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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To do all that we can in every era to help the people of the world

make the most of life and attain fulfillment in living.

Since our founding, we have always been deeply committed

to contributing to the development of society,

boldly anticipating the emergence of new needs.

This is what we mean by “Creating for Tomorrow.”

For more information, please contact me anytimesatoshi.takeno@asahi-kasei.eu