01 - 2K PU SB Auto Refinish & Ind Systems 08-10

Raw Materials for Auto Refinish & Ind Systems
Coatings, Adhesives & Specialities

Bayer – BYK Seminar Jan 2011
Coating Layers of Automotive Refinish Systems
2K-PUR Clear Coat (60µm)

Base Coat (15 µm)
2K-PUR Primer/
Surfacer (60µm)
Polyester Putty
0 - > 5 mm Wash Primer (10 µm)
Metal Body
Total film thickness : approx. 150 µm (without putty)

Historical Development of Car Refinish Systems
Medium-Oil- 2K-PUR
2K-PUR-
NC- Alkyd- or TPA- Clear Coat
Top Coat
Top Coat Top Coat CAB-
Base Coat
Alkyd- or 2K-
NC- NC or Short-Oil- 2K-PUR or EP-
PUR Surfacer
Primer Alkyd-Primer Primer/Surfacer
Wash Primer Wash Primer
NC- NC- UPE- UPE-
Putties Putties Putties Putties
1920 1950 1970 since 1980
Driven by Technology:
• Film Quality
• Optical Properties
• Efficiency

Reasons for the success of 2K PUR in Car Refinish
Robustness
Robustness: :easy
easyapplication Ecological
application Ecologicaldue
dueto
tolow
lowVOC
VOC
••Low
Lowbake
bake(max.
(max.60°C)
C)and
androom ••Lower
60° room Lowersolvent
solventcontent
contentneeded
needed
temperature
temperaturedrying
dryingpossible than
possible thanfor
forNC
NCand
andalkyd
alkyd
••Short cycles (<
Short drying cycles ( 30
drying 30min.) ••High
min.) High Solid versionsexisting
Solid versions existing
=> low dust uptake ••Waterborne
=> low dust uptake Waterborne versionsexisting
versions existing
2K PUR Systems
Quality
Qualitylike
likeOEM
OEMcoatings
coatings Efficiency
Efficiencyinintime
timeand
andmaterial
material
••High
Highgloss
gloss(without
(withoutpolishing)
polishing) ••Fast
Fastdrying
drying&&sandability
sandability=> =>
••Good
Good solvent, chemical&&
solvent, chemical car
car leaves body shop after11day
leaves body shop after day
scratch
scratchresistance
resistance ••No polishing needed
No polishing needed
••Outstanding
Outstandingdurability
durability ••Few
Fewspray-cycles
spray-cycles( (< 22passes)
passes)
••High
Highhardness
hardness&&flexibility
flexibility ••High
Highmaterial
materialefficiency
efficiency
Raw Materials for Automotive Refinish Systems
Raw Materials for 2K PUR

Automotive Refinish
Coatings
1. Historical development and chemical background of hardeners
2. Chemical background of polyols
3. Crosslinking of Oxidatively Curing Resins with IPDI-hardeners
4. 2K PUR clear and top coats
5. 2K PUR primer/surfacer
6. Hardeners
Development of Polyisocyanates for Coatings
OCN NCO
diisocyanate
+
HO OH
diol
O O
O O N N O O
H H
polyurethane
O. Bayer (1937)
In the beginning use of monomeric aromatic

isocyanates for fibres, foams etc:
NCO OCN NCO
OCN NCO
NCO
MDI TDI
-> high vapour pressure and low functionality

=> development of polyisocyanates
Use of aromatic Poly-Isocyanates

as raw materials for coatings since 1943. Basis:
NCO
N
( )n OCN O H O
O
N O H
OCN H O N
NCO NCO
O NCO
MDI-Oligomer TDI-Adduct
Desmodur® L
Advantage: high reactivity, cost effective
Disadvantage: short pot life, poor light stability Laquers
=> Development of aliphatic polyisocyanates

Aliphatic Polyisocyanates for 2K PUR Coatings
Market Introduction of Aliphatic

Types based on HDI Biuret in the early 60´s.
HDI: Hexamethylene NCO

diisocyanate OCN
x 3, + H2O, - CO2
O O
OCN NCO
N N N
H H
HDI-Biuret* NCO
Desmodur® N 100, N 75
*ideal structure
Non Yellowing
Aliphatic Polyisocyanates for 2K PUR Coatings
Market Introduction of based

HDI-Trimers in the early 80´s
O
OCN-(CH2)6 (CH2)6-NCO
N N
HDI-Isocyanurates O N O
(Trimers) (CH2)6-NCO
Desmodur® N 3300
=> lower viscosity N 3390
better monomer stability
vs. technical HDI-Biurets
Aliphatic types for 2K PUR Coatings
R R R
O N O N O O
+ 2 R-NCO O N O
3 R-NCO
[cat.] N N N N N N
R R [cat.]
R (CH2)6 R
R = OCN-(CH2)6- O
O O
Monomer (n=1) Trimer (n=3) Pentamer (n=5)

n = number of monomeric units incorporated

Aliphatic types for 2K PUR Coatings
High Viscous Desmodur N 3790 for Fast Drying
Different oligomer distribution leading to

different viscosities and different drying times
Solid Viscosity NCO- Dry Oligomer Distribution
HDI-Trimer
Content [mPas] 23°C functionality Time n=3 n=5 n>5
high viscous 100%: 15000
N 3790
90
90%: 1500
~4 ++ ~ 30% <20% ~ 50%
Standard
N 3300
100 3000 ~ 3.5 + ~ 50% <20% <30%
low viscous
N 3600
100 1200 ~ 3.1 o ~ 70% <20% <15%
Low Viscous Desmodur N 3600 for High Solids

IPDI-based for 2K-PUR coatings
Beside HDI Trimers also IPDI Trimers
(Isophorondiisocyanate) are used in 2K-PUR systems:
NCO
O
NCO
NCO N N
catalyst O N O
NCO
Desmodur® I
OCN
Desmodur® Z 4470
IPDI-based for 2K-PUR coatings
HDI-Trimer IPDI-Trimer
Tg ~ - 60°C ~ + 60°C
viscosity 3000 mPas solid

(70% in solvent) 2000 mPas
=> IPDI trimers have:

• also secondary NCO groups => lower reactivity
• significant faster physical drying
• much higher viscosity => higher VOC

Reactivity of different aliphatic polyisocyanates
100
NCO decrease in a 2K PUR high solids clear coat
90 detected via IR spectroskopy Desmodur Z 4470
80
HDI trimeres
70
Desmodur N 3790
60
Desmodur N 3390
50 Desmodur N 3600
40
30
20
10
0
0 50 100 150 200 250 300
tim e at room tem perature [h]
High Solids Clear Coat based on High Solids Polyacrylate

cured at 23°C/50% humidity; NCO/OH= 1:1
N & Z: Aliphatic Polyisocyanates
for light and color stable 2K PUR Systems
extremely flexible Z
4470
Viscosity (of 100% solids material)
N XP
3800 2565
rying
d
st er
f a < 80°C drying
N
temperature only in
N 3790° combination
75° with Desmodur N
N N types (max 3:7)
3200 3390°
N
3600
N
3900 u s+ l
sco na
N e r vi nctio
3400 low er fu
low
HDI based IPDI based
°: 100% solids version: N 3300 Drying Speed °: 100% solids version: XP 2675
*: 100% solids version: N 100 *: 100% solids version: XP 2731

Low functionality: 2.0 < F < 2.8
Medium functionality: 2.8 < F < 3.6
Key Product Data of High functionality: F >3.6
Desmodur® Type Solid content NCO

NCO-content Viscosity 23 °C
approx. [%] functionality
approx. [%] approx. [mPas]
(solvent)
N 100 HDI Biuret 100 22.0 10000
N 75 HDI Biuret 75 (MPA/X) 16.5 250
N 3200 HDI Biuret 100 23.0 2500
N 3300 HDI Trimer 100 21.8 3000
N 3390 HDI Trimer 90 (BA / SN) 19.6 550
N 3600 HDI Trimer 100 23.0 1200
N 3900 HDI Trimer 100 23.5 730
N 3790 HDI Trimer 90 (BA) 17.8 1800
N 3400 HDI Dimer 100 21.8 150
N 3800 HDI Trimer 100 11.0 6000
XP 2679 HDI Allophanate 80 (BA) 15.4 500
XP 2580 HDI Allophanate 100 20.0 500
Z 4470 IPDI Trimer 70 (MPA/X) 11.9 1500
XP 2565 IPDI Allophanate 80 (BA) 12.0 2800
HDI / IPDI
NZ 1 Dimer / Trimer 100 20.0 3000


Automotive Refinish
Coatings
6. Hardeners
Suitable Polyols for 2K PUR Coatings
Polyesters • acceptable weather resistance
• variation from hard to very flexible
• high OH - content possible
• very good pigment & wood wetting
Polyacrylates • excellent weather resistance

• high molecular weights possible
• very fast physical drying possible
• limited flexibility at low temperatures
Polyethers • poor weather resistance
• high resistance against alkaline media
• variation from hard to very flexible
• low viscosity
Polycarbonates • excellent weather resistance
• high flexibility

Hydroxyacrylates for 2K PUR Refinish Systems
Synthesis of polyacrylates for 2K-PUR systems:
hydroxy monomer
Non functional monomer
OH OH OH OH OH
R R R R R
peroxide
O O O O O O O O O O
solvent CO2R° CO2R° CO2R° CO2R
CO2R° CO2R°
hydroxy monomer: brings functionality into the acrylate
non functional monomer : adjusts physical polymer properties

hard/flexible, hydrophilic/hydrophobic etc.

Hydroxyacrylates for 2K PUR Refinish Systems
Differences between different polyacrylates:

• the higher the the higher the viscosity (lower solids) and
molecular weight the faster the physical drying
• the higher the hydroxy the higher the hardener demand

content and therefore crosslinking density in the film
better weather- & chemical resistances
• the more “hard” non the harder the film and

functional monomers the faster the physical drying
but the higher the viscosity
• the more styrene as non the faster the physical drying

functional monomer the lower the resin costs
but the poorer the weather resistance

A* Polyacrylate Polyols
for light stable, fast drying 2K PUR Coatings
[%]
5
OH content (on solids)
A 365
A 870 A 1060
4
3 A 265 A 760
A 160
2 A 450
A 960
1
Size of bubbles: durability

Drying Speed (Tack free time)

Desmophen® A* Hydroxyacrylates for 2K PUR Coatings
Desmophen® Supply Form OH-content [%] Viscosity 23 °C Properties and Applications

Supplyform / 100% Solids [mPas]
A 960 60% in SN 0.75 / 1.3 4500 Fast drying & cheap 2K PUR coatings
50% in MPA/X 5000

A 450 50% in BA
1.0 / 2.0
4000
Combination resin for improved drying
OH-content
A 160 60% in X 1.6 / 2.7 1800 Primer surfacer
Fast drying, cost effective topcoats with

A 760 60% in BA/X 1.8 / 3.0 2000
good weather stability
A 265 65% in BA 2.0 / 3.1 2300 Fast drying, cost effective topcoats
Very flexible, for weatherstable plastic

A 575 75% in X 2.8 / 3.7 3500
coatings
A 1060 60% in BA 2.4 / 4.0 4500 Fast drying claer & topcoats
A 365 65% in BA/X 2.9 / 4.5 3000 Universal resin, cost effective
Medium solid topcoats, good weather

A 870 70% in BA 3.0 / 4.3 3500
stability
A 665 65% in BA/X 3.0 / 4.6 2400 Topcoats, outstanding weather stability
BA = butylacetate ; X = xylene ; MPA = methoxy propyl acetate ; SN = solvent naphtha 100

*:Desmophen A:
Desmophen Polyesters for Coating Systems
Synthesis of polyesters for 2K-PUR systems:

Polycondensation
R-OH + HO-C-R` → R-O-C-R` + H2O↑

↑
O O
Alcohol Carboxylic Ester Water
acid
• Diols and Dicarboxylic acids result in polyesters.

• Excess of alcohol results in OH-functional polyesters.
• Triols introduce branching.

Solventborne Polyester Polyols
for various 2K PUR Coatings
651 800
*: fatty acid modified
8
OH content (on solids) [%]
°: slightly branched 650
RD 181
670°
4 1300 VP LS
2388°
680
PL 300
2
50 60 70 80
Solid Content [%]
Desmophen OH-Polyesters for 2K PUR Coatings
Desmophen® Supply Form OH-content [%] Viscosity 23 °C Properties and Applications

Supplyform / 100% Solids [mPas]
75% in BA 4500 Good wetting, high gloss, elastic, good

RD 181 75% in MPA 3.7 / 4.9 7900 chemical resistance,
75% in X 7500 also suitable for pigment pastes
100% 4.3 -
For high solid primers and topcoats (clear
1300 75% in X 3.2 / 4.3 3500
& pigmented)
75% in BA 3.2 / 4.3 1000
100% 8.6 850 (70% in MPA) For hard and chemical resistant air-drying
800 85% in BA 7.3 / 8.6 11000 2K systems with high impact and abrasion
85% in MPA 7.3 / 8.6 11000 resistance
PL 300 60% in X 2.7 / 4.5 5350 Hard, highly reactive and long potlife
60% in X 1.8 / 3.0 2750

680 70% in BA 2..2 / 3.0 3000
Industrial and large vehicle coatings
1652 100% 1.6 11000 Highest flexibility for soft feel coatings
100% 4.3 -
670 80% in BA 3.5 / 4.3 3000
High flexibility for plastic coatings
650 65% in MPA 5.3 / 8.2 20000 Commercial vehicle & aircraft coatings
with outstanding chemical resistance and
65% in MPA 14500 low temperature flexibility
651 65% in MPA/X
5.5 / 8.4
25000
BA = butylacetate ; EA = ethylacetate ; X = xylene ; MPA = methoxy propyl acetate


Automotive Refinish
Coatings
6. Hardeners
Crosslinking of Oxidatively Curing Resins
Alkyd-Top -Coat + IPDI hardener

Areas of improvement:
film hardness
chemical / solvent resistance
physical drying speed
gloss / DOI
weatherability

High Quality 2K PUR Top- & Clear Coats
1. Step: Alkyd-Top-Coat + IPDI hardener
Topcoat white based on Alkydal F 48 Alkydal F 48 Alkydal F 48 D´phen A 265
- + 10% Z 4470 + 15% Z 4470 + N 75
Potlife [h] infinite ~6 ~6 ~6
Gloss (20°) 81 81 83 94
Dust free /tack free time [h] 2 / >7 2 / >7 2/7 0,5 / 6
Pendulum hardness 30‘ 60°C 21 26 28 36

+ 7d RT 57 117 142 137
Water resistance (60‘) after 7d RT 3 1 0-1 0
Gasoline resistance (5‘) 4 4 4 0

Weather resistance
Gloss (20°) after 2 years Florida 29 62 73 90
2. Step: Real 2K PUR system

Comparison of Automotive Refinish Technologies
System NC Alkyd Alkyd + IPDI 2K-PUR
Handling 1K 1K 2K (potlife) 2K (potlife)

Drying
Sandability (Primer) -
Process time > 70 min* ca. 75 min ca. 75 min ca. 55min
Material consumption 2-3 1,2 1,2 1
Pendulum Hardness
Gloss 20° 78 79 85 90
Solvent resistance
Corrosion Resistance
W eather resistance
= perfect = good =less good = poor

Application time
time [h]
16 Top Coat curing

till polishable
14
Top Coat set to
12 touch (RT)
10 Top Coat
Application
8
Primer Surfacer
6 drying (RT)
4 Primer Surfacer
application
2
0
NC Alkyd Alkyd + IPDI 2K PUR

Accelerated weathering QUV UVA 340

100
90
80
70
Glanz (60°)
60
50
40
30
20
10
0
0 250 500 750 1000
NC Alkyd Alkyd + IPDI 2K PUR

7 days humidity test

20 days salt spray test

Reasons for the success of 2K PUR in Car Refinish
Robustness
Robustness: :easy
easyapplication Ecological
application Ecologicaldue
dueto
tolow
lowVOC
VOC
••Low
Lowbake
bake(max.
(max.60°C)
C)and
androom ••Lower
60° room Lowersolvent
solventcontent
contentneeded
needed
temperature
temperaturedrying
dryingpossible than
possible thanfor
forNC
NCand
andalkyd
alkyd
••Short cycles (<
Short drying cycles ( 30
drying 30min.) ••High
min.) High Solid versionsexisting
Solid versions existing
=> low dust uptake ••Waterborne
=> low dust uptake Waterborne versionsexisting
versions existing
2K PUR Systems
Quality
Qualitylike
likeOEM
OEMcoatings
coatings Efficiency
Efficiencyinintime
timeand
andmaterial
material
••High
Highgloss
gloss(without
(withoutpolishing)
polishing) ••Fast
Fastdrying
drying&&sandability
sandability=> =>
••Good
Good solvent, chemical&&
solvent, chemical car
car leaves body shop after11day
leaves body shop after day
scratch
scratchresistance
resistance ••No polishing needed
No polishing needed
••Outstanding
Outstandingdurability
durability ••Few
Fewspray-cycles
spray-cycles( (< 22passes)
passes)
••High
Highhardness
hardness&&flexibility
flexibility ••High
Highmaterial
materialefficiency
efficiency

Automotive Refinish
Coatings
6. Hardeners
Properties of a white Refinish Topcoat based on different Polyols
Polyol, Desmophen Alkydal F 48* A 960* A 160* A 265* 680 A 760* A 870*
OH content on solids -- 1,3 % 2,6 % 3,1 % 3,1 3,0 % 4,3 %
Polyisocyanate Desmodur - N 75 N 75 N 75 N 75 N 75 N 3390

Solid cont. at spray visc. [%] 50,8 43,6 47,2 53,6 57,2 52,8 57,8
VOC [g/l] 590 670 630 560 510 570 500
Potlife [h] >6 >6 >6 >6 >6 >6 >6
Gloss (20°) 81 89 91 94 94 91 92
Haze <10 11 <10 11 <10 <10 13
Drying time T1/T2/T3 2 / 5,5 / >7 1 / 1,5 / 5 0,5 / 5 / 6 0,5 / 5 / 6 1,5 / 5 / 6,5 0,5 / 2,5 / 4,5 1,5 / 5 / 6,5
Tackiness (30‘ 60°C) 2 0 0 0 0 0 0
Levelling (visually) 1-2 1 2 2 2 2 1
Pendulum hardness 30‘ 60°C 21 67 30 36 34 32 52
+ 1d RT 44 102 80 84 84 92 127
+ 7d RT 57 128 138 137 125 130 159
Chemical resistance
Water (60‘) 30‘60°C/1d/7d RT 4 / 4 / 3-4 4/1/0 4 / 1 / 0-1 4/1/0 4 / 1 / 0-1 4/1/0 1/1/0
Gasoline (5‘) 30‘60°C/1d/7d RT 5/4/4 5/4/4 4 / 4 / 2-3 4/4/0 4/4/1 4/1/0 4/1/0
MPA (5‘) 30‘60°C/1d/7d RT 5/5/5 5/4/4 5 / 4 / 2-3 5 /4/2 5 / 4-5 / 2 4 / 1 / 0-1 4 / 3 / 0-1
2% H2SO4 / 2% NaOH 7d RT 1/1 0-1 / 0-1 0-1 /0-1 0/0 0-1 / 0-1 0/0 0/0
Weathering Xeno 1200
Gloss (20°) 0h 80 89 90 95 94 90 91
250 h 71 85 88 93 91 89 89

Properties of a Refinish Clearcoat based on different Polyols
Polyol Alkydal F 48* A 265* A 760* A 365* A 870*
OH content on solids -- 3,1 % 3,0 % 4,5 % 4,3 %

Polyisocyanate - N 75 N 75 N 75 N 3390
Solid cont. at spray visc. 37,9 % 46,6 % 43,8 % 46,2 % 51,9 %
VOC [g/l] 620 530 560 540 480
Potlife [h] infinite ~6 ~6 ~4 ~6
Gloss (20°) 88 95 93 92 93
Haze 11 <10 <10 <10 <10
Drying time T1/T2/T3 1,5 / 4 / 5 0,5 / 3 / 6,5 0,5 / 1 / 3 1/4/8 1/5/7
Tackiness (30‘ 60°C) 1 1 0 2 0
Levelling 2 1 0 1 0
Pend. Hardness 30‘ 60°C 26 53 32 28 37
+ 1d RT 38 123 106 127 146
+ 7d RT 44 189 159 182 191
Chemical resistance
Water (60‘) 30‘60°C/1d/7d RT 4/4/1 2/1/0 4/1/0 2/1/0 3/1/0
Gasoline(5‘) 30‘60°C/1d/7d RT 5 /5/4 4/4/2 4/4/1 4/2/1 4/3/0
MPA (5‘) 30‘60°C/1d/7d RT 5/5/5 5/4/1 5/4/1 5/4/1 4/3/1
2% H2SO4 / 2% NaOH 7d RT 1/1 0-1 / 0 0/0 0/0 0/0
Immersion in water (7 d)
swelling 5 1 2 1 0
blistering 5/1 - - - -
Weathering Xeno 1200
∆E (250 h) 2,5 1,4 0,1 0,9 0,3

for light stable 2K PUR Car Refinish Top Coats
higher solids, better
[%] levelling & weather resistance
5
A 365
A 870 A 1060
4
faste
r dry
i ng s
peed
3 680 A 265 A 760
A 160
2 A 450
A 960
1
Polyacrylate Polyester Size of bubbles: durability


A* Polyacrylates for Refinish Top Coats
• Desmophen A 365, 65% in BA / X
•• OH-content:
OH-content:4,5%
4,5%on
onsolid
solid
•• Good
Goodweather
weatherstability
stability
•• Good
Goodchemical,
chemical,solvent
solventand
andfuel
fuelresistance
resistance
•• Mainly
Mainlyused
usedininair-
air-and
andforced
forceddrying
dryingapplications
applications
•• Universal
Universalresin,
resin,standard
standardgrade
grade
•• For
Forfaster
fasterdrying
dryinginincombination
combinationwith
withDesmophen
DesmophenAA450
450
•• For
Formore
moreflexibility
flexibilityinincombination
combinationwith
withDesmophen
Desmophen670
670
•• For
Forindustrial-,
industrial-,transportation
transportationand
andanti-corrosion
anti-corrosionapplications
applications

Medium solid polyol

• Desmophen A 870, 70% in BA
•• OH-content:
OH-content:4,3%
4,3%on
onsolid
solid
•• Very
Verygood
goodweathering
weatheringstability
stabilityand
andchemical
chemicalresistance
resistance
•• For
Forhigh-/
high-/medium
mediumsolid
solidcoatings
coatings( (VOC
VOC <<460
460g/l
g/l) )
•• Outstanding
Outstandingoptical
opticalproperties
properties(gloss
(gloss&&levelling)
levelling)
•• Mainly
Mainlyused
usedininair-
air-and
andforced
forceddrying
dryingapplications
applications
•• For
Forindustrial-,
industrial-,transportation-coatings
transportation-coatingsand
andautomotive
automotiverefinishing
refinishing

• Desmophen A 760, 60% in X/BA
•• OH-content
OH-contentAA760:
760:3,0%
3,0%on
onsolid
solid
•• Very
Verygood
goodweather
weatherstability
stability
•• Good
Goodsolvent
solventand
andchemical
chemicalresistance
resistance
•• Very
Veryfast
fastdrying
drying
•• Cost
Costeffective
effectivetop
topand
andclear
clearcoats
coatswith
withlow
lowhardener
hardenerdemand
demand
•• Mainly
Mainlyused
usedininair-
air-and
andforced
forceddrying
dryingapplications
applications
•• For
Forindustrial-coatings,
industrial-coatings,primarily
primarilyfor
forautomotive
automotivetopcoats
topcoats

Fast Drying 2K PUR Car Refinish Clear Coats
Desmophen A 870:
- high solid content (500 g/l)
- excellent solvent resistance
- medium drying
Desmophen A 265:
- quick drying
- high gloss, good pigment wetting
- medium durability
Desmophen A 760:
-very fast drying
- excellent solvent resistance
- lower hardener demand vs. A 870
All cured with Desmodur N 3390

10 Drying Time
9 T3: Tack free time
8 500g weight
Drying Time [h]
7 T4: 2 kg weight
6
5
4
3
2
1
0
Dust free time T3 (23°C) T4 (20 min 60°C)
(23°C)
A 870 A 265 A 760
Hardness & Gloss

200
100
180
Pendulum Hardness
160
90
140
Gloss (20°)
120 80
100
80 70
60
40 60
20
0 50
30 min 60°C + 1d 23°C +7d 23°C
A 870 A 265 A 760

Weathering
MEMA 3-71results
Ci 65 - CAM(CAM
180 (20°) 180)
100
90
80
70
Gloss (20°)
60
50
40
30
20
10
0
start 250h 500h 750h 1000h 1250h 1500h 1750h 2000h
Alkydal F 48 A 365 // N 75 LS 2383 // N 75 A 265 // N 75 A 760 // N 75

Resistance & Durability

6 6
5 5 min Gasoline 5 5 min MEK

5=very good 0=poor
4
4
3
3
2
2
1
1
0
0 -1
+ 1 d 23°C + 7d 23°C 30 min 60°C + 7d 23°C
A 870 A 265 LS 2383 A 760

P o ly o l A 870 A 265 % LS 2383 A 760
W a t e r R e s is t a n c e ( 6 0 ‘) 3 0 ‘6 0 °C /1 d R T 2 / 0 -1 2 / 0 2 -3 / 0 2 / 0
2 % H 2S O 4 / 2 % N a O H 1 d /7 d R T 0 / 0 0 / 0 0 / 0 0 / 0
W e a t h e rin g ( g lo s s re t e n t io n )
X e no 1 2 00 ++ o ++ ++
QUV B + o ++ +
F lo rid a e x p o s u re ++ + ++ ++

Car Refinish Clear Coats with low Hardener Demand
Component 1 A 265 A 760
Desmophen A 265 65% in Butylacetate BMS, D-Leverkusen 50.98 55,23

Desmophen A 760 60% in Xylol/BA (5:3) BMS, D-Leverkusen
Byk 331 50% in Butylacetate Byk Chemie, D-Wesel 0,27 0,27
Tinuvin 1130 50% in Butylacetate Ciba, CH-Basel 1,35 1,35
Tinuvin 292 50% in Butylacetate Ciba, CH-Basel 0,90 0,90
DBTL 1% in Xylene 1,35 1,35
Solvent mixture* 5,10 0,85
Coponent 2
Desmodur N 3390 90 % BMS, D-Leverkusen 12,85 12,85

Solvent mixture* 27,22 27,22
100,00 100,00
*: Xylol/Butylacetate/ Methoxypropyleacetate (1:1:1)
Formulation (component 1 +2) Ready to spray viscosity [s] (DIN 4) 20 20
NCO:OH-ratio 1,0 1,0

Clear Coats based on different Hardeners
Desmodur® N 3390 - standard HDI hardeners

Desmodur® N 75 - good reactivity
- low Tg => no physical drying
Desmodur® Z 4470 - standard IPDI hardener
- lower chemical reactivity
- high Tg => good physical drying
Desmodur N® 3390/ - standard combination
Desmodur Z® 4470 (7:3): for quick drying and good reactivity
Desmodur N® 3790 - high oligomeric HDI isocyanurate
- very good reactivity
- quick physical drying
Haze, gloss and clear coat solid contant are comparable

Films with Desmodur Z 4470 are more brittle (less good impact resistance)
6 Drying Time
5 6
Drying Time [h]
4 5
3 4
2 3
1 2
0 1
Dust Free Time Tack Free Time 0
Dus t Fre e Tim e Tack Fre e Tim e
Clear Coat based on Desmophen A 265° based on Desmop hen A 870°

Desmodur N 75 N 3390 N/Z-mixture* N 3790
*: Desmodur N 3390/Z 4470 (7:3)

5
Gasoline Resistance
5
4 4
1=poor 5=very good
3 3
2 2
1 1
0 0
+ 1d RT + 4d RT + 7d RT 1d RT 7d RT 20 min 60 °
Clear Coat based on Desmophen A 265° based on Desmop hen A 870°
A 265 + N 75 A 265 + N 3390 A 265 + N/Z-mixture A 265 + N 3790

Quickest drying:
Desmodur N 3390/Z 4470 (e.g. 7:3)
Desmodur N 3790
Best solvent resistance:

Desmodur N 75
Desmodur N 3390
Desmodur N 3790


Automotive Refinish
Coatings
6. Hardeners

for fast drying Car Refinish primers and fillers
[%]
5
A 365
A 870 A 1060
4
3 680 A 265 A 760
better sandability
A 160
2 A 450
A 960
1
faster drying
Size of bubbles: durability

Comparison of different primer/surfacers
D ryin g tim e S andable after
T1 T3 W et 800 dry 320 30 m in/60°C
2K P U R (A 160/450) 20 m in 75 m in 6 h >1d +
2K P U R (A 265) 15 m in 30 m in 2 h 2 h ++
1K P rim er Su rfacer 20 m in 45 m in 6 h >1d +
Ad h esio n 4 80 ho u rs S alt Sp ra yin g T est

on steel alu zinc on S teel on A lu (with acetic acid)
V isual A dhesion V isual A dhesion
2K P U R (A 160/450) ++ ++ ++ ++ + ++ ++
2K P U R (A 265) ++ - + -- - -- --
1K P rim er Su rfacer ++ ++ + -- - - -

A * Polyacrylates for Refinish Primers
• Desmophen A 160, 60% in X or SN
•• OH-content:
OH-content:2,6%
2,6%on
onsold
sold
•• Fast
FastDrying
Drying
•• Good
Goodrestistance
restistancetotowater
waterand
andchemicals
chemicals
•• Mainly
Mainlyused
usedininair-
air-and
andforced
forceddrying
dryingapplications
applications
•• For
Forprimers,
primers,anti-corrosion
anti-corrosionsystems
systemsand
andtop
topcoats
coats

Primer surfacer based on Desmophen A 160 : A 450
Component 1 % by wt
.
Desmophen A 160 60 % (1) 26.00 NCO/OH ratio: 1.2
Desmophen A 450 50 % (2) 7.80 Mixing ratio of components 1:2 100:10
Modaflow 1% (3) 1.31
Byl 141 4% (4) 0.26 Composition: binder 26.09
DBTL 10 % (5) 0.78 additives 1.13
Bentone 38 10 % (6) 5.22 pigments/extenders 41.59
Aerosil R 972 (7) 0.26 solvents 31.19
Solvent mixture (8) 8.00 100.00
Tronox  R-KB-2 (9) 10.10
Bayferrox  303 T (9) 0.29
Heucophos ZPA (10) 5.79
Talc AT 1 (11) 3.15
Blanc fixe M (12) 22.26
Component 2
Desmodur N 75 75 % (13) 8.78
100.00 RR 4466

A * Polyacrylates for Refinish Primers
•• OH-content:
OH-content:3,1%
3,1%on
onsolid
solid
•• Fast
Fastdrying
drying
•• Excellent
Excellentsandable
sandableprimer
primerformulation
formulationavailabele
availabele(RR4469)
(RR4469)
•• Good
Goodpigment
pigmentwetting
wetting
•• Very
Veryhigh
highgloss
glossinintop
topand
andclear
clearcoats
coats
•• Mainly
Mainlyused
usedininair-
air-and
andforced
forceddrying
dryingapplications
applications
•• For
Forindustrial-;
industrial-;car
carrefinish
refinishand
andtransportation
transportationapplications
applications

Fast Drying Filler based on Desmophen A 265
Component 1 A
Gew.-%
Desmophen A 265 65 % (1) 23,70 NCO/OH 1,0
Modaflow 1% (3) 1,06 Mixing Ratio comp. 1/comp. 2 = 1:2 100:7,5
Byk 141 4% (4) 0,20
Bentone 38 10 % (5) 3,17 Composition: bindem 20,63
Aerosil R 972 (6) 0,11 additives 0,51
Xylene 4,60 pigments / extenders 48,48
Butylacetate 4,60 solvents 30,38
Butoxyl 3,08 100,00

Tronox R-KB-2 (7) 9,03
Bayferrox  415 (7) 1,35
Füllstoff ASP 600 (8) 22,87
Micro Talc AT 1 (9) 9,44
Heucophos ZPA (10) 5,79
Zinckoxide NT (11) 0,06
Component 2
Desmodur N 75 75 % (12) 6,94

RR 4469
100,00


Automotive Refinish
Coatings
6. Hardeners

Hardeners for Solventborne 2K PUR Coatings
H
N O
R – N=C=O + R1 – OH R R1
O
Urethane
H H
R – N=C=O + H2O N N
R R + CO 2
O
Urea
Reaction of polyisocyanates with water:
• during application and drying with atmospheric humidity
= side reaction leading to additional crosslinking (moisture curing)
only problematic for very thick films or drastic climatic conditions
• during storage with moisture from solvents or atmosphere
=> sets free CO2 gas => blow up of the can/drum (bursting)
=> building of urea particles => turbidity up to gellation
Any moisture has to be excluded
Hardeners for Solventborne 2K PUR Coatings
Hardener Formulation:
Desmodur® (aliphatic or aromatic type) 40-95 parts
Solvent mixture 5-60 parts
Moisture scavenger x parts
Catalyst (only in very special cases) 0,02 parts
All equipment (vessel, container, tubes) has to be totally water free.

All raw materials have to be as low as possible in moisture content,
special “polyurethane grade” solvents (<0,05% water) should be used.
All raw materials are punped out of the delivery drum, mixed and have to be filled up
into perfectly sealed cans, drums or containers preferably under protective gas
atmosphere (or vacuum), if possible in a closed system with dehydration cartridges*
Moisture scavengers like Additive TI might be used to “be on the safe side”
Catalysts like DBTL (Addocat 201/Rheinchemie or Togokat 218/Goldschmidt TIB) might be

used to speed up reactivity; but increased water-sensitivity is the consequence
*:e.g. ADSORMAT® desciccant cartridges from Südchemie (http://www.trockenmittel.de/produkte/09_adsormat.php)

Solvents for Solventborne 2K PUR Hardeners
• Hydrocarbons
• aromatic, e.g. xylene, solvent naphtha ++
• aliphatic, e.g. white spirit -
• hydrated cycloaliphatics e.g. Dekalin, Tetralin -
• Chlorinated solvents, e.g. methylen chloride --
• Alkohols, z.B. Butanol --
• Esters, e.g. butyl acetate ++
• Glycol ether esters, e.g. methoxy propyl acetate ++
• Ketones, e.g. methyl ethyl keton +
• Glykolethers, butyl gycole --
Usually mixtures of different solvents (polaric/hydrophobic)are used

with different evaporation rate depending on requested drying time
Hardener-Solutions should not be diluted to less then 35% solids

Solvents for Solventborne 2K PUR Hardeners
Turbidity & gelling due to water/moisture in solvent during storage:
Solubility of water water content of
different solvents laboratory solvents
• butyl glycol acetate unlimited 0.2 %
• methoxy propyl acetate 22 % 0.04 %
• butylacetate 0.7 % 0.1 %
• xylene “0 %“ 0.01 %
• solvent naphtha types “0 %“
Storage stability of Desmodur N 3300 (25% solids) in different solvents

+ 0.05% water at - 3°C (21 - 35 days):
worst: solvent mixtures containing glycol esters without Additive TI
better: solvent mixtures without glycol esters and/or with Additive TI
best: mixtures with much more aromatic solvent than esters (2:1) with Additive TI
less good: mixtures with too high amount of aromatic solvents (10:1) even with Add. TI
at + 30°C (21 - 35 days):

quite similar but always better with higher MPA amounts
Catalysts for 2K-PUR Systems
Aliphatic 2K PUR-Systems
System Catalyst Advantages Disadvantages Dosage
(on solid binder)
Acrylics DBTL faster curing reduced potlife 0,02 - 0,03 %
(Dibutyltindilaurate) improved hardness
Dabco LV 33 faster through curing yellowing 0,3 - 0,5 %
(combi partner for DBTL) increased H2O reaction
K-Kat 5218 synergism with
(King Industries) pentandione (potlife)
Polyesters DBTL faster curing reduced potlife 0,02 - 0,03 %
(Dibutyltindilaurate) improved hardness
Zinc octoate faster curing high dosage 0,5 %
(Zinc oxide)
Desmorapid PP* slightly increased H2O 0,3 - 0,7 %
(Borchers) reaction
Hardener DBTL fast hardener for reduced potlife 0,02 %
(Dibutyltindilaurate) winter time increased H2O reaction

Catalysts for 2K-PUR Systems
General Remarks
• Every change in polyol or polyisocyanate

requires new adjustment of catalyst dosage
• DBTL is quite universal. It can be replaced in most
systems with tin-free catalysts (bismuth etc. but
adjustment of catalyst type and dosage is required

Thank you for your attention


01 - 2K PU SB Auto Refinish & Ind Systems 08-10

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Raw Materials for Auto Refinish & Ind Systems

Coatings, Adhesives & Specialities

2K-PUR Clear Coat (60µm)

Total film thickness : approx. 150 µm (without putty)

Coatings, Adhesives & Specialities

1920 1950 1970 since 1980

Coatings, Adhesives & Specialities

Raw Materials for 2K PUR

In the beginning use of monomeric aromatic

NCO OCN NCO

-> high vapour pressure and low functionality

Use of aromatic Poly-Isocyanates

=> Development of aliphatic polyisocyanates

Market Introduction of Aliphatic

HDI: Hexamethylene NCO

Market Introduction of based

Monomer (n=1) Trimer (n=3) Pentamer (n=5)

Coatings, Adhesives & Specialities

High Viscous Desmodur N 3790 for Fast Drying

Different oligomer distribution leading to

Low Viscous Desmodur N 3600 for High Solids

Coatings, Adhesives & Specialities

viscosity 3000 mPas solid

=> IPDI trimers have:

Coatings, Adhesives & Specialities

tim e at room tem perature [h]

High Solids Clear Coat based on High Solids Polyacrylate

Coatings, Adhesives & Specialities

Desmodur® Type Solid content NCO

N 75 HDI Biuret 75 (MPA/X) 16.5 250

N 3200 HDI Biuret 100 23.0 2500

N 3300 HDI Trimer 100 21.8 3000

N 3390 HDI Trimer 90 (BA / SN) 19.6 550

N 3600 HDI Trimer 100 23.0 1200

N 3900 HDI Trimer 100 23.5 730

N 3790 HDI Trimer 90 (BA) 17.8 1800

N 3400 HDI Dimer 100 21.8 150

N 3800 HDI Trimer 100 11.0 6000

XP 2679 HDI Allophanate 80 (BA) 15.4 500

XP 2580 HDI Allophanate 100 20.0 500

Z 4470 IPDI Trimer 70 (MPA/X) 11.9 1500

XP 2565 IPDI Allophanate 80 (BA) 12.0 2800

Coatings, Adhesives & Specialities

Raw Materials for 2K PUR

Polyacrylates • excellent weather resistance

Coatings, Adhesives & Specialities

Synthesis of polyacrylates for 2K-PUR systems:

hydroxy monomer: brings functionality into the acrylate

non functional monomer : adjusts physical polymer properties

Coatings, Adhesives & Specialities

Differences between different polyacrylates:

• the higher the hydroxy the higher the hardener demand

• the more “hard” non the harder the film and

• the more styrene as non the faster the physical drying

Coatings, Adhesives & Specialities

Size of bubbles: durability

Coatings, Adhesives & Specialities

Desmophen® Supply Form OH-content [%] Viscosity 23 °C Properties and Applications