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Raw Materials for Automotive Refinish Systems
Desmodur ®/Desmophen®
Bayhydrol®/Bayhydur ®
Roskydal®
EMEA – Europe, Middle East, Africa
This brochure provides information on
automotive refinishing as
• coating build-up
• development of 2K PUR systems
• VOC legislation
• chemical and physical aspects
• coating raw material data and
application properties
Raw Materials for Automotive Refinish Systems
Desmodur ®/ Desmophen® – Bayhydrol®/ Bayhydur ® – Roskydal®
Bayer MaterialScience AG
markets the product ranges
Desmodur®/Desmophen®,
Bayhydrol®/Bayhydur® and
Roskydal®.
Bayer MaterialScience AG –
one of the world’s leading
producers of coating raw
materials – therefore possesses
a comprehensive portfolio of
high-grade building blocks for
polyurethane coating systems.
2
3
1. Introduction Page 4
- Historical development of car refinish systems
- Reasons for the success of 2K-PUR in car refinish
- Chemistry of 2K polyurethane systems
2. VOC compliant systems Page 6
- VOC-legislation for car refinish in europe
- Bayer MaterialScience VOC compliant raw materials for car refinish
3. Desmodur ® polyisocyanate hardeners Page 7
- Aliphatic polyisocyanate hardeners for 2K-PUR coatings
- HDI-Biuret hardeners
- HDI-Isocyanurate hardeners
- IPDI-based hardeners
- Low viscous HDI-based hardeners
- Reactivity of different aliphatic polyisocyanate hardeners
- Functionality versus viscosity for different HDI based hardeners
4. Desmophen® polyols and reactive diluents Page 12
- Polyols for primers, surfacers, top and clearcoats
- Applications and properties
- Relationship between drying and VOC-value
- Reactive diluents for very high solids
5. Bayhydrol®/Bayhydur® for waterborne systems Page 16
- Waterborne 2K-PUR systems
- Polyols for waterborne 2K-PUR systems
- Hydrophilic polyisocyanates
- Polyisocyanates for waterborne 2K-PUR systems
New technologies for car refinish systems Page 19
6. Roskydal® unsaturated putty-polyesters Page 20
- Unsaturated polyesters for refinish & marble putties
- Unsaturated polyesters for spray & industrial putties
Overview
Historical development of car refinish systems
1. Introduction
NC-Top Coat
NC-Primer
NC-Putties
1920
Medium-Oil-Alkyd- or TPA-Top Coat
NC- or Short-Oil-Alkyd-Primer
NC-Putties
1950
2K-PUR-Top Coat
Wash Primer
Alkyd- or 2K-PUR Surfacer
Wash Primer
2K-PURPrimer/Surfacer
UPE-Putties
1970
2K-PURClear Coat
Base coat
UPE-Putties
since 1980
Driven by Technology: • Film Quality • Optical Properties • Efficiency
Reasons for the success of 2K-PUR in car refinish
few spray-cycles(≤ 2 passes)
broad variety of raw materials
high glosswithout polishing
Quality of OEM • DOI
• Resistance• Durability
Car leaves therefinish shop ≤ 1 d
low bake (≤ 60° C)short drying cycles
(≤ 30 min)
4
Higher Efficiency
➔
➔➔
➔
➔➔
R–N=C=O R–NH 2 CO 2H–OH+ +
Chemistry of 2K polyurethane systems
Main reaction:
Side reactions:
R–N=C=O R’–OH
H
N O
O
R’R+
CO 2+
Isocyanate + Water Amine + Carbondioxide
R–N=C=O R°–NH 2
R’–COOH
+
Isocyanate + Amine Urea/Polyurea
R–N=C=O +
Isocyanate + Carboxylic Acid Amide
Polyisocyanate + Polyol Polyurethane
H
N
O
R°R
H
N
H
N
O
RR’
5
Isocyanate + Alcohol Urethane
High Solids
Waterborne
VOC-legislation for car refinish in europe
Putties
Primer/Surfacer
Base Coat
250 g/l
540 g/l
420 g/l
250 g/l
250 g/l
420 g/l
• Standard UPE
• Styrene free systems
• 2K-PUR HS3)/-VHS2)
• 2K-PUR-waterborne
• 1K-PUR-waterborne
• 1K-Acrylic-
waterborne
Clear Coat 420 g/lDepending on the“state of the art”
• 2K-PUR-HS3) (VHS2))
• (2K-PUR-
waterborne)
Uni Topcoat 420 g/l 420 g/l
• 2K-PUR-HS3)
• (2K-PUR-
waterborne)
Automotive Refinish Current VOC1) VOC1) Value 2010 Technology
1) VOC = Volatile Organic Compounds 2) VHS = Very High Solids: VOC ≤ 250 g/l3) HS = High Solids: VOC ≤ 420 g/l
2K-PURClear Coat
Putty
High Solids Desmophen®/ Desmodur®
Waterborne Bayhydrol®/ Bayhydur®
Desmophen®/ Desmodur®
Bayhydrol®/ Bayhydur®
Roskydal®
6
2. VOC compliant systems
Bayer VOC compliant raw materials for car refinish
Styrene-Free
2K-PUR Primer/Surfacer
Desmodur®
N 100
N 75
N 3200
Type
StandardHDI-Biuret
100 22.0 10,000 F = 3.8 191 Yes
StandardHDI-Biuret
75 MPA/X* 16.5 225 F = 3.8 255 Yes
Low viscousHDI-Biuret
100 23.0 2,500 F = 3.5 183 Yes
Supply form [%]
NCO-Content [%]
Viscosity [mPa·s] at 23° C
NCO-Functionality
Equivalentweight
TSCA
Aliphatic polyisocyanate hardeners for 2K PUR coatings*
NCO
NCO
OCN
*one possible structure (ideal)
NCO
NCOOCN
NH
N RR
HN
O
O
O
R
HDI Biuret
HDI Isocyanurate (Trimer) IPDI Isocyanurate (Trimer)
R=C 6H 12
NCO
NCOOCN
N
N N RR
O
O O
R
R=C 6H 12
N N
N OO
* also in butyl acetate
MPA – methoxy propyl acetate
X – xylene7
3. Desmodur ® polyisocyanate hardeners
HDI-Biuret hardeners
Desmodur®
N 3790
N 3300
N 3390
Type
High viscosity,fast drying
90 BA 18.0 2,000 F = 4.1˜30 20
˜50 236
Standard type,solvent free
100 21.8 3,000 F = 3.5 ˜50 20 30 193
N 3600Low viscosity,for high solids
100 23.0 1,200 F = 3.2˜70 20 15 180
Standard type,solution
90 BA/SN* 19.6 550 F = 3.5 ˜50 20 30 216
Supply form [%]
NCO-Content [%]
Viscosity [mPa·s] at 23° C
NCO-Functionality
Oligomer distri-bution [%]
n=3 5 7
Equivalentweight
* also in BA – butyl acetate, SN – solvent naphta 100
Desmodur® N 3790, N 3300, N 3390 and N 3600 are all TSCA listed
n = number of monomeric units incorporated
3 R–NCO+ 2 R–NCO
[Cat.] [Cat.]
Voltage [V]
elution volume [ml]
R
R R
Monomer (n=1) Trimer (n=3) Pentamer (n=5)
O
O
O
R
R
O
O
O
R
R
O
O
O
R=OCN–(CH 2) 6–
Heptamer
Pentamer
Trimer
(CH 2) 6
8
Oligomer distribution in technical HDI-Isocyanurates
GPC of a technical HDI hardener
3. Desmodur ® polyisocyanate hardeners
HDI-Isocyanurate hardeners^
^^ ^
^
^ ^
^
IPDI-Trimer (one possible structure)
HDI-Trimer IPDI-Trimer
Tg – glass temperature approx. – 60° C approx. +60° C
Viscosity 3,000 mPas solid (2,000 mPas at 70 % in SN*)
IPDI-Trimers have:a significant faster physical drying
also secondary NCO groups
➔ lower reactivity
a significant higher viscosity
➔ higher VOC
compromise:use of IPDI hardeners in combination
with HDI-based hardeners
use of lower viscous IPDI allophanate
Desmodur® XP 2565
➔
●
●
●
➔
●
●
NCO
OCN
NCO
O
N N
N OO
Desmodur ®
Z 4470
XP 2565
NZ 1
Type
Standard IPDI-Trimer
70 MPA/X
70 SN11.9
1,500
2,000F = 3.3 360 Yes
Low viscous IPDI-Allophanate
80 BA 12.0 2.800 F = 2.5 350 Yes
Solventfree IPDI/HDI-combination
100 % 20.0 3,000 F = 2.8 210 Yes
Supply form [%]
NCO-Content [%]
Viscosity [mPa·s] at 23° C
NCO-Functionality
Equivalentweight
TSCA
9
IPDI-based hardeners
SN – solvent naphta 100
MPA – methoxy propyl acetate
X – xylene
SN – solvent naphta 100BA – butyl acetate
N 3400
XP 2410
N 3600
Desmodur ®
R
R–N N–R
R
*Desmodur® N 3600
Asymmetric Trimer: *Desmodur ® XP 2410 HDI-Uretdione: *Desmodur ® N 3400
O
OCN
NCO
NCO
NCO
O
O
O
O
R
R
R
O
OCN
ROCN
NCO
NCO
O
R=C 6H 12
R=C 6H 12
1,200 mPas*
700 mPas* 170 mPas*
R=C 6H 12
TSCAEquivalentweight
NCO-Functionality
Viscosity [mPa·s] at 23° C
NCO-Content [%]
Supply form [%]
Yes193F = 2.517021.8100Very low viscous HDI-Uretdione
Yes175F = 3.170024.0100
Very low viscous asymmetric HDI-Trimer
Yes180F = 3.21,20023.0100Low viscous HDI-Trimer
Type
O
�
10
3. Desmodur ® polyisocyanate hardeners
Low viscous HDI-based hardeners
�
Desmodur® Z 4470
HDI-Trimers:
Desmodur® N 3790
Desmodur® N 3390
Desmodur® N 3600
Desmodur® XP 2410
HDI UretdioneDesmodur® N 3400
90RelativeNCO-Content[%]
NCO Decrease detected by IR Spectroscopy
time at room temperature [h]
80
70
60
50
40
30
20
10
50 100 150 200 250 3000
*High Solids Clear Coat based on Desmophen® A VP LS 2350 – cured at 23° C/50 % humidity; NCO/OH=1:1
*100% version of Desmodur® N 3790, not commercial available
4
3.5
3
2.5
Desmodur®
viscosity [mPas]
functionality
100 300 700 1,200 3,000 15,000
N 3400
XP 2410N 3600
N 3300
N 3700*
11
Reactivity of different aliphatic polyisocyanate hardeners*
Functionality versus viscosity for different HDI-based hardeners
A160
A170Polyacrylate
60 in X
70 in BA
1.6 / 2.6
1.8 / 2.6
1,800
3,500
A 265 Polyacrylate 65 in BA 2.0 / 3.1 2,300
A 365 Polyacrylate 65 in BA/X 3:1 2.9 / 4.5 3,000
A 450 Polyacrylate50 in MPA/X
50 in BA1.0 / 2.0
5,000
4,000
A 665 Polyacrylate 65 in BA/X 3:1 3.0 / 4.6 2,400
A 870 Polyacrylate 70 in BA 3.0 / 4.3 3,500
VP LS 2350 Polyacrylate 70 in BA 2.8 / 4.0 1,200
VP LS 2383 Polyacrylate 60 in BA 2.5 / 4.2 4,500
RD 181 Polyester
75 in BA
75 in MPA
75 in X
3.7 / 4.9
4,500
7,900
7,500
670 Polyester 80 in BA 3.4 / 4.3 2,800
680 Polyester60 in X
70 in BA
1.9 / 3.1
2.1 / 3.1
2,750
3,000
1150 Polyester 100 4.7 3,500
Desmophen® Type Supply Form [%] OH-Content [%]supply form/solid
Viscosity [mPa.s]at 23° C
BA – butyl acetate
X – xylene
MPA – methoxy propyl acetate
SN 100 – solvent naphta 100
4. Desmophen® polyols and reactive diluents
12
Polyols for primers, surfacers, top and clearcoats
A160
A170●
Standard resin for 540 g/l
VOC primer/surfacers
1,060
945
Applications Primer/Surfacer
TopCoats
ClearCoats
HighSolids
A265 ●Fast drying
universal resin850● ● ●
A 365 Universal resin 585●
A 450 ●* Combination resin
for improved drying1,700●* ●* ●
A 665Outstanding QUV
UV-B resistance567● ●
A 870Suitable for 480 g/l
top- and clear coats575● ● ●
VP LS 2350Suitable for 420 g/l
clear- and top coats607● ● ●
VP LS 2383For fastest drying
clear- and top coats680● ● ●
RD 181 ●Grinding resin for
pigment pastes460●
670 ●* Combination resin
for flexibilisation485●* ●*
680 ● Universal resin945
775● ●
1150 ●* VHS in combination
with reactive diluents354●
Special applicationsand properties
Equivalentweight
* = in combination with other resins
Very fastDrying
13
Applications and properties
420
440
460
480
500
520
540
560
580
Drying time [h] till touchability
VOC-value [g/l]
2
A265
4 6 8 10 12
LS 2383
14
Relationship between drying and VOC-value (Hardener: Desmodur ® N 3390)
Hydroxyacrylates for Medium Solid 2K PUR Systems
4. Desmophen® polyols and reactive diluents
LS 2350
A 365
A 665
A 870
OH content [%]on solids
Size of bubbles: durability
Drying (tackfree)slowerfaster
LS 2383A 870
A 665A 365
A 450
A 265
Clear Coats
Primer/Surfacer
1
2
3
4
A 160
3)
2)
1)
4) 290
Yes*
Yes
Yes
TSCAEINECS
Yes*
356
167
139
Equivalentweight
~25
~80
~150
~1200100
90 in BA
100
100
Polyaspartates:
● sterically hindered ● electron deficient● secondary aliphatic amines
no blocking agentvery low odourgood compatibilitylow colour value
Synthesis and Chemical Structure of Polyaspartates
15
Reactive diluents for very high solids
Crosslinking-Reaction of Aldimines and Ketimines via Hydrolysis
Reaction via Imin-Enamin Tautomerie
Very High Solids Systems(< 250 g/l VOC)
Very lowviscouspolyols
Very lowviscous
hardener
Low viscouspolyols
Low viscoushardener
Reactivediluent
+2H2O
Very slowdrying Fast drying
NX
RR
N
R I
-2H2O
H2NX
RNH2R I
R I
O
+2
catalyst
NX
RR
N
R I
R I
NX
RR
N
R I
R I
H
H
crosslinking with
Polyisocyanate
H2N X
O
O
EtO
EtONH2
O
O
OEt
OEt
O
N
OEt
X
H
ON
O
OEt
OEtOEt
H
O
X=H3C
CH2
CH3
CH2
Viscosity at23° C [mPas]
Supply form [%]
+
++ (+)
++
Reactivity
+
clear & top coats in
comb. with 1+5;
top coats in comb.
with polyacrylate
polyols
primers & fillers in
comb. with polyols
clear & top coats in
comb. with 3+5
Applications
NH 1521(VP LS 2973)
VP LS 2965
VP LS 2142
Desmophen®
NH 1520
Polyaspartate
Polyaspartate
Ketimine
Aldimine
Type
5) Yes*279~1500100 ++clear coats & fillers in
comb. with 1+3NH 1420 Polyaspartate
6) Yes*230‹100100 ++++putties & elastomers
in comb. with 5NH 1220 Polyaspartate
*: registered “New Stuff” in Europe
BA – butyl acetate
top coat
clear coat
primer/surfacer
solid colour top
coat primer,
clear coat
solid colour top
coat primer sur-
facer
Applications
top coat
primer/surfacer
top coat
clear coat
VP LS 2290
8.4
16
5. Bayhydrol®/Bayhydur® for waterborne systems
Waterborne 2K-PUR systems
PES: Polyester, PAC: Polyacrylate, *: % on solids, °: % on supply form
DMEA – dimethyl ethanolamin
BG – butylglycol
PnB – propylenglycol butyl ether
SN 100 – solvent naphta 100
Waterborne coatings with highest quality: Waterborne 2K-PUR Coatings
Polyacrylate, Polyester or
Polyurethane Emulsion or Solution
Hydrophilic and/or
Low Viscous Hydrophobic Type
➔
Aqueous Polyol
+
Polyisocyanate
Polyols for waterborne 2K-PUR systems
8 PnB
29
22
27
*acidnumber
18
8 BG
4 BG
4 SN 100
2.5
Butyldiglycol
°Co-Solvents[%]
3.8
3.3
3.8
2.545
45
45
45
*OH-Content[%]
Supply form [%]
~1,500
~800
~2,000
Viscosity[mPa·s] at 23° C
~1,500
7.0
8.0
7.5
pH-value
A 145
VP LS 2139/2
Bayhydrol®
XP 2469
PES/PAC secondary emulsion
Polyacrylatesecondary emulsion
Polyacrylatesecondary emulsion
PES/PAC secondary emulsion
Type
244 PnB
4 SN 1003.945 ~2,000 7.8XP 2470
Polyacrylatesecondary emulsion
DMEA
DMEA
DMEA
neutralizedwith
DMEA
Triethanol-
amin
DMEA
45
28
6
TG[°C]
30
50
New:sulfonic acidmodified trimer
Bayhydur ® XP 2487/1Bayhydur ® XP 2570
OCN
OCN
O
O
N N X SO 3N N
N OO
HydrophilicPolyisocyanates
State of the art:polyether modified trimer
Bayhydur ® 3100
Emulsifier in the PIC Migration of Emulsifier
Internal emulsification(Bayhydur types) chemically linked not possible
External emulsification
Bayer MaterialScience approach
not chemically linked
Blistering,
reduction of water resistance
and gloss possible
Less blistering,
better properties
out of the film is
possible
N
H
OCN
OCN
CH 3
O
O
O OO
OO
OON N
N OO
NH
polyether modified allophanate/trimer
Bayhydur ® VP LS 2319
OCN
OCN
O
N N
N O
O
O
17
Chemical structures of hydrophilic polyisocyanate hardeners
Hydrophilic polyisocyanates
NOCN
OCN
CH 3
O
O
O OO
OO
OON N
N OO
➔ Benefits to polyether modified trimers (state of the art):– higher functionality
– low water sensitivity of the film
➔ Benefits to hydrophobic polyisocyanates:– improved dispersibility
N
H
- +NR 3H
➔ Benefits to polyether modified polyisocyanates:– lower amount of hydrophilic moieties
– higher NCO-content and drying speed
– increased hardness
– improved chemical resistance
ideal structures
Bayhydur ®
XP 2570HDI-Trimer,
ionically modified100 20.5 3,500 F = 3.0 ++ Yes
Bayhydur ®
XP 2487/1HDI-Trimer,
ionically modified100 20.5 6,000 F = 3.4 + Yes
18
Hydrophilic types Bayhydur ®
Hydrophobic, low viscous types Desmodur ®
Desmodur ®
N 3600HDI-Trimer,
low viscious100
Type SupplyForm [%]
23.4
NCO-Content
[%]
1,200
Viscosity[mPa.s]
at 23° C
F = 3.2
NCO-Functionality
- -
Handmixable
Yes
Desmodur ®
XP 2410HDI-Trimer,
very low viscious100 24.0 700 F = 3.1 - Yes
Desmodur ®
N 3400HDI-Uretdione,
very low viscious100 21.8 170 F = 2.5 - Yes
Bayhydur ®
VP LS 2319HDI-Trimer,
slightly hydrophilic100 18.0 4,500 F = 3.8 + Yes
Bayhydur ®
3100HDI-Trimer,
hydrophilic100 17.4 3,300 F = 3.2 + No
Desmodur®
XP 2565IPDI-Allophanate,
low viscious80 BA 12.0 2,800 F = 2.5 - - Yes
Bayhydur ®
VP LS 2150IPDI-Trimer,
hydrophilic70 MPA/X 13.4 600 F = 3.0 + Yes
TSCA
Polyisocyanates for waterborne 2K PUR systems
BA – butyl acetate
MPA – methoxy propyl acetate
X – xylene
19
New technologies for car refinish systems
Main technology trends driven by ecological reasons
2K-PUR Clear Coat
2K-PUR Primer/Surfacer
Wash Primer
CAB-Base Coat
Putty
High Solids1
Waterborne2
Very High Solids3
Waterborne2
1K UV curing 4
Styrene free UPE4
2K PUR putties4
New technology trend driven by economical* reasons
2K-PUR Clear Coat
2K-PUR Primer/Surfacer
Wash Primer
CAB-Base Coat
Putty
Fast Drying 2K PUR1
1K UV or Dual Cure4
Fast Drying 2K PUR1
1K UV curing 4
2K PUR putties4
1K UV curing 4
*economical reasons can be: – faster drying speed to reduce overall process time– 1K instead of 2K system to improve degree of efficiency
1 based on Desmophen® A/Desmodur® N2 based on Bayhydrol®/Bayhydur®/Desmodur®
3 based on Desmophen® NH reactive diluents/Desmodur® N4 Bayer MaterialScience products under development.
For further information please contact our Technical Service.
20
K 14M 64
Roskydal® Supply Form[%]
in styrene
825
Viscosity[mPa.s]at 23° C
Characteristics
Very high reactive,
very hard Knifing fillers/putties
for marble and stone
Very good mechanical
properties, high gloss
after polishing; hard
resins for combination
with other
Roskydal® K-typesK 27/1 70 2,200
High reactive,
very hard
K 30 65 500
High reactive,
medium hard
Highly filledcours and
fine fillers/ putties for
industrial or DIY car bodyrepair, wood and metal
applications
Ideal sole-binder for a
wide range of fillers and
putties.
Formulation in all
standard mixing
equipment
K 36 62 400
K 45 65 575
K 40T 65 Thixotropic
Thixotropic binder.
Production with Dissolver
or Butterfly-mixer up to
55° C possible
XP 2519 66 650Very high reactive,
medium flexible
Sole-binder with good
adhesion properties on all
galvanised car panel
K 65 67 725High reactive,
medium flexible
Sole-binder or in combinati-
on with Roskydal® k14M
for flexible putties with
good adhesion on all
galvanised car panel
K 68 65 750Medium reactive,
highly flexible
Special for overbaking
resistant fillers up to
180° C and plastification of
other Roskydal® K-types
Fields of application
Special Properties
Unsaturated polyesters for refinish and marble putties
6. Roskydal® unsaturated putty-polyesters
21
Roskydal® Supply Form[%]
in styrene
Viscosity[mPa.s]at 23° C
Characteristics
High reactive,
medium hard
All kinds of knifing and spray fillersfor car body
and industrialapplication
(regulation ofpotlife withaddition of
different amountsof inhibitor)
500 A 76 1,800
Very good air drying
properties in combination
withRoskydal® E-types
620 69 850High reactive,
hard
Good storage stability
with Co-salts, especially
in combination with
Roskydal® E-types
E 65 65 600Medium reactive,
elastic
Universal, air drying
combination resin with
good storage stability,
even with Co-salts
E 70 65 950
Low reactive,
very elastic,
soft
Soft resin used for
plastification of all
Roskydal® K-types
XP 2465 68 900High reactive,
medium flexible
Sole binder for UPE
fillers with longer potlife
and spray fillers
Fields of application
Special Properties
Unsaturated polyesters for spray and industrial putties
Technical Service Contacts
Europe, Middle East, Africa:
Car Refinish Systems:Jörg Schmitz
+49-214-30-57054
Holger Mundstock
+49-214-30-55578
Michael Ehlers
+49-214-30-56473
Waterborne Systems:Martin Melchiors
+49-214-30-52435
NAFTA:
Car Refinish Systems:Scott Grace
+1-412-777-7657
Dave Zielinski
+1-412-777-7652
South America:
Car Refinish Systems:Alberto Hassessian
+50-11-5694-5148
Asia:
Car Refinish Systems:Osamu Kirihara
+81-6-6497-2166
22
If you have any questions
regarding the technical details
presented in this brochure,
please contact us at:
Additional information is available on the Internet at:
www.bayercoatings.com
23
This information and our technical advice – whether verbal,
in writing or by way of trials – are given in good faith but
without warranty, and this also applies where proprietary
rights of third parties are involved. Our advice does not
release you from the obligation to verify the information
currently provided – especially that contained in our safety
data and technical information sheets – and to test our
products as to their suitability for the intended processes
and uses. The application, use and processing of our pro-
ducts and the products manufactured by you on the
basis of our technical advice are beyond our control and,
therefore, entirely your own responsibility. Our products are
sold in accordance with the current version of our General
Conditions of Sale and Delivery.
Edition: 2005-02-MH
Printed in Germany · E
Bayer MaterialScience AGCoatings, Adhesives & Sealants51368 LeverkusenGermany
www.bayercoatings.com
