WO2002036700A1 - Curable powder coating comprising copolymers of at least alkylesters and an epoxy alkylester - Google Patents

Curable powder coating comprising copolymers of at least alkylesters and an epoxy alkylester Download PDF

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Publication number
WO2002036700A1
WO2002036700A1 PCT/EP2001/011396 EP0111396W WO0236700A1 WO 2002036700 A1 WO2002036700 A1 WO 2002036700A1 EP 0111396 W EP0111396 W EP 0111396W WO 0236700 A1 WO0236700 A1 WO 0236700A1
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Prior art keywords
carbon atoms
acid
powder coating
coating compositions
curable powder
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PCT/EP2001/011396
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French (fr)
Inventor
Jean-Marc Jacques Eric Bertens
Christian Jean Charles De Cock
Helene Marie Jacqueline Claude Petit
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Resolution Research Nederland B.V.
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Priority to AU2002220582A priority Critical patent/AU2002220582A1/en
Publication of WO2002036700A1 publication Critical patent/WO2002036700A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
    • C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/068—Copolymers with monomers not covered by C09D133/06 containing glycidyl groups

Definitions

  • the invention is relating to curable powder coating compositions, derived from epoxy groups containing copolymers from ethylenically unsaturated monomers.
  • the invention is relating to 5 curable powder coating compositions comprising an epoxy group containing copolymer and an acid cross-linker.
  • Curable powder compositions were in principle known from e.g. EP-A-0773268 ; EP-A-0728163; US-A-5, 625, 028 ; Technical Bulletin of Shell Chemicals "VeoVa mass polymer 0 for outdoor durable powder coatings", August 1991, VM 5.1 and International application PCT/EP98/07331 (published as W099/33889) .
  • alkyl 5 methacrylate As monomers (b) were exemplified inter alia alkyl 5 methacrylate, wherein alkyl represented methyl, butyl, ethyl, isobutyl, 2-ethylhexyl, lauryl, stearyl, and/or styrene and/or dialkyl esters of unsaturated dibasic acid.
  • the polymerization was actually carried out in an organic solvent like xylene and in the presence of a peroxide radical polymerization catalyst.
  • a component (B) decanedicarboxylic acid was mentioned.
  • (ii) is selected from the group consisting of alkyl acrylates, alkyl methacrylates containing from 1 to 20 carbon atoms in the alkyl group, vinyl aromatic compounds and vinyl aliphatic compounds .
  • the comonomer ( ⁇ ) is preferably isobornyl methacrylate .
  • monomer component (iii) can be used a copolymerizable ethylenically unsaturated monomer different from (i) and (ii) and which is more preferably -methylstyrene dimer.
  • a copolymerizable ethylenically unsaturated monomer different from (i) and (ii) and which is more preferably -methylstyrene dimer From US-A-5, 625, 028 thermosetting resin compositions were known, which provided coatings which allegedly possessed attractive weathering properties. Said compositions comprised a semicrystalline polyester, consisting essentially of diol and/or triol residues and dicarboxylic acid residues.
  • the diol residues had been selected from the group consisting of residues of 1, 4-butanediol and 1, 6-hexanediol, and the carboxylic acid residues were consisting essentially of residues of 1, 4-cyclohexanedicarboxylic acid wherein at least 70% of said residues of 1, 4-cyclohexanedicarboxylic acid are in trans form.
  • Said polyesters had an acid number of from 30 to 100 and an inherent viscosity of from 0.1 to 0.5 dl/g measured at 25 °C in a 60/40% by weight mixture of phenol/tetrachloroethane at a concentration of 0.5 g/dl.
  • a mass copolymer LR-259 was prepared from inter alia VeoVa 10 vinyl ester monomer, styrene, methyl methacrylate, dimethyl maleate, and glycidyl methacrylate with Trigonox B (di-tert-butyl peroxide) .
  • copolymers were combined with a carboxyl- functional polyester as curing agent, prepared from hexanediol and decane dicarboxylic acid in a molar ratio of 1 mole of hexanediol per 2 moles decane dicarboxylic acid, under nitrogen purge and in reflux/azeotropic distillation equipment, using toluene as solvent, at a temperature in the range from 130 to 200 °C, in the presence of stannous octoate as catalyst and distillation of water and toluene.
  • the polyester resin showed an acid content of 207 mg KOH/g.
  • W099/33889 disclosed curable powder coating compositions, comprising: (a) a copolymer obtainable from (ai) from 5 to 10 wt% of an alkyl diester of an ethylenically unsaturated dicarboxylic acid, comprising an alkyl group, having from 1 to 4 carbon atoms; (aii) from 15 to 55 wt% of a glycidyl ester of ethyleni- cally unsaturated carboxylic acid;
  • the curing component (b) comprised a polyester resin (bii) derived from 0.2 to 0.3 mol ditrimethylol propane per mol hexahydrophthalic anhydride and having an acid value of from 4600 and 4900 mmol/kg, while the equivalent ratio between (bi) and (bii) was in the range of from 0.300 to 2.800.
  • heat curable acrylic elastomer composition comprising e.g. epoxy group containing acrylate type elastomer, polycarboxylic acid or anhydride such as tetrametylsuccinic acid, a quaternary ammonium or phosphonium compound and urea compound and from Japanese application JP-55108655 radiation resistant compositions were known, containing a copolymer of methyl-methacrylate and methacrylic ester (s) having an epoxy group, such as glycidyl methacrylate copolymer, and a dicarboxylic acid, such as 2, 5-dimethylhexanoic acid.
  • a copolymer of methyl-methacrylate and methacrylic ester (s) having an epoxy group such as glycidyl methacrylate copolymer
  • a dicarboxylic acid such as 2, 5-dimethylhexanoic acid
  • curable powder coating compositions which provide an improved combination of physical properties of the cured coating films derived therefrom, which will meet the requirements from the industrial coating industry in the near future, and more in particular the requirements to be put on automotive top coating compositions and coil coating compositions .
  • powder coating compositions which preferably can be cured at low temperatures, i.e. in the range of from 120 to 140 °C.
  • Physical properties of the cured coating films which have to be improved and/or better balanced in the final combination, are inter alia: hardness, MEK and petrol resistance, acid resistance, transparency, colouring resistance during baking, weathering resistance, mar resistance and sealer cracking resistance. Therefore it is an object of the present invention to provide curable resin powder compositions, providing cured coating films having improved one or more of the properties, as specified hereinbefore.
  • Another object of the present invention is to provide a process for the preparation of a copolymer component to be incorporated into said curable resin compositions .
  • curable resin compositions aimed at, have been surprisingly found.
  • curable powder coating compositions comprising at least:
  • alkyl ester of an ethylenically unsaturated monocarboxylic acid having from 3 to 4, and preferably 3 carbon atoms in the acid moiety, and wherein the alkyl group contains from 1 to 12 carbon atoms, and preferably from 1 to 4 carbon atoms;
  • At least one ⁇ , ⁇ , ⁇ ' , ⁇ ' -branched aliphatic dicarboxylic acid comprising from 8 to 18 carbon atoms, preferably from 10 to 18 carbon atoms.
  • Preferred embodiments of the present invention are formed by curable powder coating compositions, comprising at least:
  • alkyl ester of an ethylenically unsaturated monocarboxylic acid having from 3 to 4 and preferably 3 carbon atoms in the acid moiety, and wherein the alkyl group contains from 1 to 12 carbon atoms and preferably from 1 to 4 carbon atoms;
  • More preferred embodiments of the present invention are formed by curable powder coating compositions, comprising at least: (a) a copolymer obtainable from
  • the molar ratio between the acid groups of component (b) and epoxy groups of component (a) is in the range of from 0.70 to 1.10.
  • Preferably the molar ratio between the acid groups and epoxy groups is in the range of from 0.85 to 1.00.
  • Suitable monomers to be used as component (ai) can be selected from e.g. glycidyl methacrylate, glycidyl acrylate, glycidyl crotonate, glycidyl cinnamate, and the like. Glycidyl methacrylate or glycidyl acrylate are most preferred.
  • Suitable monomers to be used as component (aii) can be selected from e.g. methyl acrylate, ethyl acrylate, n- propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, ethyl-hexyl acrylate, isobornyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, ethylhexyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, methyl crotonate, ethyl crotonate, n-propyl crotonate, isopropyl crotonate, isobutyl cro
  • the more preferred monomers (aii) are methyl methacrylate, methyl acrylate, isobornyl acrylate or isobornyl methacrylate and the most preferred is methyl methacrylate .
  • Suitable monomers to be used as component (aiii) can be selected from e.g. styrene, vinyltoluene, dimethyl- styrene, ⁇ -methylstyrene and the like. Styrene is the most preferred monomer.
  • Monomers to be used as component (aiv) are preferably commercially available as mixtures of alkenyl esters of branched tertiary carboxylic acids, containing each from 5 to 13 carbons in the acid moiety, such as VEOVA 9, VEOVA 10 and VEOVA 11 (VEOVA is a trademark of Shell Chemical Europe Ltd.) for vinyl esters of VERSATIC acids (VERSATIC is a trademark) .
  • component (aiv) also mixtures of vinyl esters of branched tertiary carboxylic acids, having from 9 to 13 carbon atoms in their acid residue, as major component (i.e. occurring in amounts of at least 80 wt% relative to the total weight of the component (aiv) and preferably at least 90 wt%) , can be used.
  • Vinyl esters of branched tertiary carboxylic acids, having a 9 carbon atoms in their acid moiety as major component are a preferred component (aiv) for the powder coating compositions of the present invention.
  • Said preferred main component of ingredient (aiv) can be mixed with minor component (s) of vinyl esters of other branched acids ( ⁇ 20 wt% and more preferably ⁇ 10 wt%) .
  • vinyl esters of other branched acids ⁇ 20 wt% and more preferably ⁇ 10 wt%)
  • vinyl esters of branched acids having 5, 10, 11 or 13 carbon atoms in their acid residues .
  • Most preferably vinyl esters of branched carboxylic acids will be applied as sole comonomer (aiv) , which contain 9 carbon atoms in the acid residue only.
  • Suitable monomers to be used as component (av) can be selected from e.g. dimethyl maleate, diethyl maleate, di- n-propyl maleate, di-n-butyl maleate, di-isopropyl maleate, dimethyl itaconate, diethyl itaconate, di-n- propyl itaconate, di-n-butyl itaconate, di-isopropyl itaconate, di-isobutyl itaconate, and the like.
  • Preferred monomers ai) are dimethyl maleate or diethyl maleate, of which dimethyl maleate is most preferred.
  • Preferred proportions of component (ai) are in the range of from 17 to 45 wt%.
  • Preferred proportions of component (aii) are in the range of from 10 to 30 wt%.
  • Preferred proportions of component (aiii) are in the range of from 20 to 43 wt%.
  • Preferred proportions of component (aiv) are in the range of from 10 to 30 wt%.
  • Preferred proportions of component (av) are in the range of from 6 to 9 wt% .
  • Suitable representatives of component (b) are selected from ⁇ , ⁇ , ⁇ / , ⁇ -branched dicarboxylic acids of the formulae:
  • n is an integer in the range from 1 to 6 and preferably from 2 to 6 and most preferably from 2 to 4, and mixtures of said acids.
  • More preferred representatives are 2,2,6,6- tetramethyl pimelic acid, 2, 2, 5-trimethyl-5-ethyl adipic acid, 2, 2, 5, 5-tetramethyl adipic acid, 2, 2, 4-trimethyl, 4-ethyl glutaric acid or mixtures thereof.
  • di-acids to be used are 2,2,6,6- tetramethyl pimelic acid and 2, 2, 5-trimethyl-5-ethyl adipic acid, or mixtures thereof.
  • copolymer components (a) are to be included, which show an epoxy group content in the range of from 1000 to 4000 meq/kg and preferably from 2000 to 3000 " meq/kg.
  • the weight average molecular weight of the copolymer (a) components is in the range of from 2000 to 10.000 and preferably from 4000 to 7000. More preferably the copolymer components (a) are prepared by mass (or bulk) polymerization, of the components (ai) through (av) without any solvent, at a temperature in the range of from 155 to 180 °C, and in the presence of a radical polymerization catalyst such as peroxides, diazo compounds and the like of which the peroxide catalysts are preferred e.g. di-tert-butyl peroxide, di-tert . -amyl peroxide.
  • a radical polymerization catalyst such as peroxides, diazo compounds and the like of which the peroxide catalysts are preferred e.g. di-tert-butyl peroxide, di-tert . -amyl peroxide.
  • curable powder compositions of the present invention is formed by the lower curing temperature, which has to be applied, e.g. 140 °C during 30 minutes instead of the conventional temperature of 175 and higher, in combination with a good flow-out and a good stability.
  • curing catalysts can be included in the powder coating compositions in order to reach the desired low temperature curing, i.e. in the temperature range of from 100 to 140 °C.
  • said curing catalysts are the quaternary ammonium salts, such as tetra (2-4-alkyl) - ammonium halide and more in particular e.g. tetra- butylammonium bromide, tetrabutylammoniumchloride, or tin salts of carboxylic acids having from 6-16 carbon atoms, such as tin octoate.
  • the reactor is charged with the vinyl ester of tertiary branched acid monomer and dialkyl ester of ethylenically unsaturated diacid in amounts listed in the table 1 hereinafter, and heated to a temperature to 155 °C under a nitrogen blanket.
  • # resin has been made at 175 °C.
  • Cross-linking agents applied are a 50/50 mixture of 2, 2, 6, 6-tetramethyl pimelic acid and 2, 2 , 5-trimethyl-5- ethyl adipic acid, further mentioned DTA, and the dodecanoic acid, which was generally applied for a long time as cross-linking agent for corresponding prior art powder coating compositions.
  • the polymer and the cross-linker were separately coarse ground before extrusion.
  • the polymer and cross- linker were blended with degassing agent (1% benzoin) and flow control agent (1.5% Modaflow powder III) for about 30 minutes on a roller bank.
  • the mix was then extruded using a Buss PLK46 single screw extruder.
  • the extruder was operated in a temperature range of 70-90 °C with a screw speed of 80 r.p.m.
  • the resulting extrudate was flattened using cooled rolls, stabilized for 24 hours and fine milled in an Alpine AFG jet grinding mill at 1790 r.p.m. to obtain an average powder particle size below 100 micron.

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Abstract

Curable powder coating compositions, comprising at least: (a) a copolymer obtainable from at least (ai) a glycidyl ester of ethylenically unsaturated carboxylic acid; (aii) an alkyl ester of an ethylenically unsaturated monocarboxylic acid, having from 3 to 4, and preferably 3 carbon atoms in the acid moiety, and wherein the alkyl group contains from 1 to 12 carbon atoms, and preferably from 1 to 4 carbon atoms; and (b) at least one α,α,α',α'-branched aliphatic dicarboxylic acid, comprising from 8 to 18 carbon atoms, preferably from 10 to 18 carbon atoms, and shaped articles, on which said powder coating compositions have been applied in cured form.

Description

CURABLE POWDER COATING COMPRISING COPOLYMERS OF AT LEAST ALKYLESTERS AND AN EPO XY ALKYLESTERS
The invention is relating to curable powder coating compositions, derived from epoxy groups containing copolymers from ethylenically unsaturated monomers.
More in particular the invention is relating to 5 curable powder coating compositions comprising an epoxy group containing copolymer and an acid cross-linker.
Curable powder compositions were in principle known from e.g. EP-A-0773268 ; EP-A-0728163; US-A-5, 625, 028 ; Technical Bulletin of Shell Chemicals "VeoVa mass polymer 0 for outdoor durable powder coatings", August 1991, VM 5.1 and International application PCT/EP98/07331 (published as W099/33889) .
From EP-A-0773268 were known acid epoxy curing type powder coating compositions, which comprised 5 (A) an epoxy group containing acrylic resin prepared by polymerizing the monomer mixture, comprising
(a) from 35 to 65 wt% of an epoxy group containing ethylenically unsaturated monomer, and
(b) remainder amount of an ethylenically unsaturated 0 monomer which is different from the monomer (a) ,
(B) a polycarboxylic acid, and
(C) an antioxidant having a melting point of from 50 to 140 °C.
As monomers (b) were exemplified inter alia alkyl 5 methacrylate, wherein alkyl represented methyl, butyl, ethyl, isobutyl, 2-ethylhexyl, lauryl, stearyl, and/or styrene and/or dialkyl esters of unsaturated dibasic acid. The polymerization was actually carried out in an organic solvent like xylene and in the presence of a peroxide radical polymerization catalyst. A component (B) decanedicarboxylic acid was mentioned.
From EP-A-0.728163 were known powder coating compositions comprising a solid, particulate mixture of (a) 60 to 90 wt%, based on the weight of (a) and (b) of an epoxy functional copolymer having a Tg of from 25 °C to 70 °C, formed by polymerizing under free radical initiated polymerization conditions: (i) from 50 to 75 wt%, based on the weight of (i) and
(ii) of a glycidyl functional ethylenically unsaturated monomer,
(ii) from 25 to 50 wt%, based on the weight of (i) and (ii) of a copolymerizable ethylenically unsaturated monomer or mixture of monomers free of glycidyl functionality; said epoxy functional copolymer containing from 3.0 to 5.9 moles of glycidyl groups per kilogram of epoxy functional copolymer; (b) from 10 to 40 wt%, based on the weight of (a) and (b) of a polycarboxylic acid cross-linking agent; wherein the ratio of epoxy functionality is 1:0.8 to 1, and wherein the powder coating composition has a melt viscosity of less than 5 Pa . s . Preferably the copolymerizable ethylenically monomer
(ii) is selected from the group consisting of alkyl acrylates, alkyl methacrylates containing from 1 to 20 carbon atoms in the alkyl group, vinyl aromatic compounds and vinyl aliphatic compounds . The comonomer (ϋ) is preferably isobornyl methacrylate .
In addition as (co) monomer component (iii) can be used a copolymerizable ethylenically unsaturated monomer different from (i) and (ii) and which is more preferably -methylstyrene dimer. From US-A-5, 625, 028 thermosetting resin compositions were known, which provided coatings which allegedly possessed attractive weathering properties. Said compositions comprised a semicrystalline polyester, consisting essentially of diol and/or triol residues and dicarboxylic acid residues. The diol residues had been selected from the group consisting of residues of 1, 4-butanediol and 1, 6-hexanediol, and the carboxylic acid residues were consisting essentially of residues of 1, 4-cyclohexanedicarboxylic acid wherein at least 70% of said residues of 1, 4-cyclohexanedicarboxylic acid are in trans form. Said polyesters had an acid number of from 30 to 100 and an inherent viscosity of from 0.1 to 0.5 dl/g measured at 25 °C in a 60/40% by weight mixture of phenol/tetrachloroethane at a concentration of 0.5 g/dl. In Technical Bulletin of Shell Chemicals λveoVa mass polymer for outdoor durable powder coatings" , reprinted August 1991, VM 5.1 a mass copolymer LR-259 was prepared from inter alia VeoVa 10 vinyl ester monomer, styrene, methyl methacrylate, dimethyl maleate, and glycidyl methacrylate with Trigonox B (di-tert-butyl peroxide) .
These copolymers were combined with a carboxyl- functional polyester as curing agent, prepared from hexanediol and decane dicarboxylic acid in a molar ratio of 1 mole of hexanediol per 2 moles decane dicarboxylic acid, under nitrogen purge and in reflux/azeotropic distillation equipment, using toluene as solvent, at a temperature in the range from 130 to 200 °C, in the presence of stannous octoate as catalyst and distillation of water and toluene. The polyester resin showed an acid content of 207 mg KOH/g.
W099/33889 disclosed curable powder coating compositions, comprising: (a) a copolymer obtainable from (ai) from 5 to 10 wt% of an alkyl diester of an ethylenically unsaturated dicarboxylic acid, comprising an alkyl group, having from 1 to 4 carbon atoms; (aii) from 15 to 55 wt% of a glycidyl ester of ethyleni- cally unsaturated carboxylic acid;
(aiii) from 10 to 45 wt% of a phenylalkylene monomer having from 8 to 12 carbon atoms;
(aiv) from 10 to 35 wt% of an alkenyl ester of a branched tertiary carboxylic acid, the acid moiety of which contains 9 carbon atoms;
(av) from 0 to 45 wt% of an alkyl ester of an ethylenically unsaturated carboxylic acid, having from 3 to 4 carbon atoms in the acid moiety, and wherein the alkyl group contains from 1 to 12 carbon atoms, the respective percentages of the components (ai) through
(av) are relative to the total weight of the copolymer, while the sum of all actual percentages = 100%. (b) a blend of (bi) an aliphatic or cycloaliphatic dicarboxylic acid comprising from 4 to 16 carbon atoms and (bii) a polyester resin, derivable from a branched polyhydroxy alkane, having from 5 to 12 carbon atoms and an aliphatic or cycloaliphatic dicarboxylic acid, having from 4 to 16 carbon atoms, or an anhydride thereof, in a molar ratio of from 0.2 to 0.4 mol of polyhydroxyalkane per mole of aliphatic or cycloaliphatic dicarboxylic acid, the polyester (bii) having an acid value of from 4500 to 4900 mmole/kg and the blend having an acid value from 5000 to 10.000, while the molar ratio between the acid groups and epoxy groups is in the range of from 0.70 to 1.10.
More in particular, the curing component (b) comprised a polyester resin (bii) derived from 0.2 to 0.3 mol ditrimethylol propane per mol hexahydrophthalic anhydride and having an acid value of from 4600 and 4900 mmol/kg, while the equivalent ratio between (bi) and (bii) was in the range of from 0.300 to 2.800.
On the other hand were known from US 4,931,509, heat curable acrylic elastomer composition comprising e.g. epoxy group containing acrylate type elastomer, polycarboxylic acid or anhydride such as tetrametylsuccinic acid, a quaternary ammonium or phosphonium compound and urea compound and from Japanese application JP-55108655 radiation resistant compositions were known, containing a copolymer of methyl-methacrylate and methacrylic ester (s) having an epoxy group, such as glycidyl methacrylate copolymer, and a dicarboxylic acid, such as 2, 5-dimethylhexanoic acid. It will be appreciated that the physical coating properties of these types of powder coatings have to be further improved, due to economical and environmental reasons, as to those of hereinbefore discussed prior publications .
Therefore there is still a strong need for further improved curable powder coating compositions, which provide an improved combination of physical properties of the cured coating films derived therefrom, which will meet the requirements from the industrial coating industry in the near future, and more in particular the requirements to be put on automotive top coating compositions and coil coating compositions .
Moreover, it is aimed at to develop powder coating compositions which preferably can be cured at low temperatures, i.e. in the range of from 120 to 140 °C. Physical properties of the cured coating films, which have to be improved and/or better balanced in the final combination, are inter alia: hardness, MEK and petrol resistance, acid resistance, transparency, colouring resistance during baking, weathering resistance, mar resistance and sealer cracking resistance. Therefore it is an object of the present invention to provide curable resin powder compositions, providing cured coating films having improved one or more of the properties, as specified hereinbefore. Another object of the present invention is to provide a process for the preparation of a copolymer component to be incorporated into said curable resin compositions .
As a result of extensive research and experimentation, said curable resin compositions aimed at, have been surprisingly found.
Accordingly one aspect of the present invention is formed by curable powder coating compositions, comprising at least:
(a) a copolymer obtainable from at least (ai) a glycidyl ester of ethylenically unsaturated carboxylic acid;
(aii) an alkyl ester of an ethylenically unsaturated monocarboxylic acid, having from 3 to 4, and preferably 3 carbon atoms in the acid moiety, and wherein the alkyl group contains from 1 to 12 carbon atoms, and preferably from 1 to 4 carbon atoms; and
(b) at least one α,α,α' ,α' -branched aliphatic dicarboxylic acid, comprising from 8 to 18 carbon atoms, preferably from 10 to 18 carbon atoms. Preferred embodiments of the present invention are formed by curable powder coating compositions, comprising at least:
(a) a copolymer obtainable from (ai) a glycidyl ester of ethylenically unsaturated carboxylic acid;
(aii) an alkyl ester of an ethylenically unsaturated monocarboxylic acid, having from 3 to 4 and preferably 3 carbon atoms in the acid moiety, and wherein the alkyl group contains from 1 to 12 carbon atoms and preferably from 1 to 4 carbon atoms;
(aiii) a phenylalkylene monomer having from 8 to 12 carbon atoms and preferably 8 carbon atoms; (aiv) an alkenyl ester of a branched tertiary carboxylic acid the acid moiety of which contains from 5 to 13 carbon atoms and preferably 9-11 carbon atoms; and (av) an alkyl diester of an ethylenically unsaturated dicarboxylic acid, comprising an alkyl group, having from 1 to 4 carbon atoms and preferably 1 or 2; the respective percentages of the components (ai) through (av) are relative to the total weight of the copolymer, while the sum of all actual percentages = 100%. (b) at least one α,α,oC , ' -branched aliphatic dicarboxylic acid, comprising from 8 to 18 carbon atoms, preferably from 10 to 18 carbon atoms.
More preferred embodiments of the present invention are formed by curable powder coating compositions, comprising at least: (a) a copolymer obtainable from
(ai) from 15 to 55 wt% of a glycidyl ester of ethylenically unsaturated carboxylic acid; (aii) from 10 to 45 wt% of an alkyl ester of an ethylenically unsaturated monocarboxylic acid, having from 3 to 4 and preferably 3 carbon atoms in the acid moiety, and wherein the alkyl group contains from 1 to 12 carbon atoms and preferably from 1 to 4 carbon atoms; (aiii) from 0 to 45 wt% of a phenylalkylene monomer having from 8 to 12 carbon atoms and preferably 8 carbon atoms; (aiv) from 0 to 35 wt% of an alkenyl ester of a branched tertiary carboxylic acid the acid moiety of which contains from 5 to 13 carbon atoms and preferably 9-11 carbon atoms; and (av) from 0 to 10 wt% of 'an alkyl diester of an ethylenically unsaturated dicarboxylic acid, comprising an alkyl group, having from 1 to 4 carbon atoms and preferably 1 or 2; the respective percentages of the components (ai) through (av) are relative to the total weight of the copolymer, while the sum of all actual percentages = 100%. (b) at least one α,α,α' , α' -branched aliphatic dicarboxylic acid, comprising from 8 to 18 carbon atoms, preferably from 10 to 18 carbon atoms.
The molar ratio between the acid groups of component (b) and epoxy groups of component (a) is in the range of from 0.70 to 1.10. Preferably the molar ratio between the acid groups and epoxy groups is in the range of from 0.85 to 1.00.
Suitable monomers to be used as component (ai) can be selected from e.g. glycidyl methacrylate, glycidyl acrylate, glycidyl crotonate, glycidyl cinnamate, and the like. Glycidyl methacrylate or glycidyl acrylate are most preferred.
Suitable monomers to be used as component (aii) can be selected from e.g. methyl acrylate, ethyl acrylate, n- propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, ethyl-hexyl acrylate, isobornyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, ethylhexyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, methyl crotonate, ethyl crotonate, n-propyl crotonate, isopropyl crotonate, isobutyl crotonate, n-butyl crotonate, ethylhexyl crotonate, isobornyl crotonate, cyclohexyl crotonate.
The more preferred monomers (aii) are methyl methacrylate, methyl acrylate, isobornyl acrylate or isobornyl methacrylate and the most preferred is methyl methacrylate .
Suitable monomers to be used as component (aiii) can be selected from e.g. styrene, vinyltoluene, dimethyl- styrene, α-methylstyrene and the like. Styrene is the most preferred monomer.
Monomers to be used as component (aiv) are preferably commercially available as mixtures of alkenyl esters of branched tertiary carboxylic acids, containing each from 5 to 13 carbons in the acid moiety, such as VEOVA 9, VEOVA 10 and VEOVA 11 (VEOVA is a trademark of Shell Chemical Europe Ltd.) for vinyl esters of VERSATIC acids (VERSATIC is a trademark) .
It will be appreciated that as component (aiv) also mixtures of vinyl esters of branched tertiary carboxylic acids, having from 9 to 13 carbon atoms in their acid residue, as major component (i.e. occurring in amounts of at least 80 wt% relative to the total weight of the component (aiv) and preferably at least 90 wt%) , can be used. Vinyl esters of branched tertiary carboxylic acids, having a 9 carbon atoms in their acid moiety as major component, are a preferred component (aiv) for the powder coating compositions of the present invention.
Said preferred main component of ingredient (aiv) can be mixed with minor component (s) of vinyl esters of other branched acids (< 20 wt% and more preferably < 10 wt%) . Examples thereof are vinyl esters of branched acids having 5, 10, 11 or 13 carbon atoms in their acid residues . Most preferably vinyl esters of branched carboxylic acids will be applied as sole comonomer (aiv) , which contain 9 carbon atoms in the acid residue only.
Suitable monomers to be used as component (av) can be selected from e.g. dimethyl maleate, diethyl maleate, di- n-propyl maleate, di-n-butyl maleate, di-isopropyl maleate, dimethyl itaconate, diethyl itaconate, di-n- propyl itaconate, di-n-butyl itaconate, di-isopropyl itaconate, di-isobutyl itaconate, and the like. Preferred monomers ai) are dimethyl maleate or diethyl maleate, of which dimethyl maleate is most preferred.
Preferred proportions of component (ai) are in the range of from 17 to 45 wt%.
Preferred proportions of component (aii) are in the range of from 10 to 30 wt%.
Preferred proportions of component (aiii) are in the range of from 20 to 43 wt%.
Preferred proportions of component (aiv) are in the range of from 10 to 30 wt%.
Preferred proportions of component (av) are in the range of from 6 to 9 wt% .
Suitable representatives of component (b) are selected from α,α,α/ , α -branched dicarboxylic acids of the formulae:
HOOC COOH
Figure imgf000011_0001
wherein n is an integer in the range from 1 to 6 and preferably from 2 to 6 and most preferably from 2 to 4, and mixtures of said acids.
More preferred representatives are 2,2,6,6- tetramethyl pimelic acid, 2, 2, 5-trimethyl-5-ethyl adipic acid, 2, 2, 5, 5-tetramethyl adipic acid, 2, 2, 4-trimethyl, 4-ethyl glutaric acid or mixtures thereof.
Most preferred di-acids to be used are 2,2,6,6- tetramethyl pimelic acid and 2, 2, 5-trimethyl-5-ethyl adipic acid, or mixtures thereof. According to preferred embodiments of the powder coating compositions copolymer components (a) are to be included, which show an epoxy group content in the range of from 1000 to 4000 meq/kg and preferably from 2000 to 3000" meq/kg.
More in particular the weight average molecular weight of the copolymer (a) components is in the range of from 2000 to 10.000 and preferably from 4000 to 7000. More preferably the copolymer components (a) are prepared by mass (or bulk) polymerization, of the components (ai) through (av) without any solvent, at a temperature in the range of from 155 to 180 °C, and in the presence of a radical polymerization catalyst such as peroxides, diazo compounds and the like of which the peroxide catalysts are preferred e.g. di-tert-butyl peroxide, di-tert . -amyl peroxide.
An important advantage of the curable powder compositions of the present invention is formed by the lower curing temperature, which has to be applied, e.g. 140 °C during 30 minutes instead of the conventional temperature of 175 and higher, in combination with a good flow-out and a good stability.
It will be appreciated that if desired, curing catalysts can be included in the powder coating compositions in order to reach the desired low temperature curing, i.e. in the temperature range of from 100 to 140 °C. Examples of said curing catalysts are the quaternary ammonium salts, such as tetra (2-4-alkyl) - ammonium halide and more in particular e.g. tetra- butylammonium bromide, tetrabutylammoniumchloride, or tin salts of carboxylic acids having from 6-16 carbon atoms, such as tin octoate.
Another aspect of the present invention is formed by shaped articles on which cured powder coating compositions as defined hereinbefore have been applied. The invention can be further illustrated by the following examples, however without restricting its scope to these embodiments . Examples (a) Acrylic resins preparation by bulk polymerization:
The reactor is charged with the vinyl ester of tertiary branched acid monomer and dialkyl ester of ethylenically unsaturated diacid in amounts listed in the table 1 hereinafter, and heated to a temperature to 155 °C under a nitrogen blanket.
When a temperature of 155 °C is reached, the addition of the other monomers/initiator, listed in Table 1, is started. The monomers/initiator are added over a period of 5 hours via a pump. After the addition is completed, the temperature is raised to 170 °C and is maintained for 2 hours .
Table 1 - ratio is expressed in mm
Figure imgf000013_0001
* resin has been made at temp, of 165 °C,
# resin has been made at 175 °C.
The physical parameters of the obtained resins are listed in Table 2. Table 2
Figure imgf000014_0001
a: melt viscosity at 200 °C measured with ICI cone and plate .
(b) formulation and powder application (bi) formulation composition
Cross-linking agents applied are a 50/50 mixture of 2, 2, 6, 6-tetramethyl pimelic acid and 2, 2 , 5-trimethyl-5- ethyl adipic acid, further mentioned DTA, and the dodecanoic acid, which was generally applied for a long time as cross-linking agent for corresponding prior art powder coating compositions.
The characteristics of the two cross-linkers are the following:
Figure imgf000014_0002
This resin was then extruded with the cross-linker and the additives (benzoin as degassing agent and Modaflow Powder III as control flow agent) . The formulations of the powders are given in the following table : Table 3
Figure imgf000015_0001
The polymer and the cross-linker were separately coarse ground before extrusion. The polymer and cross- linker were blended with degassing agent (1% benzoin) and flow control agent (1.5% Modaflow powder III) for about 30 minutes on a roller bank. The mix was then extruded using a Buss PLK46 single screw extruder. The extruder was operated in a temperature range of 70-90 °C with a screw speed of 80 r.p.m. The resulting extrudate was flattened using cooled rolls, stabilized for 24 hours and fine milled in an Alpine AFG jet grinding mill at 1790 r.p.m. to obtain an average powder particle size below 100 micron. The powder was sieved using a 300 mesh sieve to avoid granules . The powder was then electrostatically sprayed by Gema gun onto uncoated Q-panel and cured for 30 minutes at 140 °C. (bii) Powder and coating properties
The properties of the powder resin and coating were assessed and are given in the following table:
Table 4
Figure imgf000016_0001
It will be appreciated from the preceding test data that physical stability of the two powders is comparable but the acid resistance of the DTA-based system is far better than that of DDA.

Claims

C L A I M S
1. Curable powder coating compositions, comprising at least:
(a) a copolymer obtainable from at least
(ai) a glycidyl ester of ethylenically unsaturated carboxylic acid;
(aii) an alkyl ester of an ethylenically unsaturated monocarboxylic acid, having from 3 to 4 , and preferably 3 carbon atoms in the acid moiety, and wherein the alkyl group contains from 1 to 12 carbon atoms, and preferably from 1 to 4 carbon atoms; and
(b) at least one α,α,α' , α' -branched aliphatic dicarboxylic acid, comprising from 8 to 18 carbon atoms, preferably from 10 to 18 carbon atoms.
2. Curable powder coating compositions, comprising at least:
(a) a copolymer obtainable from
(ai) a glycidyl ester of ethylenically unsaturated carboxylic acid;
(aii) an alkyl ester of an ethylenically unsaturated monocarboxylic acid, having from 3 to 4 and preferably
3 carbon atoms in the acid moiety, and wherein the alkyl group contains from 1 to 12 carbon atoms and preferably from 1 to 4 carbon atoms;
(aiii) a phenylalkylene monomer having from 8 to 12 carbon atoms and preferably 8 carbon atoms;
(aiv) an alkenyl ester of a branched tertiary carboxylic acid the acid moiety of which contains from 5 to
13 carbon atoms and preferably 9-11 carbon atoms; and (av) an alkyl diester of an ethylenically unsaturated dicarboxylic acid, comprising an alkyl group, having from 1 to 4 carbon atoms and preferably 1 or 2; the respective percentages of the components (ai) through (av) are relative to the total weight of the copolymer, while the sum of all actual percentages = 100%. b) at least one ,α, α' , α' -branched aliphatic dicarboxylic acid, comprising from 8 to 18 carbon atoms, preferably from 10 to 18 carbon atoms. 3. Curable powder coating compositions, comprising at least:
(a) a copolymer obtainable from (ai) from 15 to 55 wt% of a glycidyl ester of ethylenically unsaturated carboxylic acid; (aii) from 10 to 45 wt% of an alkyl ester of an ethylenically unsaturated monocarboxylic acid, having from 3 to 4 and preferably 3 carbon atoms in the acid moiety, and wherein the alkyl group contains from 1 to 12 carbon atoms and preferably from 1 to 4 carbon atoms; (aiii) from 0 to 45 wt% of a phenylalkylene monomer having from 8 to 12 carbon atoms and preferably 8 carbon atoms; (aiv) from 0 to 35 wt% of an alkenyl ester of a branched tertiary carboxylic acid the acid moiety of which contains from 5 to 13 carbon atoms and preferably 9-11 carbon atoms; and
(av) from 0 to 10 wt% of an alkyl diester of an ethylenically unsaturated dicarboxylic acid, comprising an alkyl group, having from 1 to 4 carbon atoms and preferably 1 or 2; the respective percentages of the components (ai) through (av) are relative to the total weight of the copolymer, while the sum of all actual percentages = 100%. (b) at least one α, α,α' , α' -branched aliphatic dicarboxylic acid, comprising from 8 to 18 carbon atoms, preferably from 10 to 18 carbon atoms.
4. Curable powder coating compositions according to claims 1-3, wherein the molar ratio between the acid groups of component (b) and epoxy groups of component (a) is in the range of from 0.70 to 1.10.
5. Curable powder coating compositions according to claim 4, wherein the molar ratio between the acid groups of component (b) and epoxy groups of component (a) is in the range of from 0.85 to 1.00.
6. Curable powder coating compositions according to claims 1-5, wherein the monomer component (ai) can be selected from e.g. glycidyl methacrylate, glycidyl acrylate, glycidyl crotonate and glycidyl cinnamate.
7. Curable powder coating compositions according to claim 6, wherein glycidyl methacrylate or glycidyl acrylate are used as comonomer component (ai) .
8. Curable powder coating compositions according to claims 1-5, wherein the monomer component is selected from methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, ethyl-hexyl acrylate, isobornyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, ethylhexyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, methyl crotonate, ethyl crotonate, n-propyl crotonate, isopropyl crotonate, isobutyl crotonate, n-butyl crotonate, ethylhexyl crotonate, isobornyl crotonate, cyclohexyl crotonate.
9. Curable powder coating compositions according to claim 8, wherein methyl methacrylate, methyl acrylate, isobornyl acrylate or isobornyl methacrylate are used as comonomer component (aii) .
10. Curable powder coating compositions according to claims 1-5, wherein monomers to be used as component (aiii) can be selected from styrene, vinyltoluene, dimethylstyrene, α-methylstyrene of which styrene is the most preferred.
11. Curable powder coating compositions according to claims 1-5, wherein to be used as component (aiv) are mixtures of alkenyl esters of branched tertiary carboxylic acids, containing each from 5 to 13 carbons in the acid moiety.
12. Curable powder coating compositions according to claims 1-5, wherein monomers to be used as component (av) can be selected from e.g. dimethyl maleate, diethyl maleate, di-n-propyl maleate, di-n-butyl maleate, di-isopropyl maleate, dimethyl itaconate, diethyl itaconate, di-n-propyl itaconate, di-n-butyl itaconate, di-isopropyl itaconate, di-isobutyl itaconate, and the like. Preferred monomers (ai) are dimethyl maleate or diethyl maleate, of which dimethyl maleate is most preferred.
13. Curable powder coating compositions according to claims 1-3, wherein the component (b) is selected from α,α,α' , α' -branched dicarboxylic acids of the formulae:
HOOC- COOH
Figure imgf000020_0001
wherein n is an integer in the range from 1 to 6 and preferably from 2 to 6 and most preferably from 2 to 4, and mixtures of said acids.
14. Curable powder coating compositions according to claim 13, wherein 2, 2, 6, 6-tetramethyl pimelic acid, 2, 2, 5-trimethyl-5-ethyl adipic acid, 2, 2, 5, 5-tetramethyl adipic acid, 2, 2, 4-trimethyl, 4-ethyl glutaric acid or mixtures thereof.
15. Curable powder coating compositions according to claim 14, wherein 2, 2, 6, 6-tetramethyl pimelic acid and
2, 2, 5-trimethyl-5-ethyl adipic acid, or mixtures thereof, are used.
16. Curable powder coating compositions according to claims 1-3, wherein copolymer components (a) are included, which show an epoxy group content in the range of from 1000 to 4000 meq/kg and preferably from 2000 to 3000 meq/kg.
17. Shaped articles on which cured powder coating compositions of claims 1-16, have been applied.
PCT/EP2001/011396 2000-11-01 2001-10-01 Curable powder coating comprising copolymers of at least alkylesters and an epoxy alkylester WO2002036700A1 (en)

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Cited By (2)

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WO2009110998A1 (en) * 2008-03-04 2009-09-11 Anderson Development Co. Resin suitable for powder coating compositions
CN104204007A (en) * 2012-02-03 2014-12-10 帝斯曼知识产权资产管理有限公司 Polymers, methods and compositions

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Publication number Priority date Publication date Assignee Title
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WO1999033889A1 (en) * 1997-12-24 1999-07-08 Shell Internationale Research Maatschappij B.V. Copolymers of ethylenically unsaturated monomers to be used in powder coatings

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WO1998037119A1 (en) * 1997-02-21 1998-08-27 Shell Internationale Research Maatschappij B.V. Outdoor durable coating compositions and acid functional polyester resins and polyglycidyl esters thereof usable therefor
WO1999033889A1 (en) * 1997-12-24 1999-07-08 Shell Internationale Research Maatschappij B.V. Copolymers of ethylenically unsaturated monomers to be used in powder coatings

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Publication number Priority date Publication date Assignee Title
WO2009110998A1 (en) * 2008-03-04 2009-09-11 Anderson Development Co. Resin suitable for powder coating compositions
US7737238B2 (en) 2008-03-04 2010-06-15 Anderson Development Co. Resin suitable for powder coating compositions
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CN104204007A (en) * 2012-02-03 2014-12-10 帝斯曼知识产权资产管理有限公司 Polymers, methods and compositions
CN104204007B (en) * 2012-02-03 2017-03-08 帝斯曼知识产权资产管理有限公司 Polymers, methods and compositions

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