Documentos de Académico
Documentos de Profesional
Documentos de Cultura
The VOC Directive 2004/42/CE limits the amount of volatile organic compounds that can
be present in decorative coatings systems at the point of application. The first phase of this
Directive is active from January 1st 2007 and applies to decorative coatings whether they are
solvent-borne or water-borne.
This Product Guide describes the binders available from Cray Valley that can be used in
decorative coatings that will comply with this first phase of the VOC Directive for 2007.
Although some of these binders, especially the water-borne types, will be suitable for use in
2010 when the 2nd phase of the Directive is implemented, there will be a need for a new
generation of high solids solvent borne systems and improved water borne systems to meet
these demands. The latest developments and product introductions will be available on the
Cray Valley Website http://www.crayvalley.com.
Resins for use in decorative coatings are identified by the following trade names
2
WATER BORNE PRODUCTS
The CRAYMUL range of emulsion polymers are all based on APEO-free surfactants and
include the following chemistries :
Vinylic copolymers
Styrene-acrylic
Acrylic
The vinylic co-polymers are stabilised by cellulosic derivatives rather than by surfactants. This
stabilisation mechanism imparts a rheology that makes them especially suitable for wall paints
applied by roller. The vinylic emulsions are more resistant to extenders and fillers thus giving
them good stability even to reactive components such as lime.
The versatility of the styrene-acrylics offers the end-user the opportunity to use the same
binder in interior and exterior paints as defined in Categories a, b and c of the Deco Directive
2004/42/CE. The high binding power of the styrene-acrylic emulsions makes them suitable
in high PVC wall paints with excellent scrub resistance. They may also be used in the more
specialised silicate systems and roofing coatings.
A pure acrylic backbone imparts high UV resistance and non-yellowing properties. Using
special monomers and technologies, acrylics can also be designed to achieve a high level of
performance (e.g. wet adhesion, combined flexibility and blocking resistance) for demanding
applications: - wood coatings, primers and faade paints.
3
With its good adhesion on difficult substrates and excellent flexibility, CRAYMUL 2510 is well
suited for high quality exterior paints and primers. Figure 1 demonstrates the outstanding
performance of this binder after 5 years exterior exposure on wood.
Wet adhesion on alkyd Wet adhesion on alkyd Wet adhesion on alkyd Wet adhesion on alkyd
Competitive product Competitive product CRAYMUL 2510 CRAYMUL 2510
Before immersion After 30 min immersion in water Before immersion After 30 min immersion in water
Fig 2:
CRAYMUL 2510 exhibits very good wet adhesion to a variety of substrates e.g. bricks, wood,
cement. Its adhesion to alkyd based paints, as demonstrated in Figure 2, makes it suitable for
renovation over existing painted surfaces.
4
CRAYMUL 2710 and CRAYMUL 2711 Anti-stain effect in a PVC 17%
were especially developed to impart topcoat without zinc oxide on Merbau
excellent stain-blocking properties allowing
the formulation of high quality renovation
Standard Craymul 2710
paints, in particular over nicotine stained
surfaces. Figure 3 shows the blocking
properties of these emulsions against soluble
wood extractives.
The nanotechnology of CRAYMUL 2134 and CRAYMUL 2514 provides high penetration
into porous substrates such as plaster, gypsum and wood. Their extremely fine particle size
enables the formulation of clear sealers that will consolidate non-cohesive substrates and
improve the adhesion of the top coat.
To demonstrate the penetration properties, the emulsions have been diluted to 15% solids
and applied to chalk. The depth of penetration was measured 30 and 60 minutes after
application. The results are illustrated in Figure 4.
10
8
Penetration in mm
Craymul 2514 Craymul 2134 Competitor 1 Competitor 2 Commercial primer A Commercial primer B
30 min 60 min
Fig 4
5
SYNAQUA - Alkyd emulsions
The SYNAQUA range has been developed to provide alkyd technology in water. The
products in this range can be formulated into compliant paints and varnishes. High gloss for
interior paints is a particular feature of the alkyd emulsions. SYNAQUA 2080 is a short oil
alkyd emulsion that exhibits gloss levels equivalent to traditional solvent borne alkyds. Figure
5 demonstrates the gloss potential.
Pictures taken by Atomic Force Microscopy of paint films cast from water and solvent borne
systems ably demonstrate the reasons for the alkyd emulsions having the potential to give such
high gloss - even without the use of coalescent solvents (Figure 6).
Fig 5
Alkyd emulsion gloss paint Standard acrylic emulsion gloss paint Solvent borne alkyd gloss paint
Figure 6
6
The ECO-labelling scheme and National Environmental schemes such as the German Blauer
Engel, the French NF environnement and the Nordic White Swan, promote the use of products
with reduced environmental impact. SYNAQUA 2090 is a short oil alkyd emulsion that does
not require the use of any metal drier to accelerate the drying process. Paints based on
SYNAQUA 2090 will conform to these strict environmental requirements. DMTA analysis of
cured films based on SYNAQUA 2090 show that a high degree of cross-linking is obtained,
comparable to systems that contain conventional driers. Figure 7 confirms the good cross-link
density (represented by E rubber) that is obtained from a drier free system based on SYNAQUA
2090 compared to a conventional drier containing alkyd emulsion.
Synaqua 2090
250
Conventional
200 Alkyd emulsion
150
E (1.00E+04 Pa)
100
50
0
Co Co+Ca+Zr No drier Zr Ca
Figure 7
Apart from their high gloss potential both SYNAQUA 2080 and SYNAQUA 2090 can be
formulated into matt and semi gloss paints.
The Cray Valley range of alkyd emulsions can be used in combination with CRAYMUL
emulsions to provide a balance of alkyd and acrylic like properties. When blended with high
MFFT acrylic emulsions the SYNAQUA emulsions facilitate film formation without the use of
coalescent agents. Figure 8 shows the effect of the addition of SYNAQUA 2080 on the MFFT
of emulsion polymers.
7
MFT of Blends
SYNAQUA 2080 / Polymeric Dispersion
25
20 21
17
15
MFT (C) 13 14
10 11
10
6 Dispersion 1
5 5 7,5
Dispersion 2
4
0 0 0 0 0 Dispersion 3
0 10 20 30 40 50 60 70 80 90 100
% Dispersion by wt
Figure 8
penetration
of the resin
the binder
remains on
the surface
Figure 9
8
SOLVENT BORNE PRODUCTS
Products in this category are the well-established long oil and medium oil alkyds that are used
to produce interior and exterior paints, varnishes and woodstains.
Long oil alkyds are usually defined as those with a fatty acid content above 55%. The main
attributes they impart to paints are:
High gloss
Excellent flow
Good drying
Gloss retention
Medium oil alkyds, those with a fatty acid content between 45 and 55%, will exhibit faster
drying and better colour retention than the long oil types. The higher molecular weight of
these alkyds makes them suitable for use in primers and undercoats. The lower solids content
of medium oil alkyds will result in lower film build compared to that achievable with long oil
alkyds.
Flexible ALKYDS
Wood expands and contracts under natural weathering. In order to provide protection to the
wood the coating must expand and contract with the substrate. Coatings that show a high
level of cracking will allow moisture ingress and UV degradation of the wood. Flexibility
within the coating reduces film cracking.
9
SYNOLAC 6005 WD 70 retains its flexibility on UV resistance of
prolonged exterior exposure and provides the perfect SYNOLAC 6005 WD 70
protection to wood. vs standard long oil alkyd
% 35
30
25
20
15
5
10
0
Hours
Figure 11
10
Modified ALKYDS - Silicone
Silicone alkyds, when used as the sole binder, are especially suitable for application to stable
substrates such as metal, and cement. They give high durability coatings that exhibit excellent
gloss retention and chalk resistance. They are also heat resistant and have found use where
high temperatures are experienced - such as chimneys and flues. The excellent durability
makes them ideal for exterior masonry paints.
High durability wood coatings can be formulated by replacing part of the normal alkyd binder
with a silicone-modified alkyd such as SYNOLAC 5600 WD 60. A 50/50 blend of
SYNOLAC 5600 WD 60 and SYNOLAC 6005 WD 70 will exhibit in a significant
improvement in gloss retention and chalk resistance whilst retaining the flexibility to avoid
cracking. Figure 12 illustrates the elastic recovery of silicone alkyd containing systems after
accelerated aging.
70
60
50
40
% recovery
30
20
10
0
0 800 1500
(TimeHours)
Flex
Flex/Si (70/30)
Flex/Si (50/50)
Flex/Si (30/70)
100% Si
Figure 12
11
UNITHANE - Urethane modified alkyds and oils
Urethane oils are used as the sole binder where fast drying, hardness and abrasion resistance
are required. The urethane oils have the highest levels of modification and are especially
designed for parquet flooring and heavy traffic areas. They exhibit excellent chemical
resistance.
The urethane alkyds show good drying characteristics but are generally less hard than the oils.
The drying, hardness and block resistance of conventional long oil alkyds can be enhanced by
combining with a urethane alkyd such as UNITHANE 655 WD 55.
250
200
150
100
50
0
100% 50% 33% 25% 0%
% Unithane 655WD55
Figure 13
30
25
20
15
10
5
0
1 4 7 20 Days
Figure 14
The viscosity of paint will decrease when a force is applied i.e. brushing, and will increase once
the force is removed. The rate at which the paint recovers after brushing will affect the flow
and levelling characteristics of the film. Rapid recovery after removal of the force will result in
good sag resistance, whilst slow recovery, although giving good flow, will lead to an
insufficient level of sag resistance.
Viscosity
Thixotropy material
Removal of shear
Time
Fig 15
Pigment suspension
Ease of application
Non-drip application
Reduced sagging
Good levelling
CRAY VALLEY is the leading producer of thixotropic resins for supply to the decorative
coatings market. The first thixotropic resins were commercialised by Cray Valley in 1952.
13
GELKYD
SUPER GELKYD
SUPER GELKYD are urethane - urea modified alkyds. They can be used for the same
applications as GELKYD but with the following additional benefits:
SUPER GELKYD are ideal materials for imparting thixotropy into low viscosity, low solids
woodstains. Woodstains based on this technology exhibit excellent in-can stability, no
syneresis, good brush loading and application properties, and good stability to polar additives.
Their compatibility with pigment pastes makes SUPER GELKYD ideally suited for use in tinter
based systems.
The high structured non-pumpable grades can be used in paints and varnishes to produce full
non-drip coatings. Generally, 30-50% of the binder should be SUPER GELKYD. Levels of
around 10-20% are suitable for structured woodstains when used in combination with long oil
alkyds.
Pumpable grades are used at higher levels and are best suited for high-volume woodstain
manufacturers. The non-pumpable grades can only be supplied in drums. The lower structured
pumpable grades can be delivered and stored in bulk to facilitate handling and distribution.
Detailed information on the use and handling of SUPER GELKYD is available upon request.
14
RHEOLOGY AND SURFACE MODIFIERS
Cray Valleys range of CRAYVALLAC coating modifiers have been developed to help
formulators improve the performance of water-based, and solvent-based coatings. These
modifiers are divided into two categories:
Rheology modifiers for the control of flow, sedimentation and sag resistance.
Surface modifiers for the control of surface lubricity and appearance.
CRAYVALLAC ANTISETTLE CVP is a hydrogenated castor oil wax and is ideally suited for use
in decorative coatings in aliphatic solvents where high mill temperatures cannot be obtained.
CRAYVALLAC MT, an amide modified hydrogenated castor wax, offers more flexibility in the
paint manufacturing process.
CRAYVALLAC SUPER is recommended for high solids coatings that are thinned in low
polarity solvents. The effects of false body are minimised with this product, thus contributing
to the reduction in VOC.
CRAYVALLAC PA3WDA20 is a pre-activated paste in high flash low aromatic white spirit
that allows easier incorporation into pigmented systems due to the shear and friction brought
about by the pigments.
Liquid rheology modifiers provide a substantially better means of flow control and are
especially suited for non-pigmented systems such as varnishes and woodstains.
CRAYVALLAC LA-250 and CRAYVALLAC LA-350 are pourable modified liquid urea
additives for use in solvent-borne and water-borne systems respectively. They are supplied as
45% solutions in Dimethylsulfoxide.
HYCRYL 0262 is an acrylic thickener especially suited for use in the formulation of water based
wall paints.
15
CRAYVALLAC SURFACE MODIFIERS
Surface modifiers are available as both micronised powders and easy to handle water-based
and solvent-based dispersions. They provide the formulator with the following surface
enhancements:
Powder waxes are readily incorporated into coating formulations using for example high-speed
dispersers. In general, micronised waxes are best incorporated by pre-mixing with the binder.
The pre-dispersed waxes (WW grades) avoid the inconvenience commonly associated with
micronised powders. By nature they are easier and more efficient to incorporate as they require
less intensive processing.
Full details of all these modifiers can be found at our dedicated CRAYVALLAC website:
http://www.crayvallac.com
16
WATER - BORNE RESINS
CRAYMUL - APEO-free Vinylic - copolymers
MAIN APPLICATION AREAS
COATINGS
COATINGS
SOLVENT
EXTERIOR
INTERIOR
TYPICAL
PRIMERS
SILICATE
WOOD
STAINS
WOOD
PAINTS
- FREE
ROOF
REFERENCE MODIFICATION STABILIZING SOLID BROOKFIELD pH MFFTC SUGGESTED USES / PROPERTIES
SYSTEM CONTENT (%) VISCOSITY
(23C) mPas
2325 Versatate CD 55 4000 5 16 A higher solids binder for use in interior and exterior wall paints
17
WATER - BORNE RESINS
CRAYMUL APEO-free Styrene - Acrylic and Acrylic emulsions
MAIN APPLICATION AREAS
COATINGS
COATINGS
SOLVENT
EXTERIOR
INTERIOR
TYPICAL
PRIMERS
SILICATE
WOOD
STAINS
WOOD
PAINTS
- FREE
ROOF
REFERENCE POLYMER TYPE STABILIZING SOLID BROOKFIELD pH MFFTC SUGGESTED USES / PROPERTIES
SYSTEM CONTENT (%) VISCOSITY
(23C) mPas
Paints and masonry primers with good water and alkali resistance.
2502 Acrylic A/NI 47 <500 8.5 6
Also suitable for woodstains
18
WATER- BORNE RESINS
SYNAQUA Alkyd Emulsions
MAIN APPLICATION AREAS
EXTERIOR
INTERIOR
VARNISH
METAL
WOOD
WOOD
TYPICAL
WALL
PAINT
STAIN
REFERENCE FATTY ACID FATTY ACID AVERAGE NON VOLATILE pH SUGGESTED USES / PROPERTIES
VISCOSITY (25C
CONTENT (%) TYPE VOLATILE(%) mPa.s)
2080 40 Linoleic rich 50 Water 7 < 1000 High or semi gloss interior and exterior coatings with low
or zero VOC, very good gloss retention and very low yellowing
19
SOLVENT - BORNE RESINS
SYNOLAC Alkyd Resins - Oxidising - Medium and long oil length
MAIN APPLICATION AREAS
EXTERIOR
INTERIOR
VARNISH
FATTY
METAL
AVERAGE
WOOD
WOOD
MAX. ACID TYPICAL
WALL
PAINT
STAIN
REFERENCE ACID FATTY ACID VOLATILE SUGGESTED USES / PROPERTIES
NON VALUE VISCOSITY
CONTENT TYPE (mgKOH/g) (25C mPa.s)
(%) VOLATILE (%)
6005 WD 70* 60 Linoleic rich 70 Low aromatic white spirit 10 1500 Exterior paints, varnishes and woodstains. 2007 compliant
60 WD 70 62 Linoleic rich 70 Low aromatic white spirit 10 4500 For fast drying decorative and marine paints and varnishes as well as
high build woodstains with excellent durability and colour retention
606 WD 75 62 Sunflower 75 Low aromatic white spirit 10 4100 Compliant decorative coatings with low yellowing
and good overall performance
608 WD 75 62 Linoleic rich 75 Low aromatic white spirit 10 4500 Decorative enamels for 2007 compliance
6862 WD 60 62 TOFA 60 Low aromatic white spirit 10 7750@ 20C Decorative enamels and special effect wall paints
1180 WD 70 64 Linseed/tung 70 Low aromatic white spirit 16 2850 Phenolic modified for yacht varnishes
6868 WD 75 68 TOFA 75 Low aromatic white spirit 10 4000@ 20C All decorative coatings - compliant for 2007
20
SOLVENT - BORNE RESINS
SYNOLAC Alkyd Resins - Silicone modified
MAIN APPLICATION AREAS
EXTERIOR
INTERIOR
VARNISH
FATTY
METAL
AVERAGE
WOOD
WOOD
MAX. ACID TYPICAL
WALL
PAINT
STAIN
REFERENCE ACID FATTY ACID VOLATILE SUGGESTED USES / PROPERTIES
NON VALUE VISCOSITY
CONTENT TYPE (mgKOH/g) (25C mPa.s)
(%) VOLATILE (%)
21
SOLVENT - BORNE RESINS
UNITHANE - Urethane Resins - Alkyds and Oils
MAIN APPLICATION AREAS
FATTY
EXTERIOR
AVERAGE
INTERIOR
VARNISH
METAL
WOOD
WOOD
MAX. ACID TYPICAL
PAINT
STAIN
REFERENCE TYPE ISOCYANATE FATTY ACID ACID NON VOLATILE SUGGESTED USES / PROPERTIES
CONTENT VOLATILE VALUE VISCOSITY
TYPE TYPE (mgKOH/g) (25C mPa.s)
(%) (%)
Low aromatic Clear and pigmented finishes for interior and exterior application
644 WD 55 Alkyd Aliphatic 54 Linoleic rich 55
white spirit
5 5250
including garden furniture and marine finishing.
Low aromatic Floor paints and interior varnishes with good balance
639 WD 60 Alkyd Aromatic 59 Linoleic rich 60
white spirit
6 1500
of hardness/flexibility and adhesion
Low aromatic General purpose urethane alkyd with good abrasion resistance
655 WD 55 Alkyd Aromatic 61 Linoleic rich 55
white spirit
3 1650
and drying properties. Can be used with blending alkyds
Low aromatic
637 WD 50 Oil Aromatic 61 Linoleic rich 50
white spirit
2 2350
High urethane content oil for hardwearing parquet floor coatings
Low aromatic High gloss and matt paints for boats and frames
1077 WD 60 Oil Aromatic 66 Drying 60
white spirit
1 5750
with good durability and fast drying
22
SOLVENT - BORNE RESINS
GELKYD - Thixotropic alkyds
MAIN APPLICATION AREAS
EXTERIOR
INTERIOR
VARNISH
FATTY
METAL
AVERAGE
WOOD
WOOD
MAX. ACID TYPICAL
WALL
PAINT
STAIN
REFERENCE ACID FATTY ACID VOLATILE SUGGESTED USES / PROPERTIES
NON VALUE VISCOSITY
CONTENT TYPE (mgKOH/g) (25C mPa.s)
(%) VOLATILE (%)
500 Medium structured, high solid resin for high quality thixotropic
3605 WD 65 60 Linoleic rich 65 Low aromatic white spirit 12
(10,000 S -1 ) paints with VOC <400 g/L
675 (10,000 S-1 High structured resin for gloss and semi-gloss paints. Gives no haze
352 WD 54 62 Linoleic rich 54 Low aromatic white spirit 10
@ 50C) in dark shades and does not affect drying
23
SOLVENT - BORNE RESINS
SUPER GELKYD - Thixotropic alkyds
MAIN APPLICATION AREAS
EXTERIOR
INTERIOR
VARNISH
FATTY
METAL
AVERAGE
WOOD
WOOD
TYPICAL
WALL
PAINT
STAIN
REFERENCE ACID FATTY ACID VOLATILE SUGGESTED USES / PROPERTIES
NON VISCOSITY (25C
CONTENT TYPE mPa.s)
(%) VOLATILE (%)
6008 WD 45 52 Linoleic rich 45 Low aromatic white spirit 400 (2,500 S-1) Pumpable version of SUPER GELKYD 6006 WDA 55
supplied in low aromatic white spirit
390 W 60 63 Linoleic rich 60 White spirit 1100 (2,500 S -1) Low structure version of SUPER GELKYD 391 W 55
24
RHEOLOGY MODIFIERS
PERFORMANCE BENEFIT APPLICATIONS
VISCOSITY
SETTLING
SAGGING
VARNISHES
CORREC-
VARNISHES
PRIMERS
TROPIC
THIXO-
UNDER-
WOOD-
RATIVE
RATIVE
PAINTS
PAINTS
SOLIDS
STAINS
ALKYD
ALKYD
ALKYD
COATS
PAINTS
BORNE
BORNE
WATER
WATER
DECO-
DECO-
STAINS
ANTI-
BASED
BASED
TION
ANTI
HIGH
SUPPLY TYPICAL INCORPORATION
AND
AND
AND
REFERENCE TYPE
FORM USER LEVEL (wt%) METHOD
ANTISETTLE
CVP
Castor oil derivative Micronised powder 0.2-1.5 High shear
CRAYVALLAC Amide modified
MT castor oil derivative
Micronised powder 0.2-2.0 High shear
CRAYVALLAC
SUPER
Amide Micronised powder 0.5-2.0 High shear
CRAYVALLAC Low shear
PA3 WDA20
Amide paste Paste 0.5-2.0
and post addition
CRAYVALLAC Low shear
LA 250
Modified urea Liquid 0.1-1.0
and post addition
CRAYVALLAC Low shear
LA 350
Modified urea Liquid 0.1-2.0
and post addition
HYCRYL 0262 Acrylic emulsion Liquid Low shear
and post addition
Recommended Suitable
25
SURFACE MODIFIERS
PERFORMANCE BENEFIT
BLOCKING
ABRASION
MATTING
RUB AND
SETTLING
SCRATCH
TANCE
TANCE
TANCE
TANCE
ANTI-
RESIS-
RESIS-
RESIS-
RESIS-
ANTI-
HEAT
SUPPLY
MAR
SLIP
REFERENCE TYPE FEATURES
FORM
CRAYVALLAC
WN-1135
Modified PP Micronised wax Matting agent in wood coatings. At lower levels (0.5-1.5%)
improves slip and water resistance in coatings
CRAYVALLAC
WF-6010
PTFE/PE Micronised wax Versatile economic wax with fine particle size that offers
good lubricity, blocking and abrasion resistance
CRAYVALLAC
WW-1074
PE Aqueous dispersion High slip, abrasion and rub resistance
CRAYVALLAC
WW-1077
PTFE/PE Aqueous dispersion
Gives exceptional slip, scuff and rub resistance for demanding applications
Recommended Suitable
PP: Polypropylene
PTFE: Polytetrafluroethylene
PE: Polyethylene
26
www.crayvalley.com
CRAY VALLEY
La Dfense 2 - 12 Place de lIris
F-92062 - PARIS LA DFENSE CEDEX - FRANCE
Tel: +33 1 47 96 98 50
Fax: +33 1 47 96 99 81
DISCLAIMER: The information contained in this document is based on trials carried out by our technical centres and data selected from the literature. It is intended to provide general
information on our products and their uses. It shall in no event constitute any warranty from our part concerning specific properties of the products or their suitability for a particular
application.