Stahl Polymers Bangkok 2016

Stahl Polymers Worldwide polymer industry solutions

Chun Leong Tan & Joan Parareda, Bangkok, May 2016

▪  Presentation of Stahl

▪  Stahl Polymers technologies

▪  Products for construction

▪  Products for inks & graphic arts

▪  Products for metal ▪  Products for plastics

▪  Products for wood coatings

▪  Crosslinkers

Content

As a market leader Stahl has a longstanding partnership with some of the world’s leading companies in various industries.

Global presence

History

Stahl Business Services Central General Services

Stahl Management Team

Stahl Polymers Wet-End Performance Coatings

Leather Finish Automotive

Leather chemicals

PielColor

Stahl Business Units

HQ Waalwijk, NL

Operational Excellence

23 11

600 38

> 1.800

Plants

Countries

People worldwide

Application Labs

Sales technicians

9

R&D centers

Worldwide coverage ■  One headquarters ■  9 R&D centers ■  11 Manufacturing sites ■  38 Application labs in 23 countries ■  1800+ Employees

Stahl’s sustainable principle

Six steps towards a more sustainable future

Step 1 > Step 2 > Step 3 > Step 4 > Step 5 > Step 6 > Raw materials Production Packaging and

distribution Product application

Product use and maintenance

End of life

High-quality, better service. We constantly challenge ourselves to develop high-quality coatings that have less impact on the environment.

Stahl Polymers

Stahl Polymers portfolio

Polyurethanes

Self-crosslinking

Waterbased PUD : PES, PE, PC and UFA

Acrylic Emulsions

Types of technology

Solventbased PU : PES and PE

Crosslinkers

Polycarbodiimides: Multifunctional and WB

Polyaziridine

Alkali soluble

OH-functional

Cationic

Adhesion promoted

Core-Shell

Metal bound

Controlled morphology

Surfactant free

Melamines

Isocyanates

1.  Monomer composition

2.  Alkali soluble

3.  Metal bound

4.  Hydroxy functional

5.  Cationic 6.  Adhesion promoted

7.  Core-shell - Controlled morphology

8.  Controlled particle size

9.  Surfactant free

10.  Self-crosslinking

11.  Dual reaction

Acrylic emulsion technologies

1. Monomer composition

Picassian® AC-049 Picassian® AC-126 Picassian® AC-107

Type Pure acrylic STY based AN based

Solids % 46 40 30

MFFT °C 10 50 ˂ 0

Key property Weather resist. Water resist. Chemical resist.

Main market Architectural coatings Exterior Wood

Coil & Industrial metal Textiles

2. Alkali soluble

Picassian® AC -275 Picassian® AC- 271

Solids % 40 48

MFFT °C 23 13

Key property Exponential viscosity curve Flat viscosity at pH>8

Main market Architectural coatings Grinding binder

Architectural coatings Roller application

3. Metal bound

Picassian® AC-233

Solids % 40

MFFT °C 64

Key property Wear resistance

Main market Architectural coatings Floor polish

▪  Neutralization of the acid with

basic metallic oxides

▪  Improves water and chemical

resistance

▪  In polymers with high Tg, enhances wear properties (floor polish)

▪  Easily removable with alkaline

cleaners

4. Hydroxy functional

Picassian® AC-176

Solids % 47

MFFT °C 37

Key property > 200 MEK rubs

Main market Coil & Industrial metal

5. Cationic

Picassian® AC-146

Solids % 40

MFFT °C 46

Key property Tannin stopper

Main market Architectural coatings Tropical wood

▪  Use of cationic monomers

instead of carboxyl groups

▪  Tannin stoppers for tropical

woods

6. Adhesion promoted

Picassian® AC-213

Solids % 38

MFFT °C 5

Key property Adhesion

Main market Architectural

7. Core-shell morphology

Picassian® AC-169

Solids % 40

MFFT °C 18

Key property High blocking resistance

Main market Architectural coatings Furniture

8. Controlled particle size

Picassian® AC-280

Solids % 50

MFFT °C 32

Key property Corrosion resistance

Main market Coil & Industrial metal

▪  Narrow distribution usually improves

transparency and compatibility

▪  Small binder particles can be

absorbed without blocking wood

pores - Wood impregnating binders ▪  Lower porosity, better film formation -

Anticorrosive binders

9. Surfactant free

Picassian® AC-122

Solids % 40

MFFT °C 35

Key property Transparency

Main market Architectural coatings Furniture

▪  Emulsions free of emulsifier agents

▪  Low molecular weight, small

particle size

▪  High wood wetting - Excellent

transparency ▪  Water resistance

10. Self crosslinking

Picassian® AC-169

Solids % 40

MFFT °C 20

Key property Short drying time

Main market Furniture

▪  When the film dries, ammonia and/or

amines evaporate and pH becomes

acidic

▪  At pH≈⋲ 4, a new reaction between

C=O groups from the polymer with a free diamine takes place

▪  Crosslinking unites different

polymer chains

11. Dual reaction

Picassian® AC-192

Solids % 40

MFFT °C 43

Key property Higher crosslinking density

Main market Architectural coatings Furniture

▪  Two different chemistries:

- Hydroxyl groups + NCO (as 2K)

- Self-crosslinking reaction (as 1K)

1.  Overview of polyurethane dispersions

2.  WB polycarbonate based PU

3.  WB solvent free polyester based PU

4.  WB solvent free polyether PU

5.  WB solvent free fatty acid modified PU 6.  WB UV-curable PU

7.  WB matt PU

8.  Solventborne PU

Polyurethane technologies

1. Overview PU dispersions ■  Prepolymer (achievement of the polymeric structure)

-  Polyol + diisocyanate + initiator

■  Dispersion phase: -  Neutralization (ex: with TEA) -  Water dispersion -  Diamine extension (achievement of desired molecular weight)

HO-R-OH + OCN-R’-NCO HO-R [-O-C-N]-R’-NCO OH  

Polyol Polyurethane Diisocyanate

Polyol Diisocyanate Diamine

Polyether Hexamethylene diisocyanate (HDI) Hydrazine

Polyester Isophorone diisocyanate (IPDI) Ethylene diamine

Polycarbonate Methylene diciclohexyl diisocyanate (H12MDI) Propylene diamine

Toluene diisocyanate (TDI) Isophorone diamine

Methylene diphenyl diisocyanate (MDI)

1. Overview PU dispersions

1. Overview PU dispersions

Polyether Polyester Polycarbonate

Hydrolytic resistance ++ - ++

Elongation +++ ++ ++

Abrasion resistance + ++ ++

Solvent and oil resist - ++ +++

Heat resistance + ++ +++

High fastness + ++ ++

Behaviour at low T + - -

UV resistance - + ++

2. Polycarbonate PU ▪  High performance coatings

▪  Excellent chemical resistance

▪  High scratch and abrasion resistance

▪  Very good adhesion on plastics

▪  Stahl Polymers example: Relca® PU-477

Relca® PU-477

Solids % 30

pH 9

Viscosity (cP) < 250

MFFT (°C) < 5

Hardness (König, s) 29

UTS (MPa) 17

100% Modulus (MPa) 6

Elongation (%) 356

R-O-C-O-R O  

2. Polycarbonate PU Recommended applications ▪  Architectural coatings:

High gloss wood flooring

▪  Architectural coatings:

PVC flooring ▪  Coil & Industrial metal

▪  Automotive plastic coatings

3. Solvent free polyester PU

▪  Glossy coatings

▪  Very good chemical resistances

▪  Excellent abrasion resistance

▪  Hard films

▪  Stahl Polymers example: Relca® PU-625

Relca® PU-625

Solids % 40

pH 7.5

Viscosity (cP) < 500

MFFT (°C) 10

Hardness (König, s) 120

UTS (MPa) 25

100% Modulus (MPa) 21

Elongation (%) 214

R-C-O-R O  

3. Solvent free polyester PU Recommended applications ▪  Architectural coatings:

Parquet flooring

▪  Furniture coatings

▪  General wood coatings

4. Solvent free polyether PUD

▪  Flexible coatings

▪  Medium chemical resistances

▪  High elongation

▪  Soft films

▪  Stahl Polymers example: Relca® PU-648

Relca® PU-648

Solids % 40

pH 8

Viscosity (cP) < 500

MFFT (°C) < 5

UTS (MPa) 10

100% Modulus (MPa) 4

Elongation (%) 528

R-O-CH2-CH2-O-R

4. Solvent free polyether PUD Recommended applications ▪  Textiles

▪  Graphic arts

5. Fatty acid modified PU

▪  Very hard films

▪  Excellent chemical resistances,

including ethanol resistance

▪  Very good “Anfeuerung”

▪  Very good scratch and black heel resistance

▪  Stahl Polymers example:

Relca® PU-476

Relca® PU-476

Solids % 36

pH 7.5

Viscosity (cP) < 500

MFFT (°C) 40

Hardness (König, s) 160

Recommended applications ▪  Architectural coatings:

Parquet flooring

▪  Wood coatings

▪  Coil & Industrial metal: Interior DTM

5. Fatty acid modified PU

6. Water-based UV-curable PU

▪  Very hard films

▪  Outstanding chemical resistances,

including ethanol

▪  Excellent scratch and black heel stain

resistance ▪  Stahl Polymers example:

Relca® UV-628

Relca® UV-628

Solids % 35

pH 7.5

Viscosity (cP) < 500

MFFT (°C) < 5

Hardness (König, s) 150 (UV cured)

Recommended applications ▪  Architectural coatings:

High gloss wood flooring

▪  Architectural coatings:

PVC flooring

6. Water-based UV-curable PU

7. Water-based matt PUD

▪  Low gloss without the use of

matting agents

▪  Very good compatibility with water-based

acrylics, polyurethanes and hybrids

▪  Soft and flexible films ▪  Very good scratch resistance

▪  Stahl Polymers example:

Relca® PD-802

Relca® PD-802

Solids % 32

pH 8.5

Viscosity (cP) 400

Recommended applications ▪  Co-binder to be used as a matting agent:

-  Architectural coatings

-  Coil & Industrial metal

-  Automotive plastic coatings -  Architectural coatings: PVC flooring

7. Water-based matt PUD

8. Solvent-based PU ▪  Excellent adhesion on plastic fims

(OPP, PET, NY,…)

▪  Suitable for flexible

packaging applications

▪  Very good dispersing, wetting and flowing properties

▪  Soft, flexible films

▪  Stahl Polymers example:

Picassian® PU-551

Picassian® PU-551

Backbone Polyether

Solids % 58

Viscosity (cP) 5250

Solvent blend ethyl acetate / ethanol

Hydroxyl value (mg KOH/g) 2.5

Density (g/mL) 0.96

8. Solvent-based PU Recommended applications ▪  Graphic arts:

Flexible packaging

Stahl Polymers’ solutions for the industry

Architectural

Picassian® PU-490 polyester PUD: ■  Good hardness and outdoor durability ■  Chemical, water and ammonia resistance ■  Scratch resistance ■  Good colour development

Relca® PU-461 polycarbonate PUD: ■  Higher hardness ■  Higher chemical resistance

Polyurethanes for flooring

Picassian® AC-290 ■  Outdoor concrete coatings ■  Water, alkali and solvent resistance ■  High breathability

Self-crosslinking acrylic

AC-290 for for outdoor concrete

%

Binder-free pigment paste (56% Tio2) 24.0

Picassian AC-290 64.0

Dowanol DPnB 3.0

Tego Foamex 825 0.3

Tego Viscoplus 3060 0.4

Water 8.3

Total 100.0

AC-290 for for outdoor concrete

Crosscut

MEK Ethanol

Water

EA

Ammonia

Graphic arts

Picassian® PU-648 ■  Textile screen inks ■  Excellent coverage and filling ■  Keeps flexibility at -30°C ■  Crosslinkable with carbodiimide or aziridine for excellent washing fastness

Solvent-free polyether PU

Picassian® AC-275 ■  For WB flexo and gravure inks ■  Grinding resin ■  Its pigment wetting ability allows higher pigment loads

Alkali soluble acrylic resin

Coil & Industrial Metal

Styrene-acrylic resins Picassian® AC-126 ▪  Standard multi-use binder

▪  For DTM and pigmented systems

▪  40% solids

Picassian® AC-280

▪  High solids (50%)

▪  Lower MFFT → lower coalescent demand

▪  Enhanced corrosion protection

Example formulation: high gloss DTM coating

Picassian AC-280 89,0 BYK 028 0,4 Butyldiglycol 2,5 Dowanol DPnP 2,5 Viscoplus 3030 0,4 Halox 515 3,0 Water 2,2

Metal

S-46 panel 250 µm wet , 55 µm dry Drying 72 h 50ºC 300  h  salt  spray  

Solvent-free polyurethane dispersions

Relca® PU-655 solvent-free polyurethane dispersion: ■  Polycarbonate based PU

■  Can be formulated to make low VOC coatings

■  Recommended for thin organic coil coatings

Electronics & Automotive Plastics

Relca® PU-477 solvent-free polyurethane dispersion: ■  High elongation ■  Excellent UV resistance ■  Very good water and chemical resistance

Solvent-free waterborne binders

Picassian® AC-191 styrene-acrylic resin: ■  Excellent adhesion on PC and ABS ■  Resistance to scratch, alcohol and hand cream ■  Hard and glossy films

Picassian® AC-126 styrene-acrylic resin: ■  45m9b245g542 ■  45kg4v24905gkvvr ■  45890vk02’62v55

Wood coatings

Furniture Self-crosslinking acrylics ▪  Picassian® AC-122

-  Excellent sandability and transparency

-  Hardness 110 s, MFFT 35ºC

▪  Picassian® AC-194

-  New version of AC-122 at 45% solids

▪  Picassian® AC-169 -  Outstanding block resistance

-  Softer than AC-122

▪  Picassian® AC-137

-  Softer than AC-169

-  Higher resistance to alkalis

Furniture Dual technology ▪  Picassian® AC-192 and AC-193

-  As 1 component → self crosslinking

-  As 2 component → OH functional, crosslinkable with isocyanates

-  One single product, two levels of performance

Furniture Other products ▪  Picassian® AC-126

-  Hard styrene-acrylic

-  “universal mixer”

▪  Relca® HY-460 and HY-614

-  Fatty acid + urethane hybrids -  Renewable raw materials

-  Highlight natural beauty of wood

▪  Picassian® AC-275

-  Alkali soluble, excellent pigment wetting ability

Outdoor wood ▪  Picassian® AC-290

-  Early water resistance, impact resistance, adhesion, vapor

permeability, sandability, UV resistance,...

▪  Picassian® AC-049

-  Long durability. It needs to be formulated carefully to

avoid dirt pickup

Outdoor wood Example formulation: high gloss enamel

Picassian AC-290 61,0 BYK 028 0,3 Butildiglycol 1,0 Pigment paste 20,0 BYK 346 0,4 Tafigel PUR 61 0,5 Water 17,0

Ammonia, water, coffee and hand cream resistance: 5

Flooring ▪  Relca® PU-476

-  Hybrid technology, renewable raw materials

-  Excellent chemical, abrasion and black heel resistances

▪  Relca® PU-625

-  Polyester PU

-  Excellent abrasion resistance

▪  Relca® UV-628 and UV-663

-  Waterborne UV-curable urethanes

-  UV-628 = polyester

-  UV-663 = polycarbonate

Flooring Example formulation: parquet with high CR

PRIMER Picassian AC-137 63,0 Relca PU-476 21,0 BYK 093 0,5 Butylglycol 5,0 Tafigel PUR 61 0,8 BYK 346 0,5 Water 9,2

TOPCOAT Relca PU-476 64,0 Picassian AC-137 21,0 Tego Foamex 822 0,5 Ethylglycol 8,0 Viscoplus 3030 0,5 BYK 346 0,5 Water 5,5

König hardness: 85 s Ethanol, ammonia and hand cream resistance: 5 Gloss  at  60°              90  

Stahl crosslinking technology

Crosslinking 2K systems In a “real 2K system” the binder is synthesized during application, by means of a

reaction between a polyol and an isocyanate crosslinker. In this case, if there is no

crosslinker there is no binder.

Polymer + crosslinker Stahl Polymers binders are already polymerized and film forming. Function of the crosslinker is to improve specific characteristics (mechanical properties, chemical

resistance,...).

Free chains 3D network

Main types of crosslinkers

▪  Polyaziridines ▪  Polyisocyanates

▪  Melamine resins

▪  Polycarbodiimides

Polyaziridines Aziridines are very effective and allow long pot lives... but they are hazardous chemicals!

Polyisocyanates Isocyanates are versatile and effective, but pot lives are short due to their sensitivity to moisture. Less severe labelling than aziridines.

Melamine resins Melamine crosslinkers react with –OH groups at high temperature (150ºC) so they are used in oven curing systems.

Polycarbodiimides (CDI) Carbodiimide groups –N=C=N- react with carboxylic groups –COOH at room temperature. Polycarbodiimide crosslinkers are label-free and allow to achieve long pot lives.

Crosslinkers comparison

Polycarbodiimide * Polyisocyanate Polyaziridine Melamine resins

Reactivity -COOH -OH, -NH2, water -COOH -OH

Pot life Up to weeks Up to 6 h 12 h Very long

GHS symbols none

R-phrases none R43/52/53 Muta. Cat 3, R22/38/41/43/68

Carc. Cat 2 R43/45/52/53

Moisture sensitivity low very high high low

Gas release none CO2 none none

(*) Not all products have all properties

Multifunctional CDIs Stahl holds patents on multifunctional polycarbodiimides. These products contain a 2nd reactive group that creates an extra crosslinking network and helps to achieve even better performance.

Summary of Stahl CDIs

Product Physical state Type Active matter (%) g/eq. (on act. matter)

Picassian® XL-701 Fluid liquid Multifunctional 50 590

Picassian® XL-702 Fluid liquid Waterborne 40 540

Picassian® XL-725 Viscous liquid Multifunctional 100 700

Picassian® XL-732 Fluid liquid Waterborne 40 460

Other Stahl crosslinkers ▪  Polyaziridine:

Picassian® XL-048, XL-706, XL-748

▪  Polyisocyanate: Picassian® XL-708, XL-720, XL-728, XL-740

▪  Melamine resins: Picassian® XL-709, XL-719, XL-749

Tips for application ▪  CDIs react with carboxylic groups. At pH ≥ 8.5 carboxylic groups are in the

inert carboxylate form, therefore: binder formulation at pH ≥ 8.5 → LONG

POT LIFE

▪  Reaction takes place at room temperature

▪  Once the coating is applied, volatile amines evaporate, pH drops and

crosslinking reaction starts

▪  2nd reactive group of multifunctional CDIs is sensitive to water, in this case pot life is up to 12 h. These products should be stored under

protective atmosphere

▪  Optimum quantity of CDI must be found out through lab work, but it is

usually 3 to 7% on binder formulation

▪  Crosslinking effectivity is evaluated by means of chemical resistance test

Examples of application

Binder CDI Chemical Resistance without CDI

Resistance with CDI

Picassian® AC-126 6% Picassian® XL-701 Ethanol 48% 3 5

Relca® HY-460 3% Picassian® XL-725 Ethanol 48% 1-2 4

Relca® PU-477 2.5% Picassian® XL-725 Ink 3 5

Relca® PU-674 7% Picassian® XL-732 Acetone 3 5

Relca® PU-625 6% Picassian® XL-701 Ethanol 48% 1 5

Summary of CDIs ▪  Polycarbodiimides are a good alternative to isocyanate and aziridine crosslinkers ▪  They react with the carboxylic groups in the binder

▪  Right combination “binder – CDI” has to be found empirically (lab tests)

▪  Benefits of CDIs include:

-  Improved chemical resistance

-  Improved adhesion

-  No classification/labelling -  Long pot lives

-  No gas release

-  Reaction at room temperature

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