Stage I Stage II Stage IV Stage I Stage II Stage IV

Stage I Stage II Stage IV Stage I Stage II Stage IV

Drying Time (Hrs) Drying Time (Hrs)

0 1 2 3 4 0 1 2 3
Drying Time (Hrs) Drying Time (Hrs)
2-PO @ 0.5 Wt.%
3 2-PO @ 0.5 Wt.%
0 1 2 3 4 0 1 2 3

2-PO @ 0.5
MEKO Wt.%
@ 0.5 Wt.% 2-PO @ 0.5 Wt.%
MEKO @ 0.5 Wt.%
Table 3: Alkyd Urethanes Satin and Gloss

Alkyd Urethane* Satin Gloss

Components Wt. % Wt. %

Alkyd Urethane Resin 85.50 90.00

White Spirit D60 Drying
Drying
Time
Time
(Hrs)
(Hrs) 6.40 Drying
Drying
Time
Time
(Hrs)5.70
(Hrs)

Siccative Agent 0 0 1 1 2 2 3 3 4 4 5 5
3.80 0 0 1 1 2 2 34.00
3 4 4 5 5

Matting
2-PO
2-PO
@@ Agent
0.50.5
Wt.%
Wt.% 3.00 2-PO
2-PO
@@0.50.5
Wt.%
Wt.% 0.00
Thickener 1.00 0.00
MEKO
MEKO@@
0.50.5
Wt.%
Wt.% MEKO
MEKO@@
0.50.5
Wt.%
Wt.%

Anti-skinning
2-PO
2-PO
@@0.35
0.35 Wt.% Agent (MEKO or 2-PO)
Wt.% 0.35 - 0.50
2-PO
2-PO
@@0.35
0.35
Wt.%
Wt.% 0.35 - 0.50

MEKO
MEKO@@
0.35
0.35
Wt.%
Wt.% MEKO
MEKO@@
0.35
0.35
Wt.%
Wt.%

Stage
Stage
I I Stage
Stage
II II Stage
Stage
IV IV Stage
Stage
I I Stage
Stage
II II Stage
Stage
IV IV

Figure 3: Drying Performance of Cobalt-based Figure 4: Drying Performance of Cobalt-based

Satin Clear Clear Gloss

Drying
Drying
Time
Time
(Hrs)
(Hrs) Drying Time
Drying (Hrs)
Time (Hrs)
0 0 1 1 2 2 3 3 4 4 0 0 1 1 2 2 3 3

2-PO
2-PO
@@0.50.5
Wt.%
Wt.% 2-PO
2-PO
@@0.50.5
Wt.%
Wt.%

MEKO
MEKO@@
0.50.5
Wt.%
Wt.% MEKO
MEKO@@
0.50.5
Wt.%
Wt.%

2-PO
2-PO
@@0.35
0.35
Wt.%
Wt.% 2-PO
2-PO
@@0.35
0.35
Wt.%
Wt.%

MEKO
MEKO@@
0.35
0.35
Wt.%
Wt.% MEKO
MEKO@@
0.35
0.35
Wt.%
Wt.%

Stage
Stage I I Stage
Stage IV IV Stage I I
Stage Stage
Stage
IV IV

C. Favorable Toxicological Profile

• In connection with EU REACh registration, an Moreover, risk characterization ratios (RCRs),
extensive panel of Phys-Chem and toxicological defined as the ratio of exposure level and DNEL,
tests have been performed on 2-PO. Based on must be below 1. The study, conducted at
the publicly available dossier for this substance4, concentrations of 2-PO as high as 0.9 wt. %,
ready conclusions may be drawn that 2-PO indicated measured exposure levels consistently
has a substantially more favorable toxicological and significantly below its DNEL, (25 mg/m3,
profile as compared to that of MEKO. based on the results of a 90-day inhalation
• The safety of 2-PO is further confirmed via study), and RCR levels also reliably well below 1.
an occupational exposure risk assessment
study by Müller-BBM GmbH, Köln, Germany5.
Based on EU REACh guidelines, occupational
exposure risks are deemed acceptable when
exposure to workers from an intended use is
less than the effect level of the substance that is
the derived no effect level (DNEL).

4
Summary
An aliphatic ketoxime, 2-pentanone oxime (2-PO),
has been shown to be an effective and safe anti-
skinning agent for air-drying alkyd coatings. In
addition to its anti-skinning effectiveness, 2-PO has
demonstrated similar if not better performance than
MEKO in all aspects of anti-skinning performance,
including, without limitation, overall drying time,
odor, color, dosage flexibility, and comparable
performance with cobalt and cobalt-free driers.
The toxicological profile of 2-PO, as made clear
by extensive studies conducted for EU REACh
registration and occupational exposure limits (OELs),
is not only discernably more favorable than that of
the prior incumbent MEKO, but also much less toxic
than other oximes tested for the same purpose.
Recognizing the need for a sustainable alternative to
MEKO, AdvanSix launched EZ-Blox® anti-skinning
agent in 2019 to key alkyd paint producers to help
them prepare for EU reclassification of MEKO.
EZ-Blox® is a 2-PO that is proven to deliver the
whole sustainability package. This includes low
toxicity – comfortably meeting the strictest European
standards; easy reformulation and manufacturing
switchover – reducing transition costs; and
performance that meets or exceeds the best known
and available oximes. Tested, proven and available
worldwide, it is becoming known as a safe, simple,
and cost-effective solution for paint manufacturers
looking to comply with REACh requirements.
Acknowledgments
§
Cèline de Lame, NLMK Europe, La Louvière, Belgium.
Note: The authors thank DÖRKEN COATINGS
(CD-Color GmbH & Co. KG) and Osmo Holz
und Color GmbH & Co. KG for providing paint
samples and giving access to their testing facilities
for Müller-BBM GmbH to collect the 2-PO and
MEKO measurements for the OEL studies, and RD
Coatings-Dothee SA for providing alkyd urethane
paint samples.
EZ-Blox® is a registered trademark of AdvanSix Inc.
November 2021
References
1. S. Tanase et al., New J. Chem., 2003, 27, 854-859.
2. J. Flapper and F.L. Duivenvoorde, “Anti-skinning
agents for alkyds: MEKO-free options” – European
Coatings Show Conference, Session 17: Testing &
Measuring I, Nürnberg, April 4, 2017.
3. Traditionally cobalt based salts, like cobalt bis(2-
ethylhexanoate)2, are the most common driers used
with oxime-based anti-skinning agents, but cobalt
driers engendered certain regulatory concern in
the mid-2000s especially in Europe, prompting
the industry to develop cobalt-free driers, primarily
manganese and iron-based complexes, as a
replacement to cobalt driers.
4. Available at: https://echa.europa.eu/brief-profile/-/
briefprofile/100.105.460.
5. Study report is proprietary to AdvanSix Inc.
About AdvanSix
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and applications that touch people’s lives, such
as building and construction, fertilizers, plastics,
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and electronics. Our reliable and sustainable
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to deliver best-in-class customer experiences
and differentiated products in the industries of
nylon solutions, chemical intermediates, and plant
nutrients, guided by our core values of Safety,
Integrity, Accountability and Respect. More
information on AdvanSix can be found at
https://www.advansix.com.
For specific information about 2-PO and EZ-Blox®:
• Call: +1.973.526.1800
• Email: ci@advansix.com
• Visit: AdvanSix.com/chemicalintermediates/
products/ez-blox/