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transcript
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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