CA2009422A1 - Resinous compositions - Google Patents
Resinous compositionsInfo
- Publication number
- CA2009422A1 CA2009422A1 CA002009422A CA2009422A CA2009422A1 CA 2009422 A1 CA2009422 A1 CA 2009422A1 CA 002009422 A CA002009422 A CA 002009422A CA 2009422 A CA2009422 A CA 2009422A CA 2009422 A1 CA2009422 A1 CA 2009422A1
- Authority
- CA
- Canada
- Prior art keywords
- granules
- composition according
- composition
- volume
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 239000008187 granular material Substances 0.000 claims abstract description 44
- 239000000843 powder Substances 0.000 claims abstract description 43
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- 229920005989 resin Polymers 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 32
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 17
- 239000008199 coating composition Substances 0.000 claims abstract description 16
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000049 pigment Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 10
- 229920000728 polyester Polymers 0.000 claims description 10
- 239000011342 resin composition Substances 0.000 claims description 10
- 229920001225 polyester resin Polymers 0.000 claims description 9
- 239000004645 polyester resin Substances 0.000 claims description 9
- 229920000647 polyepoxide Polymers 0.000 claims description 8
- 239000003822 epoxy resin Substances 0.000 claims description 7
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- 239000004814 polyurethane Substances 0.000 claims description 5
- 229920002635 polyurethane Polymers 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002861 polymer material Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920001169 thermoplastic Polymers 0.000 claims description 3
- 239000004416 thermosoftening plastic Substances 0.000 claims description 3
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 2
- 229920006149 polyester-amide block copolymer Polymers 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 26
- 239000011324 bead Substances 0.000 description 22
- 239000011248 coating agent Substances 0.000 description 19
- 239000003795 chemical substances by application Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- -1 polyethylene Polymers 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000004606 Fillers/Extenders Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000006224 matting agent Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 206010037867 Rash macular Diseases 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000007762 w/o emulsion Substances 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical class CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920012485 Plasticized Polyvinyl chloride Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 101150095130 URAD gene Proteins 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ZBTGXRBMYGTQHK-UHFFFAOYSA-N azanium;2-nonylphenolate Chemical compound N.CCCCCCCCCC1=CC=CC=C1O ZBTGXRBMYGTQHK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000002531 isophthalic acids Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003504 terephthalic acids Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
- C09D5/032—Powdery paints characterised by a special effect of the produced film, e.g. wrinkle, pearlescence, matt finish
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
ABSTRACT OF DISCLOSURE
RESINOUS COMPOSITIONS
A powder coating composition which is a dry particulate mixture of a thermosetting resin or of a thermoplastic resin and vesiculated polymer granules. The polymer granules have a volume mean diameter of from 3 to 30 microns and are formed of a polymeric material which is not melted or degraded during any of the conditions of time and temperature which arise during preparation of the compositions or subsequent use. The amount of the polymer granules in the composition is at least 40% by volume. The powder coating compositions produce a matt finish rather than the previous glossy style. The polyrneric granules preferably are spherical and the vesicles occupy from 5 to 95% of the volume of the granules. The powder compositions can be used for wide variety of uses.
RESINOUS COMPOSITIONS
A powder coating composition which is a dry particulate mixture of a thermosetting resin or of a thermoplastic resin and vesiculated polymer granules. The polymer granules have a volume mean diameter of from 3 to 30 microns and are formed of a polymeric material which is not melted or degraded during any of the conditions of time and temperature which arise during preparation of the compositions or subsequent use. The amount of the polymer granules in the composition is at least 40% by volume. The powder coating compositions produce a matt finish rather than the previous glossy style. The polyrneric granules preferably are spherical and the vesicles occupy from 5 to 95% of the volume of the granules. The powder compositions can be used for wide variety of uses.
Description
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.
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 2~094;~2 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 Z~9~2~
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~
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 Example 9 10 pvc 15% 15%
bvc 10% 20%
Polyester resin 615 533 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 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.
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.
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 2~094;~2 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 Z~9~2~
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~
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 Example 9 10 pvc 15% 15%
bvc 10% 20%
Polyester resin 615 533 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 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.
Claims (16)
1. A powder coating composition comprising a substantially dry particulate mixture of a thermosetting resin or of a thermoplastic resin and vesiculated polymer granules having a volume 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 thermoplastic resin composition to a substrate and the amount of the polymer granules being less than 40%
by volume of said mixture.
by volume of said mixture.
2. A composition according to claim 1 in which the granules are substantially spherical and have a volume mean diameter of from 5 to 20 microns.
3. A composition according to claim 1 in which the granules have vesicles which are substantially spherical in shape and have a diameter less than 20 mcirons.
4. A composition according to claim 3 in which the vesicles have a diameter of from 0.1 to 7 microns.
5. A composition according to claim 1 in which said granules contain vesicles occupying from 5% to 95% of the total volume of the granules.
6. A composition according to claim 1 in which the amount of the granules is from 5% to 30% of the volume of the mixture.
7. A composition according to claim 1 in which the thermosetting resin is selected from the class of resins consisting of epoxy resins, polyurethanes, polyester resins, epoxy-polyester hybrid resins and acrylic resins.
8. A composition according to claim 1 in which the thermoplastic resin is selected from the class consisting of polyvinyl polymers, polyamides, thermoplastic polyesters, polyolefines and cellulosic polymers.
9. A composition according to claim 1 in which titanium dioxide pigment is also present in the mixture.
10. A composition according to claim 1 in which the titanium dioxide is present in said granules in an amount of from 1% to 60% by weight of said granules.
11. A composition according to claim 1 in which the polymer granules are formed from a material selected from the class consisting of polyesters, polyester amides, polyurethanes, urea-aldehyde resins and cellulosic esters.
12. A composition according to claim 11 in which the polymer granules are formed from an unsaturated polyester resin cross-linked with an unsaturated monomer.
13. A composition according to claim 1 in which the polymer granules are core-sheath polymer particles.
14. A composition according to claim 13 in which each granule has a single vesicle.
15. A process for the manufacture of a powder coating composition which comprises mixing a thermosetting resin or of a thermoplastic resin and vesiculated polymer granules having a volume mean diameter of from 3 to 30 microns and formed of a polymer material that is not melted or not substantially degraded respectively under the conditions of temperature and time of mixing and those required to cure said thermosetting resin composition and under the conditions of temperature and time for the application subsequently of said thermoplastic resin composition to a substrate and the amount of the polymer granules being less than 40% by volume of said mixture.
16. A process according to claim 15 in which the mixture is heated to melt the resin and the mixture is extruded and cooled prior to grinding to the desired final size.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB898906495A GB8906495D0 (en) | 1989-03-21 | 1989-03-21 | Resinous compositions |
GB8906495.0 | 1989-03-21 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2009422A1 true CA2009422A1 (en) | 1990-09-21 |
Family
ID=10653747
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002009422A Abandoned CA2009422A1 (en) | 1989-03-21 | 1990-02-06 | Resinous compositions |
Country Status (10)
Country | Link |
---|---|
AU (1) | AU627840B2 (en) |
BE (1) | BE1004439A5 (en) |
CA (1) | CA2009422A1 (en) |
DE (1) | DE4008361A1 (en) |
ES (1) | ES2019238A6 (en) |
FR (1) | FR2644794A1 (en) |
GB (2) | GB8906495D0 (en) |
IT (1) | IT1239433B (en) |
NL (1) | NL9000442A (en) |
ZA (1) | ZA901200B (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ATE135022T1 (en) * | 1989-03-23 | 1996-03-15 | Dsm Nv | POWDER PAINT AND POLYESTER RESIN FOR POWDER PAINTS |
JP2913377B2 (en) * | 1994-04-22 | 1999-06-28 | 株式会社巴川製紙所 | Powder paint |
GB0002305D0 (en) * | 2000-02-01 | 2000-03-22 | Phoqus Limited | Power material for electrostatic application |
US6737467B1 (en) * | 2000-11-21 | 2004-05-18 | E. I. Du Pont De Nemours And Company | Low gloss powder coatings |
DE10231706B4 (en) * | 2002-07-13 | 2006-10-26 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Microcomposites and process for their preparation and their use |
CN112126324A (en) * | 2020-09-28 | 2020-12-25 | 湖南连心科技有限公司 | Sand grain powder coating and preparation method thereof |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3264371A (en) * | 1959-03-13 | 1966-08-02 | Polymer Corp | Fluidized bed coating process and product |
AU439432B2 (en) * | 1968-11-28 | 1972-08-15 | Dulux Australia Ltd | Polymer and coating composition |
BE759698A (en) * | 1969-12-01 | 1971-06-01 | Balm Paints Ltd | VESICULOUS POLYMER |
GB1332469A (en) * | 1969-12-22 | 1973-10-03 | Balm Paints Ltd | Polymer and process |
AU460062B2 (en) * | 1971-06-28 | 1975-04-17 | Dulux Australia Limited | Matte paint compositions |
US4489174A (en) * | 1983-07-26 | 1984-12-18 | The Sherwin-Williams Company | Vesiculated beads |
US4461849A (en) * | 1983-07-26 | 1984-07-24 | The Sherwin-Williams Company | Vesiculated beads |
JPH07122035B2 (en) * | 1986-06-12 | 1995-12-25 | 日本ペイント株式会社 | Powder paint |
-
1989
- 1989-03-21 GB GB898906495A patent/GB8906495D0/en active Pending
-
1990
- 1990-02-05 GB GB9002513A patent/GB2231334B/en not_active Expired - Fee Related
- 1990-02-06 CA CA002009422A patent/CA2009422A1/en not_active Abandoned
- 1990-02-16 ZA ZA901200A patent/ZA901200B/en unknown
- 1990-02-23 AU AU50107/90A patent/AU627840B2/en not_active Ceased
- 1990-02-23 NL NL9000442A patent/NL9000442A/en not_active Application Discontinuation
- 1990-03-15 DE DE4008361A patent/DE4008361A1/en not_active Withdrawn
- 1990-03-16 ES ES9000785A patent/ES2019238A6/en not_active Expired - Fee Related
- 1990-03-20 IT IT47773A patent/IT1239433B/en active IP Right Grant
- 1990-03-20 BE BE9000310A patent/BE1004439A5/en not_active IP Right Cessation
- 1990-03-21 FR FR9003640A patent/FR2644794A1/en not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
FR2644794A1 (en) | 1990-09-28 |
ES2019238A6 (en) | 1991-06-01 |
NL9000442A (en) | 1990-10-16 |
BE1004439A5 (en) | 1992-11-24 |
GB2231334A (en) | 1990-11-14 |
GB2231334B (en) | 1992-11-18 |
ZA901200B (en) | 1990-11-28 |
AU5010790A (en) | 1990-09-27 |
GB9002513D0 (en) | 1990-04-04 |
IT9047773A1 (en) | 1991-09-20 |
GB8906495D0 (en) | 1989-05-04 |
IT1239433B (en) | 1993-11-02 |
DE4008361A1 (en) | 1990-10-04 |
AU627840B2 (en) | 1992-09-03 |
IT9047773A0 (en) | 1990-03-20 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
FZDE | Discontinued |