Note: Descriptions are shown in the official language in which they were submitted.
2~9'~Z~
This invention relates to resinous compositions and particularly to
powder coating compositions.
Powder coating compositions are being used in increasing amounts
and in an increasing number of applications~ They have major advantages but
S due to their methods of application the coatings produced tend to be glossy
rather than of a matt finish~ There is a desirability to obtain matt finishes~
According to the present invention a powder coating composition
comprises a substantially dry particulate mixture of a thermosetting resin or
of a thermoplastic resin and vesiculated polymer granules having a volume
10 mean diameter of from 3 to 30 microns and formed of a polymer material
that is not melted or not substantially degraded respectively under any
conditions of temperature and time required to prepare said composition
and also to cure said thermosetting resin composition and under any
conditions of temperature and time required for the application of said
15 thermoplastic resin composition to a substrate and the amount of the
polymer granules being less than 40% by volume of said mixture.
The powder coating compositions of the present invention are based
on a resin which will be either a thermosetting resin or a thermoplastic resin
but con~positions based on thermosetting resins are preferred.
20 Thermosetting resins are those which when cured, usually through the action
of a curing agent, do not melt or otherwise soften on heating.
Generally speaking typical thermosetting resins are epoxy resins,
polyurethanes, polyester resins, epoxy-polyester hybrid resins and acrylic
resins. Epoxy resins are available which cure through the action of a curing
25 agent at various rates depending also on the curing temperature.
Compositions which melt, fuse and cure in 60 seconds or less are obtainable.
20094Z2
Typically curing agents based on dicyandiamide can be used particularly the
modified and substituted types.
Polyester resins such as saturated oil-free resins based on isophthalic
or terephthalic acids reacted with diols to produce hydroxyl-terminated resins
5 can be used. Such resins can be cured by reaction with an amino resin e.g.
melamine-formaldehyde resin. Polyester resins with free hydroxyl groups can
be cured with isocyanates, such as isophorone diisocyanate which is blocked
with a blocking agent, e.g. caprolactam. Such cured resins contain urethane
groups and, strictly speaking, are polyurethanes. Other polyesters containing
10 carboxyl groups can be used and these can be cured using polyepoxides, e.g.
triglycidyl isocyanurate.
Polyester-hybrids can be used as thermosetting resins and can be the
reaction product of an epoxy resin and a polyester.
Thermosetting acrylic resins such as those obtained by polymerising a
15 methacrylate on to an acrylic backbone can be used. Dibasic acids can be
used for cross-linking or curing the resin. Other suitable curing agents are
carboxy-terminated polymers.
Thermoplastic resins which can be used to form the powder coating
composition of the present invention are poly~inyl polymers, polyamides,
20 thermoplastic polyesters, polyolefines and cellulosics. Typical resins are the
plasticized polyvinyl chlorides, polyamides having suitable melting
temperatures, polyethylene, polypropylene, resins of cellulose acetate
butyrate, polyesters based on terephthalic acid and 1,4-butanediol, ethylene
chlorotrifluro-ethylene polymers, poly(vinylidene fluoride) and
25 poly(phenylene sulphide).
20~9~22
Generally speaking the powder coating compositions of the present
invention will, in the case of a thermosetting resin composition, usually also
contain a curing agent for the resin (as described hereinbefore), a flow
additive and the vesiculated polymeric granules. ln the case of a powder
5 coating composition based on a thermoplastic resin then the composition will
usually also contain a plasticizer, a stabiliser and the vesiculated polymer
granules.
The resin composition can contain pigments such as titanium dioxide
and coloured pigments and dyes as is necessary or desirable. Titanium
10 dioxide coloured dyes and/or coloured pigments can be present ir the
composition inside the vesiculated polymer granules or exterior thereof.
The granules of a polymer material contain one or more vesicles the
walls of which vesicles are provided by the polymer. Preferably the granules
are substantially spherical and the vesicles occupy form 5% to 95% of the
15 total volume of the granules. Most preferably the vesicles occupy from 20%
to 80% of the volume of the granules.
The granules have a size such that the volume mean diameter is from
3 to 30 microns and preferably from 5 to 20 microns.
Typically the vesicles in the preferred granules will be substantially
20 spherical in shape and have a diameter less than 20 microns and preferably
from 0.1 to 7 microns, most preferably 0.1 to 1 rnicron.
Generally speaking the nature of the polymer of the granules is not
critical and can be a polyester, obtained by condensation of a polycarboxylic
acid and a polyol, a polyester amide, a polyurethane, a urea-aldehyde resin, a
25 cellulosic ester or any other suitable material. Preferably the polymer is an unsaturated polyester resin cross-linked with an unsaturated monomer.
2(~09'~2
Whilst the granules can bc formed from a wide variety of different
polymers, however, the polymer should be one that is not melted, or not
substantially degraded, in the case of a thermosetting resin composition,
under the conditions of temperature and time of mixing or preparing the
S composition and later curing and, in the case of a thermoplastic composition,
under the conditions of temperature and time for the application of the
composition to a substrate.
Other types of polymer particles which may be used in the present
invention are those known as water-insoluble core-sheath polymer particles
and particularly those having a single vesicle per particle. In such particles
the core is formed of polymeric material which will swell on contact with an
appropriate substance and the sheath is formed of another polymeric
material which is permeable to the substance required to react with the core.
The polymeric granules, if desired, can contain a pigment such as
titanium dioxide pigment which can be present in the vesicles, or in the
polyrneric material or in both.
The granules can be formed by any suitable method but usually will
involve the formation of a water-in-oil emulsion of a polymeric material, such
as a polyester resin dissolved in an oil material e.g. styrene or a cross-linking
monomer. This emulsion is then dispersed in a further aqueous phase.
Polymerisation produces an aqueous dispersion of polymer granules having
vesicles.
The aqueous dispersion of polymer granules prepared by the
preferred process can be dried by the process as described in patent
specification No. GB 2 20S 154A and the dried composition then used tO
manufacture the powder coating composition. In the process described and
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claimed in specification GB 2 205 154A the aqueous dispersion is dried by
heating in a non-oxygen containing atmosphere under such conditions of
time and temperature that substantial deterioration of said particles is
minimised.
When the polymer granules contain a pigment then the amount of the
pigment can be from 1% to 60% by weight of the weight of the granules,
preferably from 5% by weight to 45% by weight.
The amount of the polymer granules in the powder coating
composition can vary over a wide range but should be less than 40% by
volume of the composition and preferably from 5% to 30% by volume.
Generally speaking there are two main methods for the manufacture
of powder coating compositions; namely a melt-mixing process or a dry-
blending process.
In a melt mixing process the resin, the vesiculated polymer granules
and any other agents are mixed together in a dry form and then heated while
undergoing mixing or extrusion prior to cooling. The heating should be
sufficient to melt the resin in the mixture but not the granules and also the
temperature and time is not sufficient to introduce unacceptable premature
curing of a thermosetting resin composition. The extruded or otherwise
mixed composition is cooled and granulated and milled to a desired final
particle size. If desired any desired final addit*es can be introduced into the
composition prior to packaging.
In a dry blending process the resin in finely divided form is mixed with
the vesiculated polymer granules and any other desired ingredients and
mixed together in a high intensity mixer. The mixed composition is cooled
and any desired post blending additions made. If desired the mixed
2~0942
composition may be classified to remove undesired oversized or undersized
particles prior to packing.
The powder coating compositions of the present invention can be
used for a wide variety of purposes and applied by any of the widely used
techniques such as electrostatic spray coating, fluid bed coating, electrostaticfluid bed coating and hot flocking. Electrostatic spray coating is the
preferred manner of application.
It will be appreciated that the powder coating compositions of the
present invention are substantially dry particulate mixtures and are
substantially free of solvents or dispersion media.
Coated products are produced having a matt finish with an even non-
blotchy appearance. Prior to the use of vesiculated polymer granules matt
finished products have not possessed the necessary appearance and some
have had an uneven blotchy finish.
The products of the present invention find use for coating a wide
range of products to be used indoors and outdoors.
The invention is illustrated in the following Examples in which all
parts are by weight.
EXAMPLE 1 (Production of Beads)
An unsaturated polyester resin was prepared by condensing together
maleic anhydride, phthalic anhydride and propylene glycol in the molar ratio
3:1:4.5. The product had an acid value of 16 mg KOH per grarn of solid
resin.
Into 44 parts of a 57% weight solids solution of the above resin in
styrene was milled 3.5 parts of titanium dioxide pigment obtainable under the
name TIOXIDE R-HD6 and 0.18 parts of magnesium oxide, until they were
2(~ 2~
thoroughly dispersed (about 30 minutes). To this mLxture was added 20 parts
of styrene and 4.9 parts of hot water (around 80C), and n~lling was
continued for 1 minute. This oil phase was then left to stand for one hour.
Separately, 0.6 parts of a 90% weight solids aqueous solution of an
ammonium nonylphenol ethoxylate sulphate surfactant were mixed with 0.18
parts of industrial methylated spirits and 0.42 parts of water. This was rnilledwith 42 parts of water at 50C, to give an aqueous phase, which was slowly
added to the oil phase with stirring. The mixture formed was milled for 10
minutes to give a water-in-oil emulsion.
45.5 parts of this emulsion were immediately added to a further
aqueous phase, containing 5 parts of a 7.5% weight solids solution of
polyvinylalcohol (as stabiliser), 1 part of a 1.5% weight solids solution of
hydroxyethyl cellulose thickener and 80 parts of water, and was milled for 3
minutes, at which point a water-in-oil-in-water system had formed, with the
oil globules averaging around 11 rnicrons in diameter.
;~ 28 parts of hot water were then added, with minimum possible milling,
followed by 0.006 parts of ferrous sulphate, dissolved in a small quantity of
water, 0.1 parts of diethylenetriamine, also dissolved in a small quantity of
water, and 0.156 parts of cumene hydroperoxide. The slurry was left
undisturbed overnight and exothermed to over 50C, ensuring complete
curing of the unsaturated polyester. This gave a 16.1% weight solids slurry of
cross-linked vesiculated pigmented polyester resin beads.
This slurry was dried by the method described and claimed in ~atent
application GB 2 205 154A, as follows. To 4000 parts of slurry were added
15 parts of 10% ammonia solution and 40 parts of a 5% solution of the
flocculating agent. This flocculating agent is the mono-acetate salt of a
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diamine derived from a fatty acid. The slurry was then heated to 70C and
stirred ulltil flocculation occurred. The batch was filtered through a
conventional vacuum filter, and was washed with clean water until no further
poly(vinyl alcohol) could be detected in the filtrate. Testing for poly(vinyl
S alcohol) consisted of rn~xing a sample of the filtrate with ten times its volume
of acetone, whereupon any poly(vinyl alcohol) present is precipitated as a
white turbidity. The resulting filter cake contained 18.4% by weight of beads
solids.
2 kg of filter cake was broken up and placed on a tray in an oven
equipped with a thermostat and able to be flushed through with nitrogen gas.
The cake was then heated to 110C in an atmosphere of nitrogen for 16
hours, after which time no further weight loss could be detected.
The dried beads formed a soft, friable white mass, which could be
brushed through a sieve of aperture 106 microns wi~hout leaving a residue.
Example 2 (Standard)
A conventional powder coating ~ith a pvc (pigment volume
concentration) of 15% was made by the following method. 692 parts of
prechipped epoxy resin (Dow 663U), 102 parts chipped flow control
masterbatch (5% by weight Modaflow flow control agent (a copolymer of
ethyl acrylate and 2-ethylhexyl acrylate)in Dow 663U epoxy resin), 40 parts
curing agent being an accelerated dicyandiarnide (Dow DEH 41) and 500
parts titanium dioxide pigment sold under the name TIOXlDE TR92 were
blended in a water-cooled Henschel rnixer. The blending was carried out at a
rotor speed of 1800 rpm for five minutes. The sides and rotor of the machine
were scraped down after the initial three minutes rnilling.
2(~942~
The resulting premix was extruded using a PR46 Buss Ko-Kneader,
running at slow speed, at 100C, then was cooled and chipped in a small
rotating knife Cumberland granulator. The chipped extrudate was then
ground in a mini-KEK pin-disc mill, and the powder produced was passed
5 through a 200 mesh sieve to remove any particles above 75 microns before
spraying.
The powder was applied, using a manual Volstatic electrostatic spray
unit with the voltage regulated to 90 kV negative, onto Bonderite DG12
(iron phosphate) panels. The powder was fused and cured to a continuous
coat by stoving the panels at 180C for 10 minutes. A Permascope, Type ES,
was used to measure the coating thickness; panels were selected with a cured
coating thickness of between 45 and 55 microns.
Colour measurements were made on the panels using a Gardner XL-
23 colorimeter. L and b values were measured on the CIE Lab scale. ~;losses
15 were measured using a Byk-Labotron Multigloss glossmeter.
Examples 3-6 (Invention)
A series of powder coatings was made, containing the dry vesiculated
pigmented polymer beads made in Example 1. The pigment volume
concentration was maintained at 15%, and the bead volume concentration
20 (bvc) was varied between 10% and 40%. The powder coatings were made by
the same method as was used in Example 2, with the beads added at the
same stage as the pigment. The quantities used, in parts by weight, were as
follows:
X(~0~ 2~
Example 3 4 5 6
pvc 15% 15% 15% 15%
bvc 10% 20% 30% 40%
Epoxy resin 613 531 449 367
5Flow control masterbatch 90 78 66 54
Curing agent 35 30 26 21
TiO2 pigment 500 500 500 500
Beads 30.4 60.7 91.4 121.4
Testing was carried out as in Example 2. The results are tabulated below.
10 Example 7 (Comparator)
A further powder coating was made up, with an inorganic extender
(calcium carbonate, Durcal 5), of substantially the same size as the beads,
used in their place. The pigment volume concentration was maintained at
15%, and an extender volume concentration (evc) of 20% was used. The
15 powder coating was made by the same method as was used in Example 2.
The quantities used, in parts by weight, were as follows:
Example 7
pvc 15%
evc 20%
20Epoxy resin 531
Flow control masterbatch 78
Curing agent 30
TiO2 pigment 500
Extender 443
2(~ 2~
12
Testing was carried out as in Example 2. The results are tabulated below.
Results of Examples 2-7
Example pvc bvc evc L b20 gloss 60 gloss
2 15~o - - 94.8 0.4 77 98
3 l5~o 10% - 94.9 1.7 32 63
4 15% 20% - 94.9 2.9 9 32
15% 30~o - 94.9 3.6 2 8
6 15% 40% - 92.0 6.4 1 2
7 15% - 20% 93.6 0.6 29 75
10 Example 6, with 40% bvc, had not fused into a continuous coating, and was
not a usable system, therefore. Example 7, with 20% evc, had a substantially
lower brightness than the standard, Example 2, or than the powder coating
with an equivalent volume of beads, Example 4. Its gloss was far higher than
that in Example 4, also, the beads evidently being the superior matting agent.
The increase in b value (i.e yellow tint) with increasing bvc was not due to
thermal degradation of the beads, as a sample of beads heated under the
same conditions showed very little change in colour. It is believed that the
particular curing agent used in these examples (Dow DEH41) is an amine.
Amines in general are known to interact with polyesters on heating to
produce yellowish or brownish products.
Example 8 (Standard)
A conventional powder coating with a pvc of 15% was made by the
following method. 691 parts of prechipped polyester resin (Uralac P2400,
from DSM Resins), 58 parts triglycidyl isocyanurate (TGIC, Araldite PT810,
from Ciba-Geigy), 93 parts chipped flow modifier (Urad P2518, from DSM
Resins), and 500 parts of a general purpose titanium dioxide pigment sold
2(~t~9~2
under the name TIOXIDE TR92 were blended in a water-cooled Henschel
mixer. The blending was carried out at a rotor speed of 1800 rpm for five
minutes. The sides and rotor o~ the machine were scraped down after an
initial three minutes milling period.
S The resulting premix was extruded using an extruder (PR46 Buss Ko-
Kneader), running at slow speed, at 100C, then was cooled and chipped in a
small rotating knife Cumberland granulator. The chipped extrudate was then
ground in a pin-disc mill (mini-KEK), and the powder produced was passed
through a 200 mesh sieve to remove any particles above 75 microns before
spraying.
The powder was applied, using a manual ele~trostatic spray unit
(Volstatic) with the voltage regulated to 90 kV negative, on to iron
phosphate panels (Bonderite DG 12). The powder was fused and cured to a
continuous coating by stoving the panels at 200C for 10 minutes. A
Permascope, Type ES, was used to measure the coating thickness, panels
were selected with a cured coating thickness of betwen 45 and 55 microns.
Colour measurements were made on the panels using Gardner XL-23
colorimeter. L and b values were measured on the CIE Lab scale. Glosses
were measured using a Byk-Labotron Multigloss glossmeter.
Examples 9-10 (Invention)
Two powder coatings were made, containing the dry vesiculated
pigmented polymer beads made in Example 1. The pigment volume
concentration was maintained at 15%, and the bead volume concentration
(bvc) was set at 10% and 20%. The powder coatings were made by the same
method as was used in Example 8, with the beads added at the same stage as
the pigment. The quantities used, in parts by weight, were as follows:
X0(~9422
14
Example 9 10
pvc 15% 15%
bvc 10% 20%
Polyester resin 615 533
S TGIC 52 45
Flow modifier 83 72
TiO2 pigment 500 500
Beads 30.8 61.6
The testing was carried out as in Example 8. The results are tabulated
10 below.
Example 11 (Comparator)
A further powder coating was made-up, with an inorganic extender
(calcium carbonate, Darcal 5), of substantially the same size as the beads,
used in their place. The pigment volume concentration was maintained at
15 15%, and an extender volume concentration (evc) of 20% was used. The
powder coating was made by the same method as was used in Example 8.
The quantities used in parts by weight, were as follows:
Example 11
pvc 15%
evc 20%
Polyester resin 533
TGIC 45
Flow modifier 72
TiO2 pigment 500
25Extender 450
~094
Testing was carried out as in Example 8. The results are tabulated
below.
Examples 12-13 (Invention; dry blending)
Further powder coatings were made up at intermediate bead volume
5 concentrations, by the blending of equal volumes of two powder coating
powders at different bvcs, to give a product of effective bvc equal to the
mean of the individual bvcs. As a check, a blend was made of the 20% bvc
system and the 0% bvc (standard) system, giving an effective bvc of 10%.
This performed identically to the powder coating made ab inito at 10% bvc.
10 Therefore, the blends of 0% bvc and 10% bvc powders (giving an effective
bvc of 5%) and of 10% bvc and 20% bvc powders (giving an effective bvc of
15%) were considered to be equivalent to powder coatings made ab inito at
5% bvc and 15 % bvc respectively. The powders were applied and tested as
in Example 8. The results are tabulated below.
Results of Examples 8-13
Example pvc bvc evc L b20 gloss 60 gloss
8 15 % - - 96.1 0.3 87 97
12 15 % 5 % - 96.4 0.6 48 74
9 15% 10% - 96.3 0.8 24 51
13 15% 15% - 96.4 0.~ 8 27
15 % 20% - 96.4 1.1 2 9
11 15 % - 20% 94.6 0.3 18 60
Example 11, with 20% evc, had a substantially lower brightness than
the standard, Example 8, or than the powder coating with an equivalent
25 volume of beads, Example 10. Its gloss was far higher than that in Example
10, also, the beads evidently being the superior matting agent. The increase
2C~U9'~Z2
in b value (i.e. yellow tint) with increasing bvc was far lower than for the
corresponding epoxy system, Example 2-6, and would not constitute a
significant drawback in use. It is noteworthy that when a graph of the 60
gloss against the bvc was plotted for Examples 8, 9, 10, 12 and 13, there was a
S linear relationship between the two variables. The majority of matting agents
have a far less straightforward effect on gloss. Thus, these beads will make it
far easier to select a bvc to give a required 60 gloss result.
