07 Hungary Interior VINNAPAS VAE Dispersions 2018e Kotschi

CREATING TOMORROW`S SOLUTIONS
VINNAPAS® VAE technology for environmentally-friendly

deco paints and coatings
Dr. Udo Kotschi, WACKER POLYMERS, March 2018
Hungary, Dr. Udo Kotschi, March 2018
VINNAPAS® VAE technology for environmentally-friendly deco paints and coatings 0 of 61
Raw materials and production process

Recipe components – overview
 Water
 (Main) monomers
(vinyl acetate, ethylene, vinyl chloride, acrylics, vinyl esters etc.)
 Functional monomers
 Stabilizers
 Initiator system
 pH adjust (buffer)
 Defoamer
 Biocide

Polymer structure of VAE
Vinyl acetate (VAM) Ethylene

 Basic raw material  Tg ~ - 100 °C (soft)
 Hydrophobic
 Polar, hydrophilic
 Permanent flexibility
 Tg ~ 28 °C (hard)
 High hydrolysis resistance
 Toughness
 Ideal co-polymerization with VAM
Copolymer structure
O O O O
O O O O

The higher the ethylene contents, the lower the Tg
Tg of copolymers depends on polymer composition (Fox equation)

Tg, [C º]
30
1 x(monomer A) x(monomer B)
= +
20 Tg(copolymer) Tg( polymer A) Tg( polymer B)
1 0.88 0.12
 
10 Tg (copolymer) 301.15 K 173.15 K
-10
-20
0 5 10 15 20 25
Ethylene fraction [wt %]

Reactivity ratio comparison
r1 r2
Vinyl acetate – ethylene 1,03 0,88
Vinyl acetate – vinyl chloride 0,25 1,64
Vinyl acetate – butyl acrylate 0,018 3,48
Vinyl acetate – methyl methacrylate 0,03 26
Vinyl acetate – styrene 0,01 56

VAE dispersion technology –
comparing copolymers of VAc/E with VAc/BA
 Besides the better plasticization with ethylene, VAE polymers provide in addition
a better consistency of the polymer
 Ideal co-polymerization of vinyl acetate and ethylene
 Vac/E polymers form a more random distribution in polymer chains and less
“blocks” of homopolymer chains like in VAc/BA polymers
Equal reactivity - VAc-E-VAc-E-VAc-E-VAc-E-VAc-E-VAc-E-VAc-
Unequal reactivity - VAc-VAc-VAc-VAc-VAc-BA-BA-BA-BA-BA

Functioning of surfactants / emulsifiers
- - - - --
- -
- -
-
-
- - - - - --
- - -
- -
- - Polymer particle
- -
- -
- - - - - -
-
-
-
-
- - - -
- - - - --
Surfactant
- -
- -
- -
- Hydrophobic Hydrophilic,
-
- chain anionic or
-
- cationic group
-
- - - -

Functioning of protective colloids
Polymer particle
Steric
hindrance
Protective colloid
Hydrophobic Hydrophilic
C-chains polar

Polymer stabilization and protection systems
Purpose of protection
 Protect polymer particles during polymerisation
 Protect polymer particles during transportation

 Viscosity control
 Control of properties (chemical compatibility, water resistance, etc.)
Type of protection systems

 Protective colloids: Chemically graft to polymer particles
 PVOH (PVA): most popular for adhesives
 Cellulose
 Surfactants: anchor to polymer particles
 Protective colloids and surfactants: very popular for coatings VAE

Emulsion polymerization –
process overview
The process and apparatus used depend on the kind of monomers

Ethylene → gas
Open vessel does not work → Autoclave
Apparatus is under ethylene pressure
 Vinyl acetate / ethylene dispersions (VAEs) are sometimes also called

“pressure polymers”
Result: dispersion of polymer VAE particles in water

 Removal of the residual monomers and other volatile ingredients by
different chemical and/or physical measures

The production of vinyl acetate ethylene dispersions must be
done under pressure
Dispersions with ethylene; high demands on equipment
Ethylene Vinyl acetate, Silo

(max. 100 bar) water, initiator, additives
Reduction
of pressure
Ethylene
(10 - 20 bar)
Filter
Polymerization
Filter
Source: Wacker Chemie AG

VINNAPAS® VAE dispersion – preferred technology for
environmentally-friendly paints in Europe

Glass transition temperature (Tg)
 SodaInfluence of vinylic co-monomers on glass transition temperature of

vinyl acetate copolymers
 Ethylene is the ideal internal softener for vinyl acetate polymer dispersions!
°C
40
30
20
10
0 %-comonomer
0 10 20 30 40 50 60
-10
-20
-30
VAc/ E VAc/ VeoVa10 VAc/ VL VAc/ EHA Vac / BA


Minimum film forming temperature (MFFT)
 The process of film formation only occurs over a defined temperature.

This temperature is called “minimum film forming temperature”
 Above this temperature, the dispersion builds a homogeneous, crack-free film
 The MFFT depends on
 Tg of the polymer
 Polymer type
 Coalescing agents

MFFT ≠ Tg
 A property of the dispersion  A property of the dispersion

(liquid) film (dry)

Minimum film forming temperature (MFFT) –
VAE in comparison to SA
VAE forms film at low temperatures w/o coalescent:
SA
SA + 2% texanol
SA + 4% texanol
VAE
0 °C 12 °C 20 °C

Minimum film forming temperature (MFFT) –
paints based on VAE in comparison to SA
VAE forms film at low temperatures w/o coalescent:
A
SA
B SA + 2% texanol
C SA + 4% texanol
VAE
0 °C 12 °C 20 °C
A B C

VINNAPAS® VAE dispersions have outstanding coalescing
properties
Tg / MFFT correlation
30
MFFT [°C]
25
20
15
10
0
0 2 6 9 16 20 24 31
-5
Tg [°C]
SA VAE

VAE dispersions versus styrene acrylics –
conclusions
In VAE, water functions as a coalescing aid (hydroplastification!)

 High scrub resistance
 No additional coalescing agent
 No migration (no fogging)
 Film formation at low temperatures (< 5 °C)
 VAE – the best option for modern low VOC paints

ECO labels or legislation in place and their impact on
coatings industry

The many shades of ‘Green’ in the European & US coatings
market
Europe
VdL
1978 1989 1991 1992 1996 1998 1999 2006 2007 2008 2010
USA

Why are solvents & VOC a concern?
A combination of
 UV coming from sun activity
 NOx produced by combustion
 Solvents from various chemicals
… leads to formation of summer smog

UV (ozone building up in troposphere)
NOx VOC
 Ozone very harmful to humans
 E.g. allergy, asthma, heart attacks and

other cardio-pulmonary issues
There are programs to decrease amount
Photo- Ground of solvent in deco paints initiated long
Summer
chemical level
smog time ago across the world
activity ozone

Indoor air quality: not neutral for human health
Most important sources of organic

indoor pollutants
 Outdoor environment
 Human activities
 Materials equipments (adhesives, caulks,

floor covering, sealants, furniture, paints,
wall covering, particle board, ….)
 Indoor smoke containing many
dangerous pollutants produced by
heating / cooking / cleaning activities
 High & efficient insulation system
prevents from good aeration / ventilation
leading to accumulation of these
pollutants in the house
 Most heaviest pollutants accumulate on
surfaces due to migration of solvent &
plasticizer, creating “fogging” effect

VINNAPAS® VAE technology for low VOC emission paints
definition of VOC in water borne coatings
Emissions:
DIN EN ISO 16000 (chamber test)
ASTM D-5116
Volatile andCompounds
Organic ASTM D-6670
Liquid paint:
ISO 11890-2 (GC-Direct Injection)
ISO 17895 (In-Can VOC)

Concerns about in-can-VOC in Europe
EU deco paint directive:

< 30 g/l (approx. 21000 ppm)
ISO 11890-2:
“mandatory but not labeling”
< 1 g/l (approx. 700 ppm)

DIN EN ISO 17895
VdL
< 15 g/l (approx. 11000 ppm)

ISO 11890-2

VINNAPAS® VAE technology for indoor paints –
VOC after ISO 11890-2 (GC – direct injection)
VINNAPAS® EP 3360 SA Comp. 1 SA Comp. 2
 VINNAPAS® EP 3360 shows less impurities.

VINNAPAS® VAE technology for low-VOC emission paints –
definition of VOC in water-borne coatings
Definition after DIN EN ISO 16000-6 (for emissions):
SVOC – semi-volatile organic compound:

 Organic compound whose boiling point is in the range from
(240 °C to 260 °C) to (380 °C to 400 °C)
VOC – volatile organic compound:

(50 °C to 100 °C) to (240 °C to 260 °C)
VVOC – very volatile organic compound:

< 0 °C to (50 °C to 100 °C)
TVOC – total volatile organic compound:

 The sum of volatile organic compounds, which elute on TENAX TA between
and including n-hexane (C6H14; 69 °C) and n-hexadecane (C16H34; 287 °C)

concerns about VOC emissions in Europe
Optional labels:
Requirements for low emission

construction products:
CH2O < 50 µg/m3 (24 h)
123
TVOC < 300 µg/m3 (72 h)
1 3 7
TSVOC < 100 µg/m3 (72 h)
4
2 Worldwide 145 low emission
construction products in the market
(2014*)
Additionally: USA: 1 Jordan: 4
* Information courtesy of TÜV SÜD Industrie Service GmbH

Mandatory label
Decree 2011-321
NOR: DEVL1104875A
Country: France
Applies to: construction, decoration
and furnishing products
Since 01.09.2013
Guideline
DIN EN ISO 16000
Similar to AgBB and DIBt
Evaluation after 28 days

Mandatory label
Decree 2011-321, NOR: DEVL1104875A, classification criteria [µg/m3]
C B A A+
Formaldehyde > 120 < 120 < 60 < 10
Acetaldehyde > 400 < 400 < 300 < 200
Toluene > 600 < 600 < 450 < 300
Tetrachrloroethylene > 500 < 500 < 350 < 250
Xylene > 400 < 400 < 300 < 200
1,2,4-Trimethylbenzene > 2000 < 2000 < 1500 < 1000
1,4-Dichlorobenzene > 120 < 120 < 90 < 60
Ethylbenzene > 1500 < 1500 < 1000 < 750
2-Butoxyethanol > 2000 < 2000 < 1500 < 1000
Styrene > 500 < 500 < 350 < 250
TVOC > 2000 < 2000 < 1500 <1000

results of VOC emissions in paints
PVC 45% PVC 75%

Recipe: LA007MM
Water 264 320 Dispersions:
Tylose MH 30000 YP2 4 4
 Standard VAE
Calgon N, (10%) 10 10 (MFFT = 2 °C; Tg = 10 °C)
Lopon 890 4 4
Agitan 295
 Standard SA
1 1
Kronos 2310
(MFFT = 20 °C; Tg = 22 °C)
171 171
Durcal 2
Coalescent: Texanol
31 58
Omyacarb 15 GU 90 162
Dorkafill 600 59 103
Agitan 295 1 1
Dispersion (50%) 302 121
Coapur XS 71 4 3
Water 59 42
1000 1000

results of VOC emissions in paints
Verification of results with TÜV SÜD:
Satin paint LA007MM (basis standard SA)
Satin paint LA007MM (basis standard VAE)

summary
Binders based on VAE technology are

an assertive option to
 formulate low-VOC emission paints,
 complying with strict requirements of
existing eco-label and legislations in
the European modern paint industry
 without losing performance.

Today labels / regulations are not only focused on solvent
content …
()
APEOs
Formaldehyde Renewables
()
VOC TiO2
Fitness for use Heavy metals

Solvents criteria:
e.g. spreading
rate, abrasion,
water resistance, White pigments
Plasticizers adhesion,
weathering, …
Conalescing Dangerous substances

agents
Note*:
Anti-freeze additives Biocides VOC = volatile organic compound

VAH = volatile aromatic hydrocarbon
()
VAH APEO = alkyl phenol ethoxylate

Mega trend sustainable development –
topics for decorative coatings
 Rising crude oil prices /

energy prices
 Raw material availability
 VOC reduction / co-solvents
 Low formaldehyde
 APEO absence
 Low energy consumption
 Low carbon footprint
 Higher efficiency (less binder)
 Longer lifetimes
 Eco-friendly packaging

Niche, trends and megatrends ….?
… can be global
… can be local
Germany:
 Paints based on renewable raw materials
 Biocide-free paints
Hungary:
 VOC- and plasticizer-free?
 VOC-emission-free?

What’s renewable?
Renewable raw materials were recognized in the ECO label (Switzerland)

Paints of the category A have to contain more than 95% of renewable raw materials
respectively mineral raw materials (all inorganic raw materials of minerals or rocks,
which exists in the nature or which are produced by them) and water, which are
available unlimited. Hydrocarbons are not integrated to mineral raw materials.
 Limitation of binder (not more than 10% of a 50% dispersion)
“FARBE, AUSBAU & FASSADE 2016” in Munich

 Presentation of the CapaGeo-paint line
 The binder is produced by 100% of renewable raw materials (mass balance

approach)

Mass balance approach
Bio acetic acid Conventional ethylene Bio VAE via certification
Conventional acetic acid VAM plant VAE plant Conventional VAE

Conventional
 No separation
of acetic acid by origin possible!
Acetic Acid
 Biomass input = renewable VAE output via certification
VAM Plant

Interior paints for allergy sufferers (CIT, MIT, BIT …)
„Biocide-free“ interior paints*
1. Dispersion paints with high pH (approx. < 11.5)
 Emulsion paint + approx. 2% waterglas (Patent: EP 1 297 079)
 Emulsion paint + approx. 2% potassium methyl siliconate (Patent: DE 10 2014 013 455
and DE 2016 002 221 respectively WO 2017144694
 Biocide free (criteria of the Blue Angel): < 2 ppm BIT, < 2 ppm MIT, < 0.5 ppm CIT
2. Dispersion modified silicate paints
 … some more solutions:
3. 2K-systems: normal interior paints + additive to destroy the biocide
4. Powder dispersion paints
* Due to that the dispersion itsself is not biocide-free, the dispersion modified silicate paint as well as the dispersion paint with high pH contains a small amount of biocide(s).

VINNAPAS® VAE dispersions for decorative paints

VINNAPAS® VAE technology for indoor paints and plasters –
overview
VINNAPAS® EP 3360 EF 3777 CEZ 3031 EZ 3019 EAF 380
Monomer base VAc/E VAc/E VAc/E/VC VAc/E/VeoVA VAc/E/A
Emulsifier
PVOH + ST ST CD + ST CD + ST ST
System
APEO-free Yes Yes Yes Yes Yes
MFFT +2 °C +1 °C +2 °C +2 °C 8 / 12
Preservation BIT/MIT BIT/MIT BIT/MIT BIT/MIT/CIT
Solids Content 60 ± 1 56 ± 1 50 ± 1 50 ± 1 51 ± 1
Viscosity 3000 - 6000 150 - 1850 6000 - 12000 2100 - 3900 600 - 1600
pH 4-6 3.5 - 5.5 4-5 4.5 - 5.5 7-9
Mat paints Mat paints

Application Universal Universal Latex paints
interior/exterior interior/exterior

Formulation latitude of VINNAPAS® VAE for interior coatings
Interior paint market
Undercritical CPVC Overcritical
High gloss Semi gloss Matt

PVC [%]
20 30 40 50 60 70 80
VINNAPAS® EP 3360
VINNAPAS® EF 3777
VINNAPAS® EZ 3019
VINNAPAS® CEZ 3031

VINNAPAS® EAF 380

VINNAPAS® EP 3360 – applications
All kinds of interior applications:

(with exception of silicate systems)
 Solvent-free and plasticizer-free interior paints
 Matt paints (wall and ceiling paints)
 Glossy paints
 Latex paints
 Silicone paints
 Matt and glossy full-shade paints
 Multicolor paints (F&L March 2013)
 Interior plasters
 Scratched plasters
 Plasters with a worm structure
 Textured coatings
 Primers
 Fillers
 Glue for glass, fabrics, and wallpapers

Formulation and film properties
 Good compatibility with a wide range of raw materials
 MFFT approx. 0 °C
 Excellent film forming properties at low temperatures
 Good film formation without the addition of coalescing agents
 No solvents or plasticizers required
 Very high binding power
 High scrub resistance in matt paints (high PVC paints)
 Good gloss / blocking behavior
 Excellent thickener response

VINNAPAS® VAE dispersions –
key performance in paints / benchmarking
High scrub resistance Ingredient Parts

 Tested in a matt paint according to Water x
RR 53 523 09 Dispex N 40 5
Natrosol plus 430 2
 PVC = 45 - 85%
Rheolate 208 2
NaOH 10% 1
Addid 800 1
Kronos 2300 71
Mistron 754 G 71
Omyalite 90 142
Omyacarb 2 GU 261
Arbocel BE 600/30 PU 40
Parmetol DF 12 2
Dispersion x
Total 1,000

Equipment for the determination of scrub resistance
DIN 53 778 part 2 EN ISO 11 998


Equipment for the determination of scrub resistance OF SC


High scrub resistance

Scrub resistance of VINNAPAS® EP 3360, VINNAPAS® EF 3777 and
VINNAPAS® EZ 3010* as a function of the PVC (RR 53 523 09 test procedure)
250
Loss of Thickness [µm]
200
150
100
EZ 3010
50
EF 3777
0 EP 3360
30 40 50 60 70 80 90
PVC [%]
*New version available

Excellent film forming properties at low temperatures

Scrub resistance of VINNAPAS® EP 3360 as a function of the PVC and
temperature (RR 53 523 09 test procedure)
80
Loss of Thickness [µm]
70
60
50
40
30
20
23°C
10
0 +5°C
45 50 55 60 65 70 75 80 85
PVC [%]

VINNAPAS® EP 3360 Competitor SA
 Emulsifier system: PVOH + ST  Emulsifier system: ST
 VINNAPAS® EP 3360 exhibits excellent hiding power.

Hiding power VINNAPAS® EP 3360 versus SA
99,7
Contrast ratio
99,6
99,5
99,4
99,3
99,2
99,1
99,0
98,9
6,0 6,5 7,0 7,5 8,0 8,5 9,0 9,5
Spreading rate [m2/liter]
Standard VAE Standard SA High performance SA EP 3888 ® EP 3360
VINNAPAS

High performance VAE dispersions like

VINNAPAS® EP 3360 have in high
PVC paints a much better hiding power
than styrene / acrylics at the same
scrub resistance!

Equipment for the determination of sheen respectively gloss
EN ISO 13 300
 Mat < 10 units at 85°
 Dead mat < 5 units at 85°

Low sheen in matt paints

Sheen (gloss 85) as a function of the PVC
Sheen (85)
4,5
4,0
3,5
3,0
2,5
2,0
1,5
30 40 50 60 70 80
PVC [%]
EP 3360
3888 EF 3777 EZ 3010*
* Newer version available

 Excellent color strength
 Excellent color stability, even in matt

interior paints After 6 weeks on the window
Competitor VINNAPAS®
binder EP 3360

VINNAPAS® EP 3360 shows advantage in wet adhesion on
glass plate substrate in comparison to styrene acrylic
Results after 1 day drying and water Results after 1 day drying and water
soak test soak test
 60% PVC formulation  70% PVC formulation
7 days 30 min. 7 days 1 hour
VINNAPAS® Styrene VINNAPAS® Styrene

EP 3360 acrylic EP 3360 acrylic

VAEs offer advantage in touch-up
Touch-up refers to the ability of a paint VAE

to maintain uniform appearance and
sheen regardless of application Low
method or temperature at which a temp.
second coat of paint is applied over the
first coat
Ambient
temp.

VINNAPAS® EP 3360 – value in use
State of the art VAE regarding prize & performance

 Performance features
 High scrub resistance
 Excellent thickener response
 Excellent color stability
 High hiding power

 Low overall formulation costs
 No coalescent agent demand
 Environmentally friendliness
 Low odor, low VOC, APEO-free

 Complies with EU directives and ECO labels

Thank
THANKyou for your attention
YOU!!


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CREATING TOMORROW`S SOLUTIONS

VINNAPAS® VAE technology for environmentally-friendly

Hungary, Dr. Udo Kotschi, March 2018

Hungary, Dr. Udo Kotschi, March 2018

Vinyl acetate (VAM) Ethylene

Hungary, Dr. Udo Kotschi, March 2018

Tg of copolymers depends on polymer composition (Fox equation)

Hungary, Dr. Udo Kotschi, March 2018

Vinyl acetate – ethylene 1,03 0,88

Vinyl acetate – vinyl chloride 0,25 1,64

Vinyl acetate – butyl acrylate 0,018 3,48

Vinyl acetate – methyl methacrylate 0,03 26

Vinyl acetate – styrene 0,01 56

Hungary, Dr. Udo Kotschi, March 2018

Equal reactivity - VAc-E-VAc-E-VAc-E-VAc-E-VAc-E-VAc-E-VAc-

Unequal reactivity - VAc-VAc-VAc-VAc-VAc-BA-BA-BA-BA-BA

Hungary, Dr. Udo Kotschi, March 2018

Hungary, Dr. Udo Kotschi, March 2018

Hungary, Dr. Udo Kotschi, March 2018

 Protect polymer particles during transportation

 Control of properties (chemical compatibility, water resistance, etc.)

Type of protection systems

Hungary, Dr. Udo Kotschi, March 2018

The process and apparatus used depend on the kind of monomers

 Vinyl acetate / ethylene dispersions (VAEs) are sometimes also called

Result: dispersion of polymer VAE particles in water

Hungary, Dr. Udo Kotschi, March 2018

Dispersions with ethylene; high demands on equipment

Ethylene Vinyl acetate, Silo

Source: Wacker Chemie AG

Hungary, Dr. Udo Kotschi, March 2018

Hungary, Dr. Udo Kotschi, March 2018

 SodaInfluence of vinylic co-monomers on glass transition temperature of

VAc/ E VAc/ VeoVa10 VAc/ VL VAc/ EHA Vac / BA

Hungary, Dr. Udo Kotschi, March 2018

 The process of film formation only occurs over a defined temperature.

 The MFFT depends on

Hungary, Dr. Udo Kotschi, March 2018

 A property of the dispersion  A property of the dispersion

Hungary, Dr. Udo Kotschi, March 2018

VAE forms film at low temperatures w/o coalescent:

Hungary, Dr. Udo Kotschi, March 2018

VAE forms film at low temperatures w/o coalescent:

Hungary, Dr. Udo Kotschi, March 2018

Hungary, Dr. Udo Kotschi, March 2018

In VAE, water functions as a coalescing aid (hydroplastification!)

 No additional coalescing agent

 No migration (no fogging)

 Film formation at low temperatures (< 5 °C)

 VAE – the best option for modern low VOC paints

Hungary, Dr. Udo Kotschi, March 2018

Hungary, Dr. Udo Kotschi, March 2018

Hungary, Dr. Udo Kotschi, March 2018

 NOx produced by combustion

 Solvents from various chemicals

… leads to formation of summer smog

 E.g. allergy, asthma, heart attacks and

Hungary, Dr. Udo Kotschi, March 2018

Most important sources of organic

 Materials equipments (adhesives, caulks,

Hungary, Dr. Udo Kotschi, March 2018

Hungary, Dr. Udo Kotschi, March 2018

EU deco paint directive:

< 1 g/l (approx. 700 ppm)