WO2024026334A1 - Thermosetting powder coating compositions - Google Patents
Thermosetting powder coating compositions Download PDFInfo
- Publication number
- WO2024026334A1 WO2024026334A1 PCT/US2023/070991 US2023070991W WO2024026334A1 WO 2024026334 A1 WO2024026334 A1 WO 2024026334A1 US 2023070991 W US2023070991 W US 2023070991W WO 2024026334 A1 WO2024026334 A1 WO 2024026334A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mole percent
- iii
- residues
- total moles
- polyester
- Prior art date
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- 239000000843 powder Substances 0.000 title claims abstract description 56
- 239000008199 coating composition Substances 0.000 title claims abstract description 48
- 229920001187 thermosetting polymer Polymers 0.000 title abstract description 4
- 229920000728 polyester Polymers 0.000 claims abstract description 67
- 239000000203 mixture Substances 0.000 claims abstract description 45
- 150000002009 diols Chemical group 0.000 claims abstract description 36
- 238000000576 coating method Methods 0.000 claims abstract description 31
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical group OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims abstract description 17
- RKLJSBNBBHBEOT-UHFFFAOYSA-N (3-hydroxy-2,2-dimethylpropanoyl) 3-hydroxy-2,2-dimethylpropanoate Chemical group OCC(C)(C)C(=O)OC(=O)C(C)(C)CO RKLJSBNBBHBEOT-UHFFFAOYSA-N 0.000 claims abstract description 15
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 15
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims abstract description 14
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical group OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 claims abstract description 14
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical group OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 26
- 239000004971 Cross linker Substances 0.000 claims description 24
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 20
- 229920005862 polyol Polymers 0.000 claims description 17
- 150000003077 polyols Chemical class 0.000 claims description 17
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 16
- 230000009477 glass transition Effects 0.000 claims description 13
- 239000001361 adipic acid Substances 0.000 claims description 8
- 235000011037 adipic acid Nutrition 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 5
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- FQXGHZNSUOHCLO-UHFFFAOYSA-N 2,2,4,4-tetramethyl-1,3-cyclobutanediol Chemical group CC1(C)C(O)C(C)(C)C1O FQXGHZNSUOHCLO-UHFFFAOYSA-N 0.000 claims 3
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 claims 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 claims 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 37
- 239000011347 resin Substances 0.000 abstract description 37
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 abstract 1
- 239000004645 polyester resin Substances 0.000 description 22
- 229920001225 polyester resin Polymers 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 20
- 238000012360 testing method Methods 0.000 description 11
- 229920013685 Estron Polymers 0.000 description 7
- DNXHEGUUPJUMQT-CBZIJGRNSA-N Estrone Chemical compound OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 DNXHEGUUPJUMQT-CBZIJGRNSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 229960003399 estrone Drugs 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000007872 degassing Methods 0.000 description 4
- 238000004110 electrostatic spray deposition (ESD) technique Methods 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical class CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000002015 acyclic group Chemical group 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- -1 hydroxyl compound Chemical class 0.000 description 3
- 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 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YWGAKIGNXGAAQR-DLPAQYCSSA-N C1([C@H]2CC(=O)N[C@@H](CC)C(=O)N3C[C@@H](Cl)[C@@H](Cl)[C@H]3C(=O)N[C@H](C(N[C@@H](CO)C(=O)N2)=O)CC)=CC=CC=C1 Chemical compound C1([C@H]2CC(=O)N[C@@H](CC)C(=O)N3C[C@@H](Cl)[C@@H](Cl)[C@H]3C(=O)N[C@H](C(N[C@@H](CO)C(=O)N2)=O)CC)=CC=CC=C1 YWGAKIGNXGAAQR-DLPAQYCSSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- WIHMDCQAEONXND-UHFFFAOYSA-M butyl-hydroxy-oxotin Chemical compound CCCC[Sn](O)=O WIHMDCQAEONXND-UHFFFAOYSA-M 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- MUTGBJKUEZFXGO-UHFFFAOYSA-N hexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21 MUTGBJKUEZFXGO-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007655 standard test method Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 2
- 229940113165 trimethylolpropane Drugs 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- 229920003319 Araldite® Polymers 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920006067 Megamid® Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- LPQOADBMXVRBNX-UHFFFAOYSA-N ac1ldcw0 Chemical compound Cl.C1CN(C)CCN1C1=C(F)C=C2C(=O)C(C(O)=O)=CN3CCSC1=C32 LPQOADBMXVRBNX-UHFFFAOYSA-N 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
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- HBPTUDIZKSGJNN-UHFFFAOYSA-N benzoic acid;cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1.OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1 HBPTUDIZKSGJNN-UHFFFAOYSA-N 0.000 description 1
- 239000006085 branching agent Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 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 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- TVIDDXQYHWJXFK-UHFFFAOYSA-N n-Dodecanedioic acid Natural products OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical class C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229940098458 powder spray Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/137—Acids or hydroxy compounds containing cycloaliphatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
Definitions
- the invention relates to powder coating compositions comprising carboxyl- functional polyesters.
- the polyesters are comprised of 2,2,4,4-tetramethyl-l,3- cyclobutanediol and trimethylolpropane.
- the invention provides polyester-based powder coating compositions useful in the coating of shaped or formed articles, which exhibit improved properties such as weathering performance and flexibility.
- the powder coating composition comprises: A. at least one carboxyl-functional polyester which comprises:!, a polyol component comprising: i. about 50 to about 87 mole percent of 2,2,4,4-tetramethyl-l,3-cyclobutanediol residues, based on the total moles of i., ii., iii. and iv.; ii.
- a diol residue selected from the group consisting of neopentyl glycol, cyclohexanedimethanol, 1,6-hexanediol, 1,4-butanediol, hydroxypivalyl hydroxypivalate, and combinations thereof, based on the total moles of i., ii., iii., and iv.; iii. 0 to about 20 mole percent of diol residues which is other than (i) and (ii), based on the total moles of i., ii., iii., and iv.; and iv.
- a dicarboxylic acid component comprising: v. about 70 to about 100 mole percent of hexahydrophthalic anhydride residues, based on the total moles of v. and vi.; and vi. 0 to about 30 mole percent of a C6-C12 acyclic diacid residues, based on the total moles of v.
- the polyester has a glass transition temperature of about 45° to 90°C, an acid number of about 20 to about 90 mg KOH/g, a number average molecular weight of about 1,000 to about 10,000 g/mole, and a weight average molecular weight of about 5,000 to about 100,000 g/mole; and B. one or more compounds reactive with the carboxyl-functional polyester.
- the powder coating composition comprises: A. at least one carboxyl-functional polyester, in an amount of about 70 to 95 weight percent, based on the total weight of A. B. and C., which comprises: 1. a polyol component comprising: i. about 60 to about 80 mole percent of 2,2,4,4-tetramethyl-l,3- cyclobutanediol residues, based on the total moles of i., ii., iii. and iv.; ii.
- diol residue selected from the group consisting of neopentyl glycol, cyclohexanedimethanol, 1,6-hexanediol, 1 ,4-butanediol, hydroxypivalyl hydroxypivalate, and combinations thereof, based on the total moles of i., ii., iii., and iv.; iii. 0 to about 20 mole percent of diol residues which is other than (i) and (ii), based on the total moles of i., ii., iii., and iv.; and iv.
- a dicarboxylic acid component comprising: v. about 75 to about 95 mole percent of hexahydrophthalic anhydride residues, based on the total moles of v. and vi.; and vi. about 5 to about 25 mole percent of a C6-C12 acyclic diacid residues, based on the total moles of v.
- the polyester has a glass transition temperature of about 45° to 90°C, an acid number of about 40 to about 60 mg KOH/g, a number average molecular weight of about 1,000 to about 10,000 g/mole, and a weight average molecular weight of about 5,000 to a about 100,000 g/mole;
- B. a glycidyl functional crosslinker in an amount of about 5 to about 30 weight percent, based on the total weight of A., B., and C.; and
- C. a P-hydroxy alkyl amide cross-linker in an amount of about 0 to about 5 weight percent, based on the total weight of A., B., and C.
- the powder composition comprises: A. at least one carboxyl-functional polyester, in an amount of about 80 to 90 weight percent, based on the total weight of A. and B., which comprises: 1. a polyol component comprising: i. about 60 to about 80 mole percent of 2,2,4,4-tetramethyl-l,3- cyclobutanediol residues, based on the total moles of i., ii., iii. and iv.; ii.
- diol residue selected from the group consisting of neopentyl glycol, cyclohexanedimethanol, 1,6-hexanediol, 1 ,4-butanediol, hydroxypivalyl hydroxypivalate, and combinations thereof, based on the total moles of i., ii., iii., and iv.; iii. 0 to about 20 mole percent of diol residues which is other than (i) and (ii), based on the total moles of i., ii., iii., and iv.; and iv.
- a dicarboxylic acid component comprising: v. about 80 to about 100 mole percent of hexahydrophthalic anhydride residues, based on the total moles of v. and vi.; and vi. 0 to about 20 mole percent of a C6-C12 acyclic diacid residues, based on the total moles of v.
- polyester has a glass transition temperature of about 45° to 90°C, an acid number of about 30 to about 80 mg KOH/g, a number average molecular weight of about 1,000 to about 10,000 g/rnole, and a weight average molecular weight of about 5,000 to a about 100,000 g/mole; and B. a P-hydroxy alkyl amide cross-linker in an amount of about 10 to about 20 weight percent, based on the total weight of A. and B.
- the invention provides a powder coating composition
- a powder coating composition comprising: A. at least one carboxyl-functional polyester which comprises:!, a polyol component comprising: i. about 50 to about 87 mole percent of 2,2,4,4-tetramethyl-l,3- cyclobutanediol residues, based on the total moles of i., ii., iii. and iv.; ii.
- a diol residue selected from the group consisting of neopentyl glycol, cyclohexanedimethanol, 1,6-hexanediol, 1 ,4-butanediol, hydroxypivalyl hydroxypivalate, and combinations thereof, based on the total moles of i., ii., iii., and iv.; iii. 0 to about 20 mole percent of diol residues which is other than (i) and (ii), based on the total moles of i., ii., iii., and iv.; and iv.
- a dicarboxylic acid component comprising: v. about 70 to about 100 mole percent of hexahydrophthalic anhydride residues, based on the total moles of v. and vi.; and vi. 0 to about 30 mole percent of a C6-C12 acyclic diacid residues, based on the total moles of v.
- the polyester has a glass transition temperature of about 45° to 90°C, an acid number of about 20 to about 90 mg KOH/g, a number average molecular weight of about 1,000 to about 10,000 g/mole, and a weight average molecular weight of about 5,000 to about 100,000 g/mole; and B. one or more compounds reactive with the carboxyl-functional polyester.
- the terms “a,” “an,” and “the” mean one or more.
- the term “and/or,” when used in a list of two or more items means that any one of the listed items can be employed by itself or any combination of two or more of the listed items can be employed. For example, if a composition is described as containing components A, B, and/or C, the composition can contain A alone; B alone; C alone; A and B in combination; A and C in combination, B and C in combination; or A, B, and C in combination.
- polyester is intended to include “copolyesters” and is understood to mean a synthetic polymer prepared by the reaction of one or more difunctional carboxylic acids and/or multifunctional carboxylic acids with one or more difunctional hydroxyl compounds and/or multifunctional hydroxyl compounds, as referred to above as comprised of a dicarboxylic acid component and a polyol component.
- the difunctional carboxylic acid can be a dicarboxylic acid and the difunctional hydroxyl compound can be a dihydric alcohol, for example, glycols and diols.
- polyol as used herein includes, but is not limited to, diols, glycols, and/or multifunctional hydroxyl compounds.
- reduce as used herein, means any organic structure incorporated into a polymer through a polycondensation and/or an esterification reaction from the corresponding monomer.
- peer as used herein, means an organic structure having a dicarboxylic acid residue and a diol residue bonded through an ester group.
- the dicarboxylic acid residues may be derived from a dicarboxylic acid monomer or its associated acid halides, esters, salts, anhydrides, and/or mixtures thereof.
- diacid includes multifunctional acids.
- dicarboxylic acid is intended to include dicarboxylic acids and any derivative of a dicarboxylic acid, including its associated acid halides, esters, half-esters, salts, halfsalts, anhydrides, mixed anhydrides, and/or mixtures thereof, useful in a reaction process with a diol to make a polyester.
- the stoichiometry of the polyol components and dicarboxylic acid components can be adjusted as needed to obtain the desired acid number (and/or hydroxyl number) in the final carboxyl-functional polyester to be utilized in the powder coating composition.
- the polyester portion of the compositions of the invention can be made by processes known in the art, for example, by processes in homogenous solution, by transesterification processes in the melt, and by two phase interfacial processes. Suitable methods include, but are not limited to, the steps of reacting one or more dicarboxylic acids with one or more diols at a temperature of 100°C to 315°C at a pressure of 0.1 to 760 mm Hg for a time sufficient to form a polyester. See U.S. Pat. No. 3,772,405 for methods of producing polyesters, the disclosure regarding such methods is hereby incorporated herein by reference.
- the carboxyl-functional polyester is comprised of all aliphatic groups or is comprised of substantially no aromatic groups. In another embodiment, the carboxyl-functional polyester comprises not more than about 10 mole percent aromatic diacid residues, such as isophthalic acid and terephthalic acid, based on the total moles of the dicarboxylic acid components.
- the polyol component comprises about 55 to 85 mole percent of 2,2,4,4-tetramethyl-l,3-cyclobutanediol residues, based on the total moles of
- dicarboxylic acid component comprises about 75 to about 100 mole percent of hexahydrophthalic anhydride residues; and 0 to about 25 mole percent of a C6-C12 acyclic diacid residues.
- the polyol component comprises about 60 to 80 mole percent of 2,2,4,4-tetramethyl-l ,3 -cyclobutanediol residues, based on the total moles of
- dicarboxylic acid component comprises about 80 to about 100 mole percent of hexahydrophthalic anhydride residues; and 0 to about 20 mole percent of a C6-C12 acyclic diacid residues.
- diol residues which is other than (i) and (ii) may include 2-butyl- 2-ethyl-l,3-propanediol (BEPD), ethylene glycol, propylene glycol, 2-methyl-l,3- propanediol (MPDiol), and mixtures thereof.
- the diol residues which is other than (i) and (ii) is selected from the group consisting of 2-methyl-l,3- propanediol and 2-butyl-2-ethyl-l,3-propanediol.
- the acyclic diacid is a C6-C12 diacid.
- Exemplary C6- C12 acyclic diacids include adipic acid, sebacic acid, and dodecanedicarboxylic acid.
- the C6-C12 acyclic diacid is adipic acid.
- the carboxyl-functional polyester has an acid number of about 20 to 90 mg KOH/g resin. In certain embodiments, the polyester has an acid number of about 30 to 80, 35 to 70, or 40 to 60 mg KOH/g.
- the carboxyl-functional polyester has a hydroxyl number of 0 to 20, 0 to 15, 0 to 10, or 0 to 5 mg KOH/g resin.
- the carboxyl-functional polyesters have a glass transition temperature of about 45° to 90°C. In certain embodiments, the polyester has a T g of about 50° to about 80°C, or about 55° to about 75°C.
- the carboxyl-functional polyester will have a number average molecular weight of about 1,000 to about 10,000 g/mole. In certain embodiments, the carboxyl-functional polyester will have a number average molecular weight of about 1,000 to about 9,000, about 1,500 to about 8,000, or about 1,500 to about 6,000 g/mole. As noted above, the carboxyl-functional polyester will have a weight average molecular weight of about 5,000 to about 100,000. In certain embodiments, the carboxyl- functional polyester will have a weight average molecular weight of about 5,000 to about 80,000 or about 5,000 to about 50,000 g/mole.
- the compounds reactive with the carboxyl-functional polyester is a cross-linker chosen from P-hydroxyalkylamides and glycidyl -functional compounds.
- the P-hydroxyalkylamide is chosen from bis(N,N'-dihydroxyethyl)adipamide, bis(N,N'-dihydroxypropyl)adipamide, or a mixture thereof.
- Commercially-available P-hydroxyalkylamides include bis(N,N'- dihydroxyethyl)adipamide (Primid® XL-552), bis(N,N'-dihydroxypropyl)adipamide (Primid® QM-1260), and Primid® SF-4510 available from EMS-GRILTECH.
- Megamid XL from MEGARA RESINS-ANASTASIOS FANIS S.A.
- glycidyl functional curing agents include triglycidyl isocyanurate based crosslinkers available from Huntsman as Araldite PT 810, PT910, and PT 912. Also suitable are glycidyl acrylates and glycidyl methacrylates such as those commercially available as GMA 300G, 400G and 500 from Estron Chemical.
- the compound reactive with the carboxyl-functional polyester is an epoxy resin.
- exemplary epoxy resins include those having a molecular weight of about 300 to about 4000, and have approximately 0.05 to about 0.99 epoxy groups per 100 grams of resin (i.e., 100-2000 weight per epoxy (WPE)).
- WPE weight per epoxy
- Such resins are widely known and commercially available under the EPON® mark (Hexion), ant the Araldite® mark (Huntsman).
- the polyester is present in an amount of about 70 to about 97 percent, by weight, and either: (a) the one or more compounds reactive with the carboxyl-functional polyester or (b) the cross-linker, is present in an amount of about 3 to about 30 percent, by weight, based on the total amount of polyester and the one or more compounds or cross-linker.
- the coating composition of the present invention the carboxyl- functional polyester is present in an amount of about 70 to 95, 75 to 95, or 80 to 90 weight percent and either: (a) the one or more compounds reactive with the carboxyl- functional polyester or (b) the cross-linker, is present in an amount of about 5 to 30, 5 to 25, or 10 to 20 weight percent, based on the total amount of polyester and the one or more compounds or cross-linker.
- the invention provides a powder coating composition
- a powder coating composition comprising: A. at least one carboxyl-functional polyester, in an amount of about 80 to 90 weight percent, based on the total weight of A. and B., which comprises: 1. a polyol component comprising: i. about 60 to about 80 mole percent of 2,2,4,4-tetramethyl-l,3- cyclobutanediol residues, based on the total moles of i., ii., iii. and iv.; ii.
- diol residue selected from the group consisting of neopentyl glycol, cyclohexanedimethanol, 1,6-hexanediol, 1 ,4-butanediol, hydroxypivalyl hydroxypivalate, and combinations thereof, based on the total moles of i., ii., iii., and iv.; iii. 0 to about 20 mole percent of diol residues which is other than (i) and (ii), based on the total moles of i., ii., iii., and iv.; and iv.
- a dicarboxylic acid component comprising: v. about 80 to about 100 mole percent of hexahydrophthalic anhydride residues, based on the total moles of v. and vi.; and vi. 0 to about 20 mole percent of a C6-C12 acyclic diacid residues, based on the total moles of v.
- polyester has a glass transition temperature of about 45° to 90°C, an acid number of about 30 to about 80 mg KOH/g, a number average molecular weight of about 1,000 to about 10,000 g/mole, and a weight average molecular weight of about 5,000 to a about 100,000 g/mole; and B. a P-hydroxyalkylamide cross-linker in an amount of about 10 to about 20 weight percent, based on the total weight of A. and B.
- the P-hydroxyalkylamide cross-linker will be present in an amount of about 3 to about 20 weight percent, based on the total weight of A. and B.
- the carboxyl-functional polyester of the invention comprises an acyclic diacid to further improve the flexibility in order to meet the need of certain applications such as, for example, automotive wheel powder coating, that require higher flexibility.
- this invention further provides a powder coating composition
- a powder coating composition comprising: A. at least one carboxyl-functional polyester, in an amount of about 70 to 95 weight percent, based on the total weight of A. B. and C., which comprises: 1. a polyol component comprising: i. about 60 to about 80 mole percent of 2,2,4,4-tetramethyl-l,3- cyclobutanediol residues, based on the total moles of i., ii., iii. and iv.; ii.
- diol residue selected from the group consisting of neopentyl glycol, cyclohexanedimethanol, 1,6-hexanediol, 1 ,4-butanediol, hydroxypivalyl hydroxypivalate, and combinations thereof, based on the total moles of i., ii., iii., and iv.; iii. 0 to about 20 mole percent of diol residues which is other than (i) and (ii), based on the total moles of i., ii., iii., and iv.; and iv.
- a dicarboxylic acid component comprising: v. about 75 to about 95 mole percent of hexahydrophthalic anhydride residues, based on the total moles of v. and vi.; and vi. about 5 to about 25 mole percent of a C6-C12 acyclic diacid residues, based on the total moles of v.
- the polyester has a glass transition temperature of about 45° to 90°C, an acid number of about 40 to about 60 mg KOH/g, a number average molecular weight of about 1,000 to about 10,000 g/mole, and a weight average molecular weight of about 5,000 to a about 100,000 g/mole;
- B. a glycidyl functional crosslinker in an amount of about 5 to about 30 weight percent, based on the total weight of A., B., and C.; and
- C. a P-hydroxyalkylamide cross-linker in an amount of about 0 to about 5 weight percent, based on the total weight of A., B., and C
- acyclic diacid examples include C6 to C12 linear diacid such as adipic acid, sebacic acid, and dodecanedicarboxylic acid.
- the powder coating compositions of the invention may further comprise waxes, pigments, fillers, degassing agents, flow agents, and/or other additives.
- pigments include inorganic and organic pigments such as titanium dioxide, iron oxide, chromium oxide, zinc sulfide, zinc phosphate, mica, azo compounds, and the like.
- Suitable fillers include silicates, sulfates, and carbonates.
- additives include degassing agents, antioxidants, and UV stabilizers.
- Exemplary weathering stabilizers that can be used in these embodiments include are hindered amine light stabilizers and UV absorbers.
- degassing agents examples include cyclohexane dimethanol dibenzoate, benzoin, and benzoin derivatives.
- flow control agents examples include Byk® 361 N (BYK) and Resiflow® PV-5 (Estron). Further examples of typical additives for powder coating compositions can be found in U.S. Patent No. 10,916,539, incorporated herein by reference.
- the powder coating compositions of the invention may be prepared by any methods known in the art.
- the powders of the carboxyl-functional polyester and the crosslinker are mixed along with any desired additives at room temperature to obtain a premix.
- the premix is then extruded at an elevated temperature such as, for example, 80° to 130°, 90° to 125°, or 100° to 120 °C, to yield an extrudate, which is then cooled to solidify the mixture.
- the resulting solid is then made into powder by milling and subsequently sieved to classify the size of the particles.
- the powder coating of the present invention desirably has particle sizes less than about 120 pm, less than 110 pm, or less than 100 pm.
- the powder coating composition may be applied to an article, such as, a substrate by a common method such as electrostatic spray deposition (ESD) or fluidized bed application at a thickness of about 1 to about 10 mils (1 mil - 25 pm).
- ESD electrostatic spray deposition
- the coating may be cured at 140° to 230°C, 140° to 200°C, 140° to 180°C, or 140° to 160°C for 10 minutes to one hour, or other suitable conditions, and allowed to cool.
- the powder coating compositions of the invention can be applied to a substrate or shaped or formed article.
- a further aspect of the present invention is a shaped or formed article, of which at least a portion has been coated with the coating compositions of the present invention.
- the substrate can be any common substrate such as aluminum, tin, steel or galvanized sheeting, and the like.
- ESD electrostatic spray deposition
- the coating can be cured at a temperature of about 140°C to about 230°C for a time period that ranges from about 10 minutes to about 60 minutes and allowed to cool.
- thermoset powder coating compositions of the invention can be described by Erichsen cupping test in accordance with ISO-1520.
- the cured powder coating compositions of the invention exhibit an Erichsen cupping test rating of 3 mm or more, 3.5 mm or more, 4mm or more, 4.25 mm or more, or 5 mm or more for the onset of cracking, and with no delamination of > 7mm.
- the cured coating compositions on such articles exhibit improved performance characteristics.
- articles coated with the cured compositions of the invention can exhibit an Erichsen crack rating of 3 mm or more according to the method of ISO-1520.
- NPG 2,2-dimethyl-l,3-propanediol (neopentyl glycol) - available from Sigma- Aldrich
- BEPD 2-butyl-2-ethyl-l,3-propanediol available from Sigma- Aldrich
- HPHP ⁇ hydroxypivalyl hydroxypivalate from Eastman Chemical Co.
- Adipic adipic acid available from Sigma- Aldrich
- TPP triphenylphosphite - available from Sigma- Aldrich
- Al AQT 36 Aluminum test panel available from Q-Panel Inc.
- P EPQ Hostanox® P-EPQ® powder (Qari ant)
- GMA 300 - glycidyl functional acrylate crosslinker available from Estron Inc.
- GMA 500 - glycidyl functional acrylate crosslinker available from Estron Inc.
- Resiflow® PL-200 - flow and wetting additive available from Estron Inc.
- Irganox® 1076 an antioxidant available from BASF
- Tinuvin® 405 is a UV absorber from BASF
- Tinuvin® 144 is a hindered amine light stabilizer from BASF
- the resin was prepared in a two-liter reaction kettle equipped with a heating mantle, mechanical stirrer, thermocouple, nitrogen blanket (1.0 standard cubic feet per hour), oil-heated partial condenser (103 °C - 105°C), condensate trap, and water-cooled total condenser (15°C).
- the condensate trap, kettle top and adapter from the kettle to the column were wrapped in aluminum foil and fiberglass tape to facilitate water removal.
- 786.7 grams HHPA, 186.4 grams adipic acid, 586.4 grams TMCD and 1.7 grams TPP were charged to the reactor. The reactor was then heated from room temperature to 100°C at l°C/minute to obtain a homogeneous melt.
- the reaction is held at 235°C until the target acid number, 55 mg KOH/g, was reached.
- Resins 1 to 8 were synthesized according to the mole ratios of the components listed in Table 1 and the weights of the components charged as listed in Table 2.
- Comparative Example 1 Synthesized Comparative Carboxyl-Functional Polyester Resins (Comparative Resins Cl to C8)
- Comparative Resins Cl to C8 were synthesized according to the mole ratios of the components listed in T able 3 and the weights of the components charged as listed in Table 4.
- T g Glass transition temperature
- M n Number average molecular weight
- M w weight average molecular weight
- Acid number was measured by using a procedure based on ASTM D7253-1 entitled “Standard Test Method for Polyurethane
- Powder coating compositions (P1 to P8) were prepared respectively by using Resins 1 to 8. Each coating composition was weighed into a container. The compositions were then milled using a Vitamix mill. The resulting milled compositions were extruded on a two-zone twin screw extruder at 320 RPM and 60-70% torque. Zone 1 was heated to 100°C while Zone 2 was at 110°C. The compositions were cooled on a twin roll chiller at 2-5 °C and collected in a plastic bag. The compositions were allowed to fully cool to room temperature overnight. They were then powdered using a Strand mill. The resulting powder compositions were sieved using 106-micron mesh. The sieved powder coating compositions were then considered ready to spray. The compositions are listed in Table 7.
- Coating formulations were prepared according to the method described in Example 4 by using comparative resins Cl to C8. Their compositions are listed in Table 8.
- Powder coating compositions P1 to P8 prepared using the procedure from Example 4 were applied to the metal substrate using a Parker Ionics GX700C Powder Gun System electrostatic powder spray apparatus.
- the composition was applied to AQT-36 aluminum panels purchased from Q-Panel Inc and on Bl 000 pretreated cold rolled steel purchased from ACT inc.
- the compositions were cured in an oven at 200C for 25 minutes (5 minutes ramp to temp, 20 minutes at metal temperature).
- the resulting film thickness of the coating was targeted to be between 45-75 microns. The actual range was wider.
- Coating composition flexibility was tested using an Erichsen indenter following ISO 1520:2006E. Coating thickness was determined using a Fischer Permascope calibrated on ACT B1000. Film build was targeted to be between 50-75 microns. Before Erichson cupping is run, the cured panels are equilibrated at room temperature for 24 hrs.
- the painted panel is placed in the Erichson indenter with the coating facing away from the indenter ball and secured by the retainer ring.
- the indenter ball is driven into the panel at a rate of 0.1 -0.3 mm/s.
- the onset of visual cracking is measured in mm of indention.
- Comparative Coatings were prepared by using powder coating compositions CPI to CP8 prepared using the procedure from Comparative Example 3 and tested according to the method described in Example 5. The results are listed in Table 10.
- Powder coating compositions were preprepared according to Example 4 by using Resins 9 to 18. The compositions are listed in Table 13. [0065] Table 13. List of Powder Coating Compositions CP9 to CPI 8 (in grams)
- Coatings were prepared by using powder coating compositions P9 to Pl 8 prepared from Example 7 and tested according to the method of ASTM D522. The results are listed in Table 14. As shown by the data, coatings based on resins 10 to 18, which comprise a linear diacid, adipic acid or dodecanedicarboxylic acid (DDDA), in each resin composition, have superior flexibility over the coating based on resin 9 without linear diacid, as tested by the Conical Mandrel method. This property is particularly desirable for automotive wheel powder coating applications. [0068] Table 14. Powder Coating Test Results According to the Rating from 0 to 5 below:
- Example 9 Synthesis of Polyester Resins with Various Monomers (Resins 19 to 25)
- Additional polyester resins having various monomers were prepared and evaluated according to the methods described previously. Their compositions in mole ratios are listed in Table 15; their weights charged in grams are listed in Table 16; their resin properties are listed in Table 17; their powder coating compositions are listed in Table 18; and their coating test results are listed in Table 19. [0070] Table 15. List of Polyester Resin Compositions in Mole Ratios (Resins 19 to
- Comparative polyester resins having a lower ratio (6 mole %) of the branching agent, TMP were prepared and evaluated according to the methods described previously. Their compositions in mole ratios are listed in Table 20; their weights charged in grams are listed in Table 21; their resin properties are listed in Table 22; their powder coating compositions are listed in Table 23; and their coating test results are listed in Table 24.
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Abstract
The invention provides polyester-based powder coating compositions useful in the coating of shaped or formed articles, which exhibit improved properties such as weathering performance and flexibility. In general, the polyesters are comprised of residues of 2,2,4,4-tetramethyl-1,3-cyclobutanedio; a diol residue selected from the group consisting of neopentyl glycol, cyclohexanedimethanol, 1,6-hexanediol, 1,4-butanediol, hydroxypivalyl hydroxypivalate, and combinations thereof; residues of trimethylolpropane; and residues of hexahydrophthalic anhydride. The polyester component of the compositions is formulated as predominantly carboxyl-functional and have an acid number of about 20 to 90 mg KOH/g of resin, and thus are suitably cross-linked in a thermosetting powder coating composition system with cross-linking compounds known to react with such carboxyl groups.
Description
THERMOSETTING POWDER COATING COMPOSITIONS
Field of the Invention
[0001] The invention relates to powder coating compositions comprising carboxyl- functional polyesters. The polyesters are comprised of 2,2,4,4-tetramethyl-l,3- cyclobutanediol and trimethylolpropane.
Background of the Invention
[0002] There have been increasing demands for powder coatings in the industry due to their good corrosion protection and outdoor durability. Various types of resin technologies are used for powder coatings. These include epoxy, polyester, acrylic, and the hybrids thereof. For outdoor applications, polyester, fluoropolymer, and acrylic resins are commonly used. Polyesters generally provide a good balance of desirable coating properties such as appearance and impact resistance, while acrylic resin and fluoropolymer typically exhibit better weatherability. Thus, it would be highly desirable to develop a polyester-based powder coating composition having good weatherability while also possessing a glass transition temperature (Tg) suitable for powder coating systems.
Summary of the Invention
[0003] In summary, the invention provides polyester-based powder coating compositions useful in the coating of shaped or formed articles, which exhibit improved properties such as weathering performance and flexibility. In one or more embodiments herein, the powder coating composition comprises: A. at least one carboxyl-functional polyester which comprises:!, a polyol component comprising: i. about 50 to about 87 mole percent of 2,2,4,4-tetramethyl-l,3-cyclobutanediol residues, based on the total moles of i., ii., iii. and iv.; ii. about 5 to about 35 mole percent of a diol residue selected from the group consisting of neopentyl glycol, cyclohexanedimethanol, 1,6-hexanediol, 1,4-butanediol, hydroxypivalyl hydroxypivalate, and combinations thereof, based on the total moles of i., ii., iii., and iv.; iii. 0 to about 20 mole percent of diol residues which is other than (i) and (ii), based on the total moles of i., ii., iii., and iv.; and iv. about 8 to about 25 mole percent of trimethylolpropane residues, based on the total moles of i., ii.,
iii. and iv.; a dicarboxylic acid component comprising: v. about 70 to about 100 mole percent of hexahydrophthalic anhydride residues, based on the total moles of v. and vi.; and vi. 0 to about 30 mole percent of a C6-C12 acyclic diacid residues, based on the total moles of v. and vi.; wherein the polyester has a glass transition temperature of about 45° to 90°C, an acid number of about 20 to about 90 mg KOH/g, a number average molecular weight of about 1,000 to about 10,000 g/mole, and a weight average molecular weight of about 5,000 to about 100,000 g/mole; and B. one or more compounds reactive with the carboxyl-functional polyester.
[0004] In further embodiments herein, the powder coating composition comprises: A. at least one carboxyl-functional polyester, in an amount of about 70 to 95 weight percent, based on the total weight of A. B. and C., which comprises: 1. a polyol component comprising: i. about 60 to about 80 mole percent of 2,2,4,4-tetramethyl-l,3- cyclobutanediol residues, based on the total moles of i., ii., iii. and iv.; ii. 8 to about 28 mole percent of diol residue selected from the group consisting of neopentyl glycol, cyclohexanedimethanol, 1,6-hexanediol, 1 ,4-butanediol, hydroxypivalyl hydroxypivalate, and combinations thereof, based on the total moles of i., ii., iii., and iv.; iii. 0 to about 20 mole percent of diol residues which is other than (i) and (ii), based on the total moles of i., ii., iii., and iv.; and iv. about 12 to about 17 mole percent of trimethylolpropane residues, based on the total moles of i., ii., iii., and iv.; 2. a dicarboxylic acid component comprising: v. about 75 to about 95 mole percent of hexahydrophthalic anhydride residues, based on the total moles of v. and vi.; and vi. about 5 to about 25 mole percent of a C6-C12 acyclic diacid residues, based on the total moles of v. and vi.; wherein the polyester has a glass transition temperature of about 45° to 90°C, an acid number of about 40 to about 60 mg KOH/g, a number average molecular weight of about 1,000 to about 10,000 g/mole, and a weight average molecular weight of about 5,000 to a about 100,000 g/mole; B. a glycidyl functional crosslinker in an amount of about 5 to about 30 weight percent, based on the total weight of A., B., and C.; and C. a P-hydroxy alkyl amide cross-linker in an amount of about 0 to about 5 weight percent, based on the total weight of A., B., and C.
[0005] In even further embodiments herein the powder composition comprises: A. at least one carboxyl-functional polyester, in an amount of about 80 to 90 weight percent,
based on the total weight of A. and B., which comprises: 1. a polyol component comprising: i. about 60 to about 80 mole percent of 2,2,4,4-tetramethyl-l,3- cyclobutanediol residues, based on the total moles of i., ii., iii. and iv.; ii. 8 to about 28 mole percent of diol residue selected from the group consisting of neopentyl glycol, cyclohexanedimethanol, 1,6-hexanediol, 1 ,4-butanediol, hydroxypivalyl hydroxypivalate, and combinations thereof, based on the total moles of i., ii., iii., and iv.; iii. 0 to about 20 mole percent of diol residues which is other than (i) and (ii), based on the total moles of i., ii., iii., and iv.; and iv. about 12 to about 17 mole percent of trimethylolpropane residues, based on the total moles of i., ii., iii., and iv.; 2. a dicarboxylic acid component comprising: v. about 80 to about 100 mole percent of hexahydrophthalic anhydride residues, based on the total moles of v. and vi.; and vi. 0 to about 20 mole percent of a C6-C12 acyclic diacid residues, based on the total moles of v. and vi.; wherein the polyester has a glass transition temperature of about 45° to 90°C, an acid number of about 30 to about 80 mg KOH/g, a number average molecular weight of about 1,000 to about 10,000 g/rnole, and a weight average molecular weight of about 5,000 to a about 100,000 g/mole; and B. a P-hydroxy alkyl amide cross-linker in an amount of about 10 to about 20 weight percent, based on the total weight of A. and B.
Detailed Description
[0006] In a first aspect, the invention provides a powder coating composition comprising: A. at least one carboxyl-functional polyester which comprises:!, a polyol component comprising: i. about 50 to about 87 mole percent of 2,2,4,4-tetramethyl-l,3- cyclobutanediol residues, based on the total moles of i., ii., iii. and iv.; ii. about 5 to about 35 mole percent of a diol residue selected from the group consisting of neopentyl glycol, cyclohexanedimethanol, 1,6-hexanediol, 1 ,4-butanediol, hydroxypivalyl hydroxypivalate, and combinations thereof, based on the total moles of i., ii., iii., and iv.; iii. 0 to about 20 mole percent of diol residues which is other than (i) and (ii), based on the total moles of i., ii., iii., and iv.; and iv. about 8 to about 25 mole percent of trimethylolpropane residues, based on the total moles of i., ii., iii. and iv. ; a dicarboxylic acid component comprising: v. about 70 to about 100 mole percent of hexahydrophthalic anhydride residues, based on the total moles of v. and vi.; and vi. 0
to about 30 mole percent of a C6-C12 acyclic diacid residues, based on the total moles of v. and vi.; wherein the polyester has a glass transition temperature of about 45° to 90°C, an acid number of about 20 to about 90 mg KOH/g, a number average molecular weight of about 1,000 to about 10,000 g/mole, and a weight average molecular weight of about 5,000 to about 100,000 g/mole; and B. one or more compounds reactive with the carboxyl-functional polyester.
[0005] It should be understood that the following is not intended to be an exclusive list of defined terms. Other definitions may be provided in the description, such as, for example, when accompanying the use of a defined term in context. As used herein, the terms “a,” “an,” and “the” mean one or more. As used herein, the term “and/or,” when used in a list of two or more items, means that any one of the listed items can be employed by itself or any combination of two or more of the listed items can be employed. For example, if a composition is described as containing components A, B, and/or C, the composition can contain A alone; B alone; C alone; A and B in combination; A and C in combination, B and C in combination; or A, B, and C in combination.
[0006] The term "polyester", as used herein, is intended to include "copolyesters" and is understood to mean a synthetic polymer prepared by the reaction of one or more difunctional carboxylic acids and/or multifunctional carboxylic acids with one or more difunctional hydroxyl compounds and/or multifunctional hydroxyl compounds, as referred to above as comprised of a dicarboxylic acid component and a polyol component. Typically, the difunctional carboxylic acid can be a dicarboxylic acid and the difunctional hydroxyl compound can be a dihydric alcohol, for example, glycols and diols. The term "polyol " as used herein includes, but is not limited to, diols, glycols, and/or multifunctional hydroxyl compounds. The term "residue", as used herein, means any organic structure incorporated into a polymer through a polycondensation and/or an esterification reaction from the corresponding monomer. The term "repeating unit", as used herein, means an organic structure having a dicarboxylic acid residue and a diol residue bonded through an ester group. Thus, for example, the dicarboxylic acid residues may be derived from a dicarboxylic acid monomer or its associated acid halides, esters, salts, anhydrides, and/or mixtures thereof. Furthermore, as used herein,
the term "diacid" includes multifunctional acids. As used herein, therefore, the term "dicarboxylic acid" is intended to include dicarboxylic acids and any derivative of a dicarboxylic acid, including its associated acid halides, esters, half-esters, salts, halfsalts, anhydrides, mixed anhydrides, and/or mixtures thereof, useful in a reaction process with a diol to make a polyester.
[0007] The stoichiometry of the polyol components and dicarboxylic acid components can be adjusted as needed to obtain the desired acid number (and/or hydroxyl number) in the final carboxyl-functional polyester to be utilized in the powder coating composition.
[0008] The polyester portion of the compositions of the invention can be made by processes known in the art, for example, by processes in homogenous solution, by transesterification processes in the melt, and by two phase interfacial processes. Suitable methods include, but are not limited to, the steps of reacting one or more dicarboxylic acids with one or more diols at a temperature of 100°C to 315°C at a pressure of 0.1 to 760 mm Hg for a time sufficient to form a polyester. See U.S. Pat. No. 3,772,405 for methods of producing polyesters, the disclosure regarding such methods is hereby incorporated herein by reference.
[0009] In one embodiment, the carboxyl-functional polyester is comprised of all aliphatic groups or is comprised of substantially no aromatic groups. In another embodiment, the carboxyl-functional polyester comprises not more than about 10 mole percent aromatic diacid residues, such as isophthalic acid and terephthalic acid, based on the total moles of the dicarboxylic acid components.
[0010] In another embodiment, the polyol component comprises about 55 to 85 mole percent of 2,2,4,4-tetramethyl-l,3-cyclobutanediol residues, based on the total moles of
1., ii., iii. and iv.; ii. about 5 to about 30 mole percent of a diol residue selected from the group consisting of neopentyl glycol, cyclohexanedimethanol, 1,6-hexanediol, 1,4- butanediol, hydroxypivalyl hydroxypivalate, and combinations thereof, based on the total moles of i., ii., iii., and iv.; iii. 0 to about 20 mole percent of diol residues which is other than (i) and (ii), based on the total moles of i., ii., iii., and iv.; and iv. about 10 to about 20 mole percent of trimethylolpropane residues, based on the total moles of i.,
11., iii. and iv.; and wherein the dicarboxylic acid component comprises about 75 to
about 100 mole percent of hexahydrophthalic anhydride residues; and 0 to about 25 mole percent of a C6-C12 acyclic diacid residues.
[0011] In another embodiment, the polyol component comprises about 60 to 80 mole percent of 2,2,4,4-tetramethyl-l ,3 -cyclobutanediol residues, based on the total moles of
1., ii., iii. and iv.; ii. about 8 to about 28 mole percent of a diol residue selected from the group consisting of neopentyl glycol, cyclohexanedimethanol, 1,6-hexanediol, 1,4- butanediol, hydroxypivalyl hydroxypivalate, and combinations thereof, based on the total moles of i., ii., iii., and iv.; iii. 0 to about 20 mole percent of diol residues which is other than (i) and (ii), based on the total moles of i., ii., iii., and iv.; and iv. about 12 to about 17 mole percent of trimeth ylolpropane residues, based on the total moles of i.,
11., iii. and iv.; and wherein the dicarboxylic acid component comprises about 80 to about 100 mole percent of hexahydrophthalic anhydride residues; and 0 to about 20 mole percent of a C6-C12 acyclic diacid residues.
[0012] Examples of diol residues which is other than (i) and (ii) may include 2-butyl- 2-ethyl-l,3-propanediol (BEPD), ethylene glycol, propylene glycol, 2-methyl-l,3- propanediol (MPDiol), and mixtures thereof. In one embodiment, the diol residues which is other than (i) and (ii) is selected from the group consisting of 2-methyl-l,3- propanediol and 2-butyl-2-ethyl-l,3-propanediol.
[0013] In embodiments herein, the acyclic diacid is a C6-C12 diacid. Exemplary C6- C12 acyclic diacids include adipic acid, sebacic acid, and dodecanedicarboxylic acid. In some embodiments, the C6-C12 acyclic diacid is adipic acid.
[0014] As noted above, the carboxyl-functional polyester has an acid number of about 20 to 90 mg KOH/g resin. In certain embodiments, the polyester has an acid number of about 30 to 80, 35 to 70, or 40 to 60 mg KOH/g.
[0015] In certain embodiments, the carboxyl-functional polyester has a hydroxyl number of 0 to 20, 0 to 15, 0 to 10, or 0 to 5 mg KOH/g resin.
[0016] As noted above, the carboxyl-functional polyesters have a glass transition temperature of about 45° to 90°C. In certain embodiments, the polyester has a Tg of about 50° to about 80°C, or about 55° to about 75°C.
[0017] As noted above, the carboxyl-functional polyester will have a number average molecular weight of about 1,000 to about 10,000 g/mole. In certain embodiments, the carboxyl-functional polyester will have a number average molecular weight of about 1,000 to about 9,000, about 1,500 to about 8,000, or about 1,500 to about 6,000 g/mole. As noted above, the carboxyl-functional polyester will have a weight average molecular weight of about 5,000 to about 100,000. In certain embodiments, the carboxyl- functional polyester will have a weight average molecular weight of about 5,000 to about 80,000 or about 5,000 to about 50,000 g/mole.
[0018] In certain embodiments, the compounds reactive with the carboxyl-functional polyester is a cross-linker chosen from P-hydroxyalkylamides and glycidyl -functional compounds. In certain embodiments, the P-hydroxyalkylamide is chosen from bis(N,N'-dihydroxyethyl)adipamide, bis(N,N'-dihydroxypropyl)adipamide, or a mixture thereof. Commercially-available P-hydroxyalkylamides include bis(N,N'- dihydroxyethyl)adipamide (Primid® XL-552), bis(N,N'-dihydroxypropyl)adipamide (Primid® QM-1260), and Primid® SF-4510 available from EMS-GRILTECH. Also commercially available is Megamid XL from MEGARA RESINS-ANASTASIOS FANIS S.A.
[0019] Commercially-available glycidyl functional curing agents include triglycidyl isocyanurate based crosslinkers available from Huntsman as Araldite PT 810, PT910, and PT 912. Also suitable are glycidyl acrylates and glycidyl methacrylates such as those commercially available as GMA 300G, 400G and 500 from Estron Chemical.
[0020] In other embodiments, the compound reactive with the carboxyl-functional polyester is an epoxy resin. Exemplary epoxy resins include those having a molecular weight of about 300 to about 4000, and have approximately 0.05 to about 0.99 epoxy groups per 100 grams of resin (i.e., 100-2000 weight per epoxy (WPE)). Such resins are widely known and commercially available under the EPON® mark (Hexion), ant the Araldite® mark (Huntsman).
[0021] In the coating compositions of the invention, in certain embodiments the polyester is present in an amount of about 70 to about 97 percent, by weight, and either: (a) the one or more compounds reactive with the carboxyl-functional polyester or (b) the cross-linker, is present in an amount of about 3 to about 30 percent, by weight, based
on the total amount of polyester and the one or more compounds or cross-linker. In another embodiment, the coating composition of the present invention the carboxyl- functional polyester is present in an amount of about 70 to 95, 75 to 95, or 80 to 90 weight percent and either: (a) the one or more compounds reactive with the carboxyl- functional polyester or (b) the cross-linker, is present in an amount of about 5 to 30, 5 to 25, or 10 to 20 weight percent, based on the total amount of polyester and the one or more compounds or cross-linker.
[0022] In another aspect, the invention provides a powder coating composition comprising: A. at least one carboxyl-functional polyester, in an amount of about 80 to 90 weight percent, based on the total weight of A. and B., which comprises: 1. a polyol component comprising: i. about 60 to about 80 mole percent of 2,2,4,4-tetramethyl-l,3- cyclobutanediol residues, based on the total moles of i., ii., iii. and iv.; ii. 8 to about 28 mole percent of diol residue selected from the group consisting of neopentyl glycol, cyclohexanedimethanol, 1,6-hexanediol, 1 ,4-butanediol, hydroxypivalyl hydroxypivalate, and combinations thereof, based on the total moles of i., ii., iii., and iv.; iii. 0 to about 20 mole percent of diol residues which is other than (i) and (ii), based on the total moles of i., ii., iii., and iv.; and iv. about 12 to about 17 mole percent of trimethylolpropane residues, based on the total moles of i., ii., iii., and iv.; 2. a dicarboxylic acid component comprising: v. about 80 to about 100 mole percent of hexahydrophthalic anhydride residues, based on the total moles of v. and vi.; and vi. 0 to about 20 mole percent of a C6-C12 acyclic diacid residues, based on the total moles of v. and vi.; wherein the polyester has a glass transition temperature of about 45° to 90°C, an acid number of about 30 to about 80 mg KOH/g, a number average molecular weight of about 1,000 to about 10,000 g/mole, and a weight average molecular weight of about 5,000 to a about 100,000 g/mole; and B. a P-hydroxyalkylamide cross-linker in an amount of about 10 to about 20 weight percent, based on the total weight of A. and B.
[0023] In certain embodiments, the P-hydroxyalkylamide cross-linker will be present in an amount of about 3 to about 20 weight percent, based on the total weight of A. and B.
[0024] In certain embodiments, the carboxyl-functional polyester of the invention comprises an acyclic diacid to further improve the flexibility in order to meet the need of certain applications such as, for example, automotive wheel powder coating, that require higher flexibility.
[0025] Thus, this invention further provides a powder coating composition comprising: A. at least one carboxyl-functional polyester, in an amount of about 70 to 95 weight percent, based on the total weight of A. B. and C., which comprises: 1. a polyol component comprising: i. about 60 to about 80 mole percent of 2,2,4,4-tetramethyl-l,3- cyclobutanediol residues, based on the total moles of i., ii., iii. and iv.; ii. 8 to about 28 mole percent of diol residue selected from the group consisting of neopentyl glycol, cyclohexanedimethanol, 1,6-hexanediol, 1 ,4-butanediol, hydroxypivalyl hydroxypivalate, and combinations thereof, based on the total moles of i., ii., iii., and iv.; iii. 0 to about 20 mole percent of diol residues which is other than (i) and (ii), based on the total moles of i., ii., iii., and iv.; and iv. about 12 to about 17 mole percent of trimethylolpropane residues, based on the total moles of i., ii., iii., and iv.; 2. a dicarboxylic acid component comprising: v. about 75 to about 95 mole percent of hexahydrophthalic anhydride residues, based on the total moles of v. and vi.; and vi. about 5 to about 25 mole percent of a C6-C12 acyclic diacid residues, based on the total moles of v. and vi.; wherein the polyester has a glass transition temperature of about 45° to 90°C, an acid number of about 40 to about 60 mg KOH/g, a number average molecular weight of about 1,000 to about 10,000 g/mole, and a weight average molecular weight of about 5,000 to a about 100,000 g/mole; B. a glycidyl functional crosslinker in an amount of about 5 to about 30 weight percent, based on the total weight of A., B., and C.; and C. a P-hydroxyalkylamide cross-linker in an amount of about 0 to about 5 weight percent, based on the total weight of A., B., and C
[0026] Examples of said acyclic diacid include C6 to C12 linear diacid such as adipic acid, sebacic acid, and dodecanedicarboxylic acid.
[0027] In other embodiments, the powder coating compositions of the invention may further comprise waxes, pigments, fillers, degassing agents, flow agents, and/or other additives. Examples of pigments include inorganic and organic pigments such as titanium dioxide, iron oxide, chromium oxide, zinc sulfide, zinc phosphate, mica, azo
compounds, and the like. Suitable fillers include silicates, sulfates, and carbonates. Examples of additives include degassing agents, antioxidants, and UV stabilizers. Exemplary weathering stabilizers that can be used in these embodiments include are hindered amine light stabilizers and UV absorbers. Examples of degassing agents include cyclohexane dimethanol dibenzoate, benzoin, and benzoin derivatives. Examples of flow control agents include Byk® 361 N (BYK) and Resiflow® PV-5 (Estron). Further examples of typical additives for powder coating compositions can be found in U.S. Patent No. 10,916,539, incorporated herein by reference.
[0028] The powder coating compositions of the invention may be prepared by any methods known in the art. In a typical method, the powders of the carboxyl-functional polyester and the crosslinker are mixed along with any desired additives at room temperature to obtain a premix. The premix is then extruded at an elevated temperature such as, for example, 80° to 130°, 90° to 125°, or 100° to 120 °C, to yield an extrudate, which is then cooled to solidify the mixture. The resulting solid is then made into powder by milling and subsequently sieved to classify the size of the particles. The powder coating of the present invention desirably has particle sizes less than about 120 pm, less than 110 pm, or less than 100 pm.
[0029] The powder coating composition may be applied to an article, such as, a substrate by a common method such as electrostatic spray deposition (ESD) or fluidized bed application at a thickness of about 1 to about 10 mils (1 mil - 25 pm). The coating may be cured at 140° to 230°C, 140° to 200°C, 140° to 180°C, or 140° to 160°C for 10 minutes to one hour, or other suitable conditions, and allowed to cool.
[0030] See also: User’s Guide to Powder Coating, 4th Ed., Nicholas Liberto, editor, Society of Manufacturing Engineers (2003).
[0031] As noted above, the powder coating compositions of the invention can be applied to a substrate or shaped or formed article. Thus, a further aspect of the present invention is a shaped or formed article, of which at least a portion has been coated with the coating compositions of the present invention. The substrate can be any common substrate such as aluminum, tin, steel or galvanized sheeting, and the like. The coating composition can be coated onto a substrate using techniques known in the art, for example, by electrostatic spray deposition (ESD) or fluidized bed application at a
thickness of about 1 to about 10 mils (1 mil = 25 pm). The coating can be cured at a temperature of about 140°C to about 230°C for a time period that ranges from about 10 minutes to about 60 minutes and allowed to cool.
[0032] One mechanical property of the cured (i.e., thermoset) powder coating compositions of the invention can be described by Erichsen cupping test in accordance with ISO-1520. In some embodiments, the cured powder coating compositions of the invention exhibit an Erichsen cupping test rating of 3 mm or more, 3.5 mm or more, 4mm or more, 4.25 mm or more, or 5 mm or more for the onset of cracking, and with no delamination of > 7mm.
[0033] Thus, in certain embodiments, the cured coating compositions on such articles exhibit improved performance characteristics. For example, articles coated with the cured compositions of the invention can exhibit an Erichsen crack rating of 3 mm or more according to the method of ISO-1520.
[0034] The invention can be further illustrated by the following Examples of certain embodiments thereof, although it will be understood that these Examples are included merely for the purposes of illustration and are not intended to limit the scope of the invention unless otherwise specifically indicated.
Examples
[0035] In these Examples, the following abbreviations are used:
TMCD - 2,2,4,4-tetramethyl-l,3-cyclobutanediol - from Eastman Chemical Co.
TMP- trimethylol propane - available from Sigma-Aldrich
NPG= 2,2-dimethyl-l,3-propanediol (neopentyl glycol) - available from Sigma- Aldrich
CHDM - 1 ,4-cyclohexanedimethanol from Eastman Chemical Co.
MP Diol ~ 2-methyl-l,3-propanediol from Eastman Chemical Co.
BEPD = 2-butyl-2-ethyl-l,3-propanediol available from Sigma- Aldrich
HPHP ~ hydroxypivalyl hydroxypivalate from Eastman Chemical Co.
HHPA - hexahydrophthalic anhydride - available from Sigma- Aldrich
DDDA - Dodecanedioic acid available from Sigma- Aldrich
Adipic = adipic acid available from Sigma- Aldrich
Succinic = succinic acid available from Sigma-Aldrich
TPP = triphenylphosphite - available from Sigma- Aldrich
Butyl stannoic acid available from Sigma-Aldrich
Al AQT 36 = Aluminum test panel available from Q-Panel Inc.
CRS B1000 - Steel test panel available from ACT Inc.
P EPQ = Hostanox® P-EPQ® powder (Qari ant)
Primid® XL 552 - hydroxyl alkyl amide crosslinker available from Estron Inc.
GMA 300 - glycidyl functional acrylate crosslinker available from Estron Inc.
GMA 500 - glycidyl functional acrylate crosslinker available from Estron Inc.
Resiflow® PL-200 - flow and wetting additive available from Estron Inc.
Benzoin - degassing agent available from Estron Inc.
Irganox® 1076 - an antioxidant available from BASF
Staphyloid AC 4030 - A plasticizer available from Danick Specialties and Support.
Tinuvin® 405 is a UV absorber from BASF
Tinuvin® 144 is a hindered amine light stabilizer from BASF
Example 1. Synthesis of Carboxyl-Functional Polyester Resin (Resin 1)
[0036] The resin was prepared in a two-liter reaction kettle equipped with a heating mantle, mechanical stirrer, thermocouple, nitrogen blanket (1.0 standard cubic feet per hour), oil-heated partial condenser (103 °C - 105°C), condensate trap, and water-cooled total condenser (15°C). The condensate trap, kettle top and adapter from the kettle to the column were wrapped in aluminum foil and fiberglass tape to facilitate water removal.
[0037] 786.7 grams HHPA, 186.4 grams adipic acid, 586.4 grams TMCD and 1.7 grams TPP were charged to the reactor. The reactor was then heated from room temperature to 100°C at l°C/minute to obtain a homogeneous melt. Agitation was then started at 300 rpm and the temperature was increased to 165°C at l°C/minute. An exotherm was observed from 140°C to 180°C. After the exotherm, acid number was taken to ensure complete reaction of the TMCD, and the reactor was allowed to cool to 150°C.
[0038] At 150°C and under agitation, 84.7 grams NPG, 72 grams TMP and 1.7 grams butylstannoic acid were added. The temperature was then set to 165 °C. Once the temperature stabilized at 165°C, the temperature was increased to 235°C at 0.1°C/min.
The reaction is held at 235°C until the target acid number, 55 mg KOH/g, was reached.
Example 2. Synthesized Carboxyl-Functional Polyester Resins (Resins 1 to 8)
[0039] Using the same method as Example 1, Resins 1 to 8 were synthesized according to the mole ratios of the components listed in Table 1 and the weights of the components charged as listed in Table 2.
[0040] Table 1. List of Synthesized Polyester Resin Compositions in Mole Ratios
[0041] Table 2. List of Synthesized Polyester Resin Compositions (Weight Charged)
Comparative Example 1. Synthesized Comparative Carboxyl-Functional Polyester Resins (Comparative Resins Cl to C8)
[0042] Using the same method as Example 1, Comparative Resins Cl to C8 were synthesized according to the mole ratios of the components listed in T able 3 and the weights of the components charged as listed in Table 4.
[0043] Table 3. List of Synthesized Comparative Polyester Resin Compositions in Mole Ratios
[0044] Table 4. List of Synthesized Comparative Polyester Resin Compositions
Example 3. Resin Properties of Synthesized Polyester Resins [0045] Glass transition temperature (Tg) was determined using a Q2000 differential scanning calorimeter (DSC) from TA Instruments, New Castle, DE, US, at a scan rate of 20°C/min. Number average molecular weight (Mn) and weight average molecular weight (Mw) were measured by gel permeation chromatography (GPC) using polystyrene equivalent molecular weight. Acid number was measured by using a procedure based on ASTM D7253-1 entitled “Standard Test Method for Polyurethane
Raw Materials: Determination of Acidity as Acid Number for Polyether Polyols,” and hydroxyl number was measured using a procedure based on ASTM E222-1 entitled “Standard Test Methods for Hydroxyl Groups Using Acetic Anhydride.” Viscosity was measured using a CAP 2000 viscometer at 200°C. [0046] Table 5. Resin Properties of Synthesized Polyester Resins 1 to 8
Comparative Example 2. Resin Properties of Synthesized Comparative Polyester
Resins
[0047] Table 6. Resin Properties of Synthesized Comparative Polyester Resins Cl to
Example 4. Preparation of Powder Coating Compositions Pl to P8
[0048] Powder coating compositions (P1 to P8) were prepared respectively by using Resins 1 to 8. Each coating composition was weighed into a container. The compositions were then milled using a Vitamix mill. The resulting milled compositions were extruded on a two-zone twin screw extruder at 320 RPM and 60-70% torque. Zone 1 was heated to 100°C while Zone 2 was at 110°C. The compositions were cooled on a twin roll chiller at 2-5 °C and collected in a plastic bag. The compositions were allowed to fully cool to room temperature overnight. They were then powdered using a Strand mill. The resulting powder compositions were sieved using 106-micron mesh. The sieved powder coating compositions were then considered ready to spray. The compositions are listed in Table 7.
Comparative Example 3. Preparation of Comparative Powder Coating Compositions CPI to CP8
[0050] Coating formulations were prepared according to the method described in Example 4 by using comparative resins Cl to C8. Their compositions are listed in Table 8.
Example 5. Coating Preparation and Testing
[0052] Powder coating compositions P1 to P8 prepared using the procedure from Example 4 were applied to the metal substrate using a Parker Ionics GX700C Powder Gun System electrostatic powder spray apparatus. The composition was applied to AQT-36 aluminum panels purchased from Q-Panel Inc and on Bl 000 pretreated cold rolled steel purchased from ACT inc. The compositions were cured in an oven at 200C for 25 minutes (5 minutes ramp to temp, 20 minutes at metal temperature). The resulting
film thickness of the coating was targeted to be between 45-75 microns. The actual range was wider.
Testing
[0053] Coating composition flexibility was tested using an Erichsen indenter following ISO 1520:2006E. Coating thickness was determined using a Fischer Permascope calibrated on ACT B1000. Film build was targeted to be between 50-75 microns. Before Erichson cupping is run, the cured panels are equilibrated at room temperature for 24 hrs.
[0054] The painted panel is placed in the Erichson indenter with the coating facing away from the indenter ball and secured by the retainer ring. The indenter ball is driven into the panel at a rate of 0.1 -0.3 mm/s. The onset of visual cracking is measured in mm of indention.
[0055] The chart below shows the onset of cracking for the coatings:
[0057] Comparative Example 4. Comparative Coating Preparation and Testing
[0058] Comparative Coatings were prepared by using powder coating compositions CPI to CP8 prepared using the procedure from Comparative Example 3 and tested according to the method described in Example 5. The results are listed in Table 10.
Example 6. Synthesis of Additional Carboxyl-Functional Polyester Resins (Resins 9 to 18}
[0060] Using the same method as described in Example 1, Resins 9 to 18 were synthesized according to the mole ratios of the components listed in Table 11. Their resin properties are listed in Table 12.
[0061] Table 11. List of Synthesized Polyester Resin Compositions in Mole Ratios
[0063] Example 7. Preparation of Powder Coating Compositions P9 to Pl 8
[0064] Powder coating compositions were preprepared according to Example 4 by using Resins 9 to 18. The compositions are listed in Table 13.
[0065] Table 13. List of Powder Coating Compositions CP9 to CPI 8 (in grams)
[0066] Example 8. Coating Preparation and Testing
[0067] Coatings were prepared by using powder coating compositions P9 to Pl 8 prepared from Example 7 and tested according to the method of ASTM D522. The results are listed in Table 14. As shown by the data, coatings based on resins 10 to 18, which comprise a linear diacid, adipic acid or dodecanedicarboxylic acid (DDDA), in each resin composition, have superior flexibility over the coating based on resin 9 without linear diacid, as tested by the Conical Mandrel method. This property is particularly desirable for automotive wheel powder coating applications. [0068] Table 14. Powder Coating Test Results According to the Rating from 0 to 5 below:
Example 9. Synthesis of Polyester Resins with Various Monomers (Resins 19 to 25) [0069] Additional polyester resins having various monomers were prepared and evaluated according to the methods described previously. Their compositions in mole ratios are listed in Table 15; their weights charged in grams are listed in Table 16; their resin properties are listed in Table 17; their powder coating compositions are listed in Table 18; and their coating test results are listed in Table 19.
[0070] Table 15. List of Polyester Resin Compositions in Mole Ratios (Resins 19 to
[0072] Table 17. Resin Properties of Synthesized Polyester Resins 19 to 25
[0073] Table 18. List of Powder Coating Compositions P19 to P25 (in grams)
[0074] Table 19. Erichsen Cupping Results of the Powder Coatings P19 to P25
Comparative Example 5. Synthesis of Polyester Resins with Lower TMP Ratio (Resins C9 to C10)
[0075] Comparative polyester resins having a lower ratio (6 mole %) of the branching agent, TMP, were prepared and evaluated according to the methods described previously. Their compositions in mole ratios are listed in Table 20; their weights charged in grams are listed in Table 21; their resin properties are listed in Table 22; their powder coating compositions are listed in Table 23; and their coating test results are listed in Table 24.
[0078] Table 22. Resin Properties of Synthesized Polyester Resins C9 to CIO
[0079] Table 23. List of Powder Coating Compositions CP9 to CP10 (in grams)
Claims
1. A powder coating composition comprising:
A. at least one carboxyl-functional polyester which comprises:
1. a polyol component comprising: i. about 50 to about 87 mole percent of 2,2,4,4-tetramethyl- 1,3-cyclobutanediol residues, based on the total moles of i., ii., iii. and iv.; ii. about 5 to about 35 mole percent of a diol residue selected from the group consisting of neopentyl glycol, cyclohexanedimethanol, 1 ,6-hexanediol, 1 ,4-butanediol, hydroxypivalyl hydroxypivalate, and combinations thereof, based on the total moles of i., ii., iii., and iv.; iii. 0 to about 20 mole percent of diol residues which is other than (i) and (ii), based on the total moles of i., ii., iii., and iv.; and iv. about 8 to about 25 mole percent of trimethylolpropane residues, based on the total moles of i., ii., iii. and iv.;
2. a dicarboxylic acid component comprising: v. about 70 to about 100 mole percent of hexahydrophthalic anhydride residues, based on the total moles of v. and vi.; and vi. 0 to about 30 mole percent of a C6-C12 acyclic diacid residues, based on the total moles of v. and vi. ; wherein the polyester has a glass transition temperature of about 45° to 90°C, an acid number of about 20 to about 90 mg KOH/g, a number average molecular weight of about 1,000 to about 10,000 g/mole, and a weight average molecular weight of about 5,000 to about 100,000 g/mole; and
B. one or more compounds reactive with the carboxyl-functional polyester.
2 A powder coating composition comprising:
A. at least one carboxyl-functional polyester, in an amount of about 70 to 95 weight percent, based on the total weight of A. B. and C., which comprises:
1 . a polyol component comprising: i. about 60 to about 80 mole percent of 2,2,4,4-tetramethyl- 1,3-cyclobutanediol residues, based on the total moles of i., ii., iii. and iv.; ii. 8 to about 28 mole percent of a diol residue selected from the group consisting of neopentyl glycol, cyclohexanedimethanol, 1,6- hexanediol, 1,4-butanediol, hydroxypivalyl hydroxypivalate, and combinations thereof, based on the total moles of i., ii., iii., and iv.; iii. 0 to about 20 mole percent of diol residues which is other than (i) and (ii), based on the total moles of i., ii., iii., and iv.; and iv. about 12 to about 17 mole percent of trimethylolpropane residues, based on the total moles of i., ii., iii., and iv.;
2. a dicarboxylic acid component comprising: v. about 75 to about 95 mole percent of hexahydrophthalic anhydride residues, based on the total moles of v. and vi.; and vi. about 5 to about 25 mole percent of a C6-C12 acyclic diacid residues, based on the total moles of v. and vi.; wherein the polyester has a glass transition temperature of about 45° to 90°C, an acid number of about 40 to about 60 mg KOH/g, a number average molecular weight of about 1,000 to about 10,000 g/mole, and a weight average molecular weight of about 5,000 to a about 100,000 g/mole;
B. a glycidyl functional crosslinker in an amount of about 5 to about 30 weight percent, based on the total weight of A., B., and C.; and
C. a P-hydroxyalkylamide cross-linker in an amount of about 0 to about 5 weight percent, based on the total weight of A., B., and C.
A powder coating composition comprising:
A. at least one carboxyl-functional polyester, in an amount of about 80 to weight percent, based on the total weight of A. and B., which comprises:
1. a polyol component comprising: i. about 60 to about 80 mole percent of 2,2,4, 4-tetramethyl- 1 ,3-cyclobutanediol residues, based on the total moles of i., ii., iii. and iv.; ii. 8 to about 28 mole percent of a diol residue selected from the group consisting of neopentyl glycol, cyclohexanedimethanol, 1,6- hexanediol, 1,4-butanediol, hydroxypivalyl hydroxypivalate, and combinations thereof, based on the total moles of i., ii., iii., and iv.; iii. 0 to about 20 mole percent of diol residues which is other than (i) and (ii), based on the total moles of i., ii., iii., and iv.; and iv. about 12 to about 17 mole percent of trimethylolpropane residues, based on the total moles of i., ii., iii., and iv.;
2. a dicarboxylic acid component comprising: v. about 80 to about 100 mole percent of hexahydrophthalic anhydride residues, based on the total moles of v. and vi. ; and vi. 0 to about 20 mole percent of a C6-C12 acyclic diacid residues, based on the total moles of v. and vi. ; wherein the polyester has a glass transition temperature of about 45° to 90°C, an acid number of about 30 to about 80 mg KOH/g, a number average molecular weight of about 1,000 to about 10,000 g/mole, and a weight average molecular weight of about 5,000 to a about 100,000 g/mole; and
B. a P-hydroxyalkylamide cross-linker in an amount of about 10 to about 20 weight percent, based on the total weight of A. and B.
4. The composition of claim 1, wherein the compounds reactive with the carboxyl- functional polyester is a cross-linker chosen from [3-hydroxyalkylamides and glycidyl- functional compounds.
5. The composition of claim 1, wherein the compound reactive with the carboxyl- functional polyester is an epoxy resin.
6. The composition of claim 1, wherein the compounds reactive with the carboxyl- functional polyester is a cross-linker chosen from P-hydroxyalkylamides, and wherein the P-hydroxyalkylamides is selected from the group consisting of bis(N,N'- dihydroxyethyl)adipamide, bis(N,N'-dihydroxypropyl)adipamide, and a mixture thereof.
7. The composition of claim 1, wherein the polyol component comprises about 55 to 85 mole percent of 2,2,4,4-tetramethyl-l,3-cyclobutanediol residues, based on the total moles of i. , ii. , iii. and iv. ; ii. about 5 to about 30 mole percent of a diol residue selected from the group consisting of neopentyl glycol, cyclohexanedimethanol, 1,6- hexanediol, 1,4-butanediol, hydroxypivalyl hydroxypivalate, and combinations thereof, based on the total moles of i., ii., iii., and iv.; iii. 0 to about 20 mole percent of diol residues which is other than (i) and (ii), based on the total moles of i., ii., iii., and iv.; and iv. about 10 to about 20 mole percent of trimethylolpropane residues, based on the total moles of i., ii., iii. and iv.; and wherein the dicarboxylic acid component comprises about 75 to about 100 mole percent of hexahydrophthalic anhydride residues; and 0 to about 25 mole percent of a C6-C12 acyclic diacid residues.
8. The composition of claim 1 , wherein the polyol component comprises about 60 to 80 mole percent of 2,2,4,4-tetramethyl-l,3-cyclobutanediol residues, based on the total moles of i. , ii. , iii. and iv. ; ii. about 8 to about 28 mole percent of a diol residue selected from the group consisting of neopentyl glycol, cyclohexanedimethanol, 1,6- hexanediol, 1,4-butanediol, hydroxypivalyl hydroxypivalate, and combinations thereof, based on the total moles of i., ii., iii., and iv.; iii. 0 to about 20 mole percent of diol residues which is other than (i) and (ii), based on the total moles of i., ii., iii., and iv.; and iv. about 12 to about 17 mole percent of trimethylolpropane residues, based on the total moles of i., ii., iii. and iv.; and wherein the dicarboxylic acid component
comprises about 80 to about 100 mole percent of hexahydrophthalic anhydride residues; and 0 to about 20 mole percent of a C6-C12 acyclic diacid residues.
9. The composition of claims 1-8, wherein the diol residues which are other than (i) and (ii) are selected from the group consisting of 2 -methyl- 1,3-propanediol and 2- butyl-2-ethyl- 1 ,3-propanediol.
10. The composition of claims 1 -9, wherein the C6-C12 acyclic diacid is chosen from dodecanedioic acid, adipic acid, and sebacic acid.
11. The composition of claims 1-10, wherein the C6-C12 acyclic diacid is adipic acid.
12. The composition of claims 1-11, wherein the polyester has an acid number of about 40 to about 60 mg KOH/g.
13. The composition of claims 1-12, wherein the polyester has a glass transition temperature of about 55 to about 75°C.
14. The composition of claims 1-13, wherein the polyester is present in an amount of about 70 to about 97 percent, by weight, and either: (a) the one or more compounds reactive with the carboxyl-functional polyester or (b) the cross-linker, is present in an amount of about 3 to about 30 percent, by weight, based on the total amount of polyester and the one or more compounds or cross-linker.
15. An article coated with the coating composition of claims 1-14, wherein the composition is cured.
16. The article of claim 15, wherein the cured coating exhibits an Erichsen crack rating of 3 mm or more according to the method of ISO- 1520.
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US3772405A (en) | 1972-02-02 | 1973-11-13 | Eastman Kodak Co | Process for preparing aromatic diester containing copolyesters and products obtained thereby |
US5637654A (en) * | 1996-08-12 | 1997-06-10 | Mcwhorter Technologies | Low temperature cure carboxyl terminated polyesters |
US20160115274A1 (en) * | 2014-10-27 | 2016-04-28 | Eastman Chemical Company | Carboxyl functional curable polyesters containing tetra-alkyl cyclobutanediol |
WO2016187095A1 (en) * | 2015-05-19 | 2016-11-24 | Eastman Chemical Company | Aliphatic polyester coating compositions containing tetramethyl cyclobutanediol |
WO2020023775A1 (en) * | 2018-07-25 | 2020-01-30 | Ppg Industries Ohio, Inc. | A product coated with an aqueous or powder coating composition comprising an acrylic polyester resin |
US10916539B2 (en) | 2017-08-31 | 2021-02-09 | Fuji Electric Co., Ltd. | Semiconductor device having a transistor portion that includes an output resistive portion |
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2023
- 2023-07-26 WO PCT/US2023/070991 patent/WO2024026334A1/en unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US3772405A (en) | 1972-02-02 | 1973-11-13 | Eastman Kodak Co | Process for preparing aromatic diester containing copolyesters and products obtained thereby |
US5637654A (en) * | 1996-08-12 | 1997-06-10 | Mcwhorter Technologies | Low temperature cure carboxyl terminated polyesters |
US20160115274A1 (en) * | 2014-10-27 | 2016-04-28 | Eastman Chemical Company | Carboxyl functional curable polyesters containing tetra-alkyl cyclobutanediol |
WO2016187095A1 (en) * | 2015-05-19 | 2016-11-24 | Eastman Chemical Company | Aliphatic polyester coating compositions containing tetramethyl cyclobutanediol |
US10916539B2 (en) | 2017-08-31 | 2021-02-09 | Fuji Electric Co., Ltd. | Semiconductor device having a transistor portion that includes an output resistive portion |
WO2020023775A1 (en) * | 2018-07-25 | 2020-01-30 | Ppg Industries Ohio, Inc. | A product coated with an aqueous or powder coating composition comprising an acrylic polyester resin |
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