The advantages of ultra-low viscosity HDI trimer and high flexure HDI prepolymer for polyaspartic coatings
ASAHI KASEI Europe GmbH
Research & Development Center
(Performance Coating Materials Division)
Satoshi Takeno
11th September 2019
@ Chicago, USA
2
Corporate profile
Trade name
Employees*
Head office Paid-in capital*
President
Founding
Asahi Kasei Corp.
1922 39,283
Tokyo, Japan ¥103.3 billion
Hideki Kobori
Fiscal 2018 results
Net sales ¥2,170.4 billionOperating income ¥209.6 billion
旭化成 [持株機能] 旭化成 [持株機能]旭化成 [持株機能]
Asahi Kasei Corp. [holding company function]
Head Office
* As of March 31, 2019
Diversified chemical company with three business sectors
Material Health CareHomes
• Asahi Kasei Corp. [operating function]
• Asahi Kasei Microdevices Corp.
• Asahi Kasei Homes Corp.• Asahi Kasei Construction
Materials Corp.
• Asahi Kasei Pharma Corp.
• Asahi Kasei Medical Co., Ltd.
• ZOLL Medical Corporation
3
Global network
Material Homes Health Care Administrative & Other
Europe
NorthAmerica
Central andSouth America
Oceania
Asia
Japan
Manufacturing, sales, and R&D sites of the Asahi Kasei Group are located in more than 20 countries around the world to meet a wide range of needs in the global market
4
Agenda
1) Introduction
2) Polyaspartic coatings
3) Application:
Ultra-low viscosity HDI trimer
High flexure HDI prepolymer
4) Summary
1) Introduction
6
VOC regulation in USA
VOC(Volatile Organic Compounds) Reduction
High-solidcoating
Water-bornecoating
Non-solventcoating
Ultra-low viscosity HDI trimer is suitable for high-solid & non-solvent coatings(such as polyaspartic, airless spray etc.)
Originally, “Clean Air Act” is a United States federal law designed to control air pollution,OTC(Ozone Transport Commission), CARB(California Air Resources Board), SCAQMD(South Coast Air Quality Management District)
2) Polyaspartic coatings
8
Polyaspartic coatings…
Polyaspartic is one of aliphatic polyurea: Faster drying & Low VOCReaction of an amino group with an isocyanate group
Polyurea Aromatic polyurea
Aliphatic polyurea
Waterproof material, Inside pipeline etc.
Coatings(Floor, Bed liner, Heavy corrosion protection etc.)
PolyasparticN
R,,
Polyurethane Aromatic polyurethane
Aliphatic polyurethane
Flexible/Rigid forms, Waterproof material, Adhesive, Sealant
Coatings, Gravure ink, Adhesive, TPU(Automotive, Architecture, Heavy corrosion protection etc.)
<=> Reaction of a hydroxyl group with an isocyanate group
3) Application: Ultra-low viscosity HDI trimer
10
Type GradeSolids
[wt%]
NCO
[wt%]
Viscosity[mPa.s/25℃]
Trimer
Ultra-low vis
100
23.0 300
Low vis 23.3 500
Standard vis 21.7 2,600
Ultra-low visCoating NV
57wt%
Standard visCoating NV
50wt%
(Three dimensions surface smoothness instrument)
Ultra-low viscosity HDI trimer=> Not only reduction of solvent usage but also excellent appearance surface
Ultra-low viscosity HDI trimer
OCN (CH2)6 NC
N
CN
C
(CH2)6
(CH2)6
O
OO
NCO
NCORaw material; HDI monomer
NCO
CH2
CH2
CH2
CH2
CH2
CH2
NCO
Prepolymerization
Advantages of ultra-low viscosity HDI trimer
11
Ultra-low viscosity HDI trimer: test condition
Aspartic esterSolids[wt%]
Amine Value[mgKOH/g]
Viscosity[mPa.s/25℃]
Feature
Aspartic acid,N,N-(methylenedi-4,1-cyclohexanediyl)bis-, tetraethyl ester
100201 1,190 Standard
Aspartic acid,N,N-methylenebis(2-methyl-4,1-cyclohexanediyl)bis-, tetraethyl ester
191 1,490 Low reactivity
a.
b.
HDI polyisocyanateSolids[wt%]
NCO content[wt%]
Viscosity[mPa.s/25℃]
Ultra-low vis100
23.0 300Low vis 23.3 500
Standard vis 21.7 2,600
Mixing conditions・a/b=1/1 or 3/1(wt% ratio)・Compound ratio: NCO/NH=1.1・Coating solid: NV=90% diluted by Butyl acetate
Coating conditions・Film thickness(dry): 80-100μm(3-4mil)・Drying method: 23℃/50%Humidity
Evaluation・High-solid property: Mixed viscosity・Tack-free time: Drying time・Hardness: König pendulum・Chemical resistance・Weatherability: Q-UV
Aspartic ester: a.
Aspartic ester: b.
12
Ultra-low viscosity HDI trimer: test result (1)
High-solid property: Mixed viscosity * Coating solid: NV=100wt%. Aspartic ester a/b=1/1(wt% ratio) condition.
Ultra-low vis Low vis Standard vis
Viscosity[mPa.s/25℃] <1,500 <2,000 3,000<
Especially ultra-low viscosity HDI trimer is suitable for non-solvent formulation
Standard visLow visUltra-low vis
0.5hr
1.0hr
1.5hr
2.0hr
0.5hr
1.0hr
1.5hr
2.0hr
0.5hr
1.0hr
1.5hr
2.0hr
2.5hr
3.0hr
3.5hr
4.0hr
2.5hr
3.0hr
3.5hr
4.0hr
2.5hr
3.0hr
3.5hr
4.0hr
Tack-free Tack-freeTack-free
* Evaluate residual cotton on film after loading 100g of weight on 1g of cotton ball for 1 minute. Aspartic ester a/b=3/1(wt% ratio) condition.
Tack-free time: Drying time
Low viscosity HDI trimers are equivalent to standard
* Polyaspartic is much faster than polyurethane
(8hrs or more)
13
Ultra-low viscosity HDI trimer: test result (2)
Weatherability: Q-UV
Hardness: König pendulum
TUL TLA TKA
Kö
nig
pen
du
lum
[c
ou
nts
]
Rigid
Soft
0
20
40
60
80
100
0 500 1000 1500 2000
TUL
TLA
TKA
6hr
1day
2day
5day
Ultra-low vis Low vis
Ultra-low vis
Low vis
Exposure time [hrs]
Glo
ss r
eten
tio
n [
%]
Low viscosity HDI trimers are almost equivalent to standard
IPA Xylene H2SO4 NaOH
Ultra-low vis Poor Fair Good Good
Low vis Poor Fair Good Good
Standard vis Fair Good Good Good
Chemical resistance
Standard vis
Standard vis
14
Polyaspartic coatings: Starting Point Formulation(SPF)
Grade Weight [g] Function
<Component A = Resin part>
Aspartic ester a 128.6 Aspartic ester resin
Aspartic ester b 385.8 Aspartic ester resin
Additive a 0.9 Surface wetting
Additive b 4.5 Surface wetting
Additive c 4.5 Defoamer
Molecular sieve 8.8 Moisture scavenger
<Component B = Hardener part>
Ultra-low viscosity HDI trimer 355.7 HDI polyisocyanate
<Component C>
Butyl acetate to application viscosity 111.2 Solvent
<Total> 1,000.0
VOC content (not including solid material) 140 g/L
Non-volatiles : 87% NCO/NH : 1.10 Mixing : 1,000 rpm / 5 min.
Drying : 23℃ / 50%RH for 7 days Dry film thickness : 80-100 micron meter
15
Ultra-low viscosity HDI trimer: test result summary
Ultra-low vis Low vis
Low viscosity HDI trimers=> Keeping coating performances while VOC reduction
(drying time, hardness, chemical resistance, weatherability)
* Ultra-low viscosity HDI trimer is suitable for non-solvent formulation
Standard vis
3) Application: High flexure HDI prepolymer
17
High flexure
Type GradeSolids
[wt%]
NCO
[wt%]
Viscosity[mPa.s/25℃]
HDI
prepolymer
High flexure
100 9.0 6,000
High flexure HDI prepolymer
Advantages of high flexure HDI prepolymer
High flexure HDI prepolymer=> Only hardener changeing become excellent bending test (no crack)
R
O C
O C
O
O
O C
O
HN
HN
HN
(CH2)6
(CH2)6
(CH2)6
NCO
NCO
NCO
:flexible units
Structure image
Figure: Bending test, coated rubber
crack
Trimer
18
High flexure HDI prepolymer: test condition
Aspartic esterSolids[wt%]
Amine Value[mgKOH/g]
Viscosity[mPa.s/25℃]
Feature
Aspartic acid,N,N-(methylenedi-4,1-cyclohexanediyl)bis-, tetraethyl ester
100201 1,190 Standard
Aspartic acid,N,N-methylenebis(2-methyl-4,1-cyclohexanediyl)bis-, tetraethyl ester
191 1,490 Low reactivity
a.
b.
PolyisocyanateSolids[wt%]
NCO content[wt%]
Viscosity[mPa.s/25℃]
High flexure100
9.0 6,000High flexure/low vis=4/1 11.9 3,300
High flexure/low vis=3/2 14.7 1,600
Mixing conditions・a/b=1/1 or 3/1(wt% ratio)・Compound ratio: NCO/NH=1.1・Coating solid: NV=90% diluted by Butyl acetate
Coating conditions・Film thickness(dry): 80-100μm(3-4mil)・Drying method: 23℃/50%Humidity
Evaluation・Toughness: Tensile test・Tack-free time: Drying time・Hardness: König pendulum・Chemical resistance・Weatherability: Q-UV
Aspartic ester: a.
Aspartic ester: b.
19
High flexure HDI prepolymer: test result (1)
Toughness: Tensile test
By using high flexure/low vis blend formulation, flexibility can be adjusted.
High flexure/low vis=3/2High flexure/low vis=4/1High flexure
0.5hr
1.0hr
1.5hr
2.0hr
0.5hr
1.0hr
1.5hr
2.0hr
0.5hr
1.0hr
1.5hr
2.0hr
2.5hr
3.0hr
3.5hr
4.0hr
2.5hr
3.0hr
3.5hr
4.0hr
2.5hr
3.0hr
3.5hr
4.0hrTack-free
Tack-free
* Evaluate residual cotton on film after loading 100g of weight on 1g of cotton ball for 1 minute. Aspartic ester a/b=3/1(wt% ratio) condition.
Tack-free time: Drying time
Elongation [%]
Str
ess
str
engt
h[M
Pa]
By using high flexure/low vis blend formulation, drying time can be adjusted.
* Polyaspartic is much faster than polyurethane(8hrs or more)
High flexure High flexure/low vis=4/1
High flexure/low vis=3/2
20
High flexure/low vis=4/1
High flexure HDI prepolymer: test result (2)
Rigid
Soft
Weatherability: Q-UV
Hardness: König pendulum
6hr1day
2day
5day
High flexure
Exposure time [hrs]
Glo
ss r
eten
tio
n [
%]
IPA Xylene H2SO4 NaOH
High flexure Poor Poor Good Good
High flexure/low vis=4/1
Poor Poor Good Good
High flexure/low vis=3/2
Poor Poor Good Good
Chemical resistance
High flexure/low vis=3/2
High flexureHigh flexure/low vis=4/1
High flexure/low vis=3/2
High flexure HDI prepolymer isthe most flexible and weatherability.
21
Grade Weight [g] Weight [g] Function
<Component A = Resin part>
Aspartic ester a 79.2 91.1 Aspartic ester resin
Aspartic ester b 237.5 273.3 Aspartic ester resin
Additive a 0.5 0.6 Surface wetting
Additive b 2.7 3.2 Surface wetting
Additive c 2.7 3.2 Defoamer
Molecular sieve 5.5 6.3 Moisture scavenger
<Component B = Hardener part>
High flexure HDI prepolymer 339.3(80%) 305.0(70%) HDI polyisocyanate
Low viscosity HDI trimer 84.8(20%) 130.7(30%) HDI polyisocyanate
<Component C>
Butyl acetate to application viscosity 247.8 186.6 Solvent
<Total> 1,000.0 1,000.0
VOC content (not including solid material) 270 g/L 210g/L
Non-volatiles : 74%, 80% NCO/NH : 1.10 Mixing : 1,000 rpm / 5 min.
Drying : 23℃ / 50%RH for 7 days Dry film thickness : 80-100 micron meter
Polyaspartic coatings: Starting Point Formulation(SPF)
22
High flexure HDI prepolymer: test result summary
High flexure High flexure/low vis=4/1
High flexure/low vis blend formulation=> Adjusting coating film performance
(drying time, hardness and flexibility, weatherability)
* High flexure HDI prepolymer is the most flexible and weatherability, so is especially suitable for heavy corrosion protection application
High flexure/low vis=3/2
4) Summary
24
Polyaspartic coatings (Soft type)
Advantages of low viscosity HDI trimers
Polyaspartic coatings (Hard type)
► Reduced VOC
► Keeping coating performances(= drying time, hardness, chemical resistance and weatherability)
Comparison of ultra-low viscosity HDI trimer with low viscosity HDI trimer
► Suitable for non-solvent formulation
Summary
Advantages of high flexure HDI prepolymer
► Better flexibility than HDI trimer
► Excellent weatherability
* High flexure HDI prepolymer/low viscosity HDI trimer blend formulation can be adjusted
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