Water Borne Self-Matting Polyamide Technology© The Lubrizol Corporation 2019, All Rights Reserved. WHAT WE ADD MAKES THE DIFFERENCE. TM Water Borne Self-Matting Polyamide Technology

© The Lubrizol Corporation 2019, All Rights Reserved.

WHAT WE ADD MAKES THE DIFFERENCE.TM

Water Borne Self-Matting Polyamide Technology

Eric Broz

Coatings Trends & Technologies Conference

September 10, 2019

© The Lubrizol Corporation 2019, All Rights Reserved. 2WHAT WE ADD MAKES THE DIFFERENCE.TM

TYPICAL POLYURETHANE

Diluent-OHHO-

Polyol

(Soft segment)

Poly-Isocyanate

(Hard segment)

Acid

(Water dispersing)

Process Aid

(Viscosity control)

Polyamide

Technology

+ -NCOOCN- + -OHHO- +


SEGMENTED POLYMERS – THERMOPLASTIC ELASTOMERS

Segments of soft blocks and hard blocks

Physical and mechanical properties dependent of segment properties and intermolecular interactions

Common soft segments in PUD are made of polyester, polyether, or polycarbonate polyols

Chemical and physical properties strongly influenced by soft segment

SoftHard

Crystalline

Amorphous


DIFFERENT TYPES OF POLYOLS – SOFT SEGMENTS IN PUD

Lubrizol has invented a new building block for synthesizing polymers, in particular,

new waterborne polyurethane dispersions.

Polyether polyol Good hydrolytic stability

Poor UV resistance

Polycarbonate polyol Good UV and hydrolytic stability

High price and limited composition

variability

Polyester polyol Good mechanical properties and UV

resistance

Poor hydrolytic stability

Polyamide polyol – previously

believed to be not suitable for soft

segment, no commercial

availability


PROBLEMS WITH POLYAMIDE OLIGOMERS

• Tendency to form crystalline, high melting, structures due to strong intermolecular

hydrogen bonding

• Viscosity usually too high to handle in common PUD processes

• Additional synthesis step needed to convert amine or carboxyl chain-ends to hydroxyl

(cost)

• Raw material availability

• Isocyanates may react with amide

• Moisture hold-up

Many reports on attempts to make polyamide-urethane polymers, but

little commercial success so far…


POLYMERS WITH POLYAMIDE SEGMENTS

FUNCTIONAL POLYAMIDES were developed with amine and/or hydroxyl

terminations and controlled:

• Molecular weight

• Hydrophobicity

• Hydrogen bonding

• Branching/rings

URETHANE WITH A CHEMICALLY INERT SOFT

SEGMENT AND VERY HIGH HARD SEGMENT COMPATIBILITY

POLYAMIDE based URETHANES are NOT:

• Impossible to process in any form …

• Water sensitive: swells/blushes at ambient …

• Brittle without any elongation or strength whatsoever …


ADVANTAGES OF POLYAMIDE POLYURETHANEM

ECH

AN

ICA

L &

CH

EMIC

AL • High Hardness

• Excellent Chemical Resistance

AD

HES

ION • Nylon/Polyamides

• Glass

• Polar surfaces

HY

DR

OLY

TIC

& T

HER

MA

L ST

AB

ILIT

Y • Hydrolytic:• AMIDE >> ESTER

• Thermal:• AMIDE >> ETHER


PERFORMANCE EVALUATION OF URETHANES

Waterborne PUD

Soft Segment Type:

POLYESTER

POLYETHER

POLYCARBONATE

POLYAMIDE


POLYAMIDE TECHNOLOGYCURRENT APPLICATIONS

Applications:

• Industrial Metal Coatings

• Wood Coatings

• Masonry Flooring Systems

Features:

• High Hardness

• Excellent Chemical Resistance

• Film Clarity


NWFA – INDUSTRY OUTLOOK EXPECTED DEMAND – FINISH TYPE

Current Trend --- Lower Gloss; Natural-Look Coatings for Wood Flooring

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

ConjugatedOils

Conv Varnish High-Gloss Low-Gloss MoistureCure

Natural Oils UV / LED Cure Waterbased Wax

More Demand Less DemandPercentages reflect NWFA Members who anticipate a higher or lower demand for finish types. Source: 2018 NWFA


• Matte appearance is caused by a reduction in the amount of specular reflected light; this is linked to surface roughness

• One of the more common techniques of matting uses the addition of large, non-soluble particles to create a micro-texture surface during film formation (i.e. Silica, Kaolin, Bentonite, Waxes)

• Develop resins with very large particles mixed in to create surface roughness and generate topography on the surface

TRADITIONAL MATTING TECHNIQUE


PRO AND CONS OF TRADITIONAL MATTING ADDITIVES

Traditional matting agents are efficient, but have a large opportunity for improvement

Wide variety of matting

additives allow formulation flexibility for

specific applications

Tend to negatively impact performance

properties

Soft settling of non-soluble particles leads to stability

issues and shelf life constraints


IMPACT OF MATTING ADDITIVES ON A TYPICAL RESIN

Using matting additives to lower gloss has a significant NEGATIVE impact on both durability & appearance

0

20

40

60

80

100

60° 85°

Gloss

0

4

8

12

16

Haze

0

25

50

75

100

Taber Abrasion1000 Cycles CS-17 Wheel (mg loss)

Pencil Hardness4H

3H

2H

H

F

PUD PUD Matted w/Silica

Decrease in Hardness

7X Increase in Haze

56% Increase in mg Loss

3 coats on Maple laminate panels Formulated to ≤275g/L US VOC


Polymer Physical Characteristics*

Appearance (wet) Milky White Dispersion Total Solids by Weight, % 35.0 ± 1.0 Total Solids by Volume, % 34.2 ± 1.0 Density, lbs. /gal (g/ml) 8.69 (1.04) Brookfield Viscosity, cps < 500 pH 7.5 – 8.5 Volatile Organic Compounds, wt. % 0.85 TEA Freeze-Thaw Stability Protect from freezingNMP, NEP, and APEO-Free VOC - Can formulate to <275 g/L (USA) / 110 g/L EU VOC

*Property values represent typical results only and are not to be considered specifications

SELF-MATTING POLYAMIDE POLYURETHANEAPPLICATIONS AND PROPERTIES

Recommended Applications

• Wood interior applications requiring high performance in a matte finish

• Metal and general topcoat applications needing a flat look with great color saturation


• As the self-matting coating dries, micro scale viscosity and surface tension abnormalities generate a matted surface

• This resin does NOT contain large particles commonly used to create self matting coatings, leading to improved stability

• This resin can reach a 60° gloss of 16 GU without the use of matting additives (gloss can be reduced further with a small amount of polymeric matting agent)

NEW SELF-MATTING PUD

Self-Matting Polyamide PUD Matted Commercial Control

7.0 μm

6.0

5.0

4.0

3.0

2.0

1.0

0.0


SELF-MATTING TIME LAPSE VIDEO10X MAGNIFICATION


0

4

8

12

16

Haze

0

50

100

Taber Abrasion1000 Cycles CS-17 Wheel (mg loss)

0

20

40

60

80

100

60° 85°

Gloss

SELF-MATTING VS. TRADITIONALLY MATTEDPUD RESIN

Self-matting PUD reaches lower gloss than traditionally matted PUD without sacrificing either durability or appearance

PUD PUD Matted w/Silica Self-matting PUD

Pencil Hardness4H

3H

2H

H

F



SELF-MATTING PUD CHEMICAL RESISTANCE

Self-matting PUD outperforms traditionally matted commercial products and performs on par with high gloss coatings

0

5

10

DI Water (4hr) 1% Spic N Span(4hr)

Veg Oil (4hr) 50% EtOH/DIwater (1hr)

Naphtha (1hr) Cola (1hr) Budweiser (1hr) Perspiration (1hr)

MFMA Chemical Resistance (1hr Recovery)

Self Matting PUD Self Crosslinking PUD Acrylic #1 Acrylic #2

0

5

10

MEK(1hr) Formula409 (1hr)

Mustard(1hr)

Water(24hr)

IPA (24hr) Ketchup(24hr)

Vinegar(24hr)

Old English(24hr)

Grape Juice(24hr)

Hot Coffee(24hr)

Red Wine(24hr)

Windex(24hr)

Chemical Resistance on Wood

Self-matting PUD High Gloss Commercial Control Low Gloss Commercial Control



SELF-MATTING PUD TABER ABRASION AND HARDNESS

Self-matting PUD performs significantly better for both hardness and abrasion resistance compared to SB and WB commercial products

169.4

195.8

214.6

81.9

131.5

124.3

0 50 100 150 200 250

WB A

WB B

SB A

WB Self Matting PUD

WB C

WB D

mg loss

Taber Abrasion ( CS-17 wheels 1000 cycles)

0

10

20

30

40

50

60

WB A WB B SB A WB SelfMatting

PUD

WB C WB D

Konig Hardness – ASTM D4366

3 coats on Maple laminate panels

Formulated to ≤275g/L US VOC


PIGMENTED SELF-MATTING PUD IN A PIGMENTED TOPCOAT

Pigmenting the self-matting PUD improves chemical and corrosion resistance and maintains color when exposed to UV

0

2

4

6

8

10

Salt Spray(1000hr)

Humidity(1000hr)

Skydrol

EtOHMEK

Sulf 1%

16hr

Chemical Resistance in a Metal Topcoat Pigmented System

Red White Black0 20 40 60 80 100 120 140 160

Red

White

Black

Impact Resistance ASTM

Back Front


ACCELERATED WEATHERING (UV-A METHOD SAE2020J)

∆E is under 1.0 after 2000 hours of exposure without the use of weathering agents

0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

1.8

2

250 500 750 1000 1500 1750 2000

∆E

HOURS

∆E for UV-A Method SAE2020J

White R706

0

2

4

6

8

10

12

14

16

Intial 250 500 750 1000 1500 1750 2000

60

°G

loss

hours

60° Gloss Retention in UV-A SAE2020J

Red White


ACCELERATED WEATHERING (XENON ASTM D6695-03B CYCLE 6)

∆b is under 0.5 after 2000 hours of exposure without the use of weathering agents

0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

1.8

2

250 500 750 1000 1500 1750 2000

∆E

Hours

∆E for Xenon

White R706

-0.3

-0.2

-0.1

0

0.1

0.2

0.3

250 500 750 1000 2000

∆b

Hours

Yellowing (∆b) in Xenon

White R706 Black 1300


COLOR SATURATION OF SELF-MATTING PUDAS A TOPCOAT

L*=26.01a*=0.19b*=-0.43

L*=26.56a*=0.22b°=-0.36

ΔE=0.56

Clear coat on top of black primer


SELF-MATTING PUD WITH EXTERNAL CROSSLINKER

Addition of external crosslinker positively impacts black heel and barrier properties

0.00

1.00

2.00

3.00

4.00

5.00

6.00

BH

M R

atin

g (b

est=

10

)

Black Heel Mark

Self-matting PUD Low Gloss Commercial Control Isocyanate Crosslinker Aziridine Crosslinker

0

1

2

3

4

5

6

7

8

9

10

DI Water(4hr)

1% Spic NSpan (4hr)

Veg Oil (4hr) 50%EtOH/DI

water (1hr)

Naphtha(1hr)

Cola (1hr) Budweiser(1hr)

Perspiration(1hr)

MFMA Chemical Resistance (Before Recovery)



Proven durability to protect high value end use

Forms a hard, tough film with

exceptional abrasion

resistance

Achieving low gloss in high performance coatings with

little to no matting additive

Formulation flexibility due

to less matting additives

Low gloss without

sacrificing properties

Simplify manufacturing & reduce raw material cost

FEATURES & BENEFITS


Superior Chemical

Resistance

Stain resistance maintains coating

appearance in many

environments

FEATURES & BENEFITS

Forms a hard, tough film with

exceptional abrasion

resistance

Proven durability to protect high value end use


High clarity in a low

gloss formulation

Visual appeal of natural color & texture of wood

Topcoat preserves vibrant color for a more attractive finish

FEATURES & BENEFITS


IN SUMMARY

Waterborne, self-crosslinking, self-matting polyurethane dispersion using patented polyamide polyol technology

• Naturally low gloss (16 GU @ 60°) with no matting additives*

• Exceptional hardness, abrasion, and chemical resistance

• Extremely clear film*Gloss can be further reduced with small amounts of polymeric matting agent

This technology allows formulators to create coatings with beautiful matte finishes and superior durability and protection; while

extending the service life


PERFORMANCE AND AESTHETICS?

NO need to sacrifice performance for matte

aesthetics

If I only had one slide…..


ACKNOWLEDGEMENTS

Dechant, Amanda

Puckrin, Rebecca

Pafford, Robert

Pajerski, Anthony

Peralta, Miriam

Smith, Ryan

Weiner, Jon

Cremona, Dominic

Skoff, Israel

Erdodi, Gabor

Baron, Steve

Latas, Dan

Donati, Pete

Stanislawcyzk, Vic

Swech, Chris

Schneiders, Larry

Sterne, Nick

Wolfinger, Mark


The information contained herein is believed to be reliable, but no representations, guarantees or warranties of any kind are made as to its

accuracy, suitability for particular applications or the results to be obtained. The information is based on laboratory work with small scale

equipment and does not necessarily indicate end product performance. Because of the variations in methods, conditions and equipment

used commercially in processing these materials, no warranties or guarantees are made as to the suitability of the products for the

applications disclosed. Full-scale testing and end product performance are the responsibility of the user. Lubrizol Advanced Materials, Inc.

shall not be liable for and the customer assumes all risk and liability of any use or handling of any material beyond Lubrizol

Advanced Materials, Inc.’s direct control. The SELLER MAKES NO WARRANTIES, EXPRESS OR IMPLIED, INCLUDING, BUT NOT LIMITED TO, THE

IMPLIED WARRANTIES OF MERCHANTABILITY AND FITNESS FOR A PARTICULAR PURPOSE. Nothing contained herein is to be considered as

permission, recommendation, nor as an inducement to practice any patented invention without permission of the patent owner.

THANK YOU

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Water Borne Self-Matting Polyamide Technology© The Lubrizol Corporation 2019, All Rights Reserved. WHAT WE ADD MAKES THE DIFFERENCE. TM Water Borne Self-Matting Polyamide Technology