CN1360619A - Curable composition - Google Patents
Curable composition Download PDFInfo
- Publication number
- CN1360619A CN1360619A CN00810254A CN00810254A CN1360619A CN 1360619 A CN1360619 A CN 1360619A CN 00810254 A CN00810254 A CN 00810254A CN 00810254 A CN00810254 A CN 00810254A CN 1360619 A CN1360619 A CN 1360619A
- Authority
- CN
- China
- Prior art keywords
- component
- composition
- acid
- total amount
- polyester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000000203 mixture Substances 0.000 title claims abstract description 89
- 229920000728 polyester Polymers 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 239000003973 paint Substances 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 20
- -1 hydrogen terephthalic acid diglycidyl esters Chemical class 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 18
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 17
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 10
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 9
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000004793 Polystyrene Substances 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 6
- NEPKLUNSRVEBIX-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OCC2OC2)C=CC=1C(=O)OCC1CO1 NEPKLUNSRVEBIX-UHFFFAOYSA-N 0.000 claims description 5
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 4
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 claims description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims 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 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000011521 glass Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000004593 Epoxy Substances 0.000 abstract description 4
- 229920001577 copolymer Polymers 0.000 abstract description 3
- 239000008199 coating composition Substances 0.000 abstract description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 5
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 description 5
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000000207 volumetry Methods 0.000 description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 3
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 3
- MKBBSFGKFMQPPC-UHFFFAOYSA-N 2-propyl-1h-imidazole Chemical compound CCCC1=NC=CN1 MKBBSFGKFMQPPC-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 241000723346 Cinnamomum camphora Species 0.000 description 3
- 241000675108 Citrus tangerina Species 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229960000846 camphor Drugs 0.000 description 3
- 229930008380 camphor Natural products 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000012628 flowing agent Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000001327 prunus amygdalus amara l. extract Substances 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 235000019580 granularity Nutrition 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 150000003628 tricarboxylic acids Chemical class 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- SEULWJSKCVACTH-UHFFFAOYSA-N 1-phenylimidazole Chemical compound C1=NC=CN1C1=CC=CC=C1 SEULWJSKCVACTH-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- ODGCZQFTJDEYNI-UHFFFAOYSA-N 2-methylcyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)C=CCCC1C(O)=O ODGCZQFTJDEYNI-UHFFFAOYSA-N 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- SVLTVRFYVWMEQN-UHFFFAOYSA-N 5-methylcyclohex-3-ene-1,2-dicarboxylic acid Chemical compound CC1CC(C(O)=O)C(C(O)=O)C=C1 SVLTVRFYVWMEQN-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- HGINCPLSRVDWNT-UHFFFAOYSA-N acrylaldehyde Natural products C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 210000004905 finger nail Anatomy 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000003960 organic solvent 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
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of 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
- 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
- C09D5/033—Powdery paints characterised by the additives
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Abstract
Curable compositions which are suitable especially as powder coating compositions comprising: (A) from 80 to 97.9 percent by weight, based on the total amount of components (A), (B) and (C), of a polyester component having an acid number in total of from 10 to 40 mg of KOH per gram of the component and consisting of one or more polyesters containing free carboxyl groups; (B) from 0.2 to 2 percent by weight, based on the total amount of components (A), (B) and (C), of a component consisting of one or more polymers or copolymers that each have an epoxy value of at least 3 equivalents per kilogram and a molecular weight (number average Mn) of from 800 to 20000 and that contain identical or different structural repeating units of formula (I): wherein R<1> and R<2> are each independently of the other a hydrogen atom or a methyl group; and (C) a component consisting of one or more monomeric polyglycidyl compounds having an epoxy value of at least 3.5 equivalents per kilogram and a maximum molecular weight of 600, the amount of component (C) in percent by weight, based on the total amount of components (A), (B) and (C), corresponding to the difference between 100 and the sum of the percentage amounts of components (A) and (B) based on the total amount of components (A), (B) and (C); and (D) an accelerator for the reaction of epoxy groups with carboxyl groups.
Description
The present invention relates to based on the curable compositions of acid polyester and some multi-shrinking glyceryl compound and powder paint compositions on this basis.
JP-A-is clear to disclose a kind of curable compositions and they purposes as powder paint compositions with 57-108166, and said composition comprises:
(A) polyester of 60-96 weight part, it has the softening temperature of acid number, 80-150 ℃ of 20-200mg KOH/g and the molecular weight (number average) of 1000-10 000,
(B) the containing glycidyl and have an acrylate copolymer of 300-5000 molecular weight (number average) of 3-40 weight part,
(C) other Resins, epoxy of 1-20 weight part, it especially can be terephthalic acid diglycidyl ester or triglycidyl isocyanurate and
(D) be used for the promotor of epoxy group(ing) and carboxyl reaction.
Use contains the polymkeric substance of identical or different formula (I) structural repeat unit or multipolymer as component (B):
Radicals R wherein
1And R
2Be hydrogen atom or methyl independently of one another.
From above quantitative data as can be seen, described composition contains at least approximately component (B) of 2.5wt%, based on component (A), (B) and gross weight (C).Therefore yet the flow characteristics of composition is still unsatisfactory usually and when this composition is used to produce powdered resin coating, especially has the danger that the known orange peel shape of generation is peeled off effect, that is to say, will form the very coating of uneven surface.
The present invention is based on following wonderful discovery: the flow characteristics of foregoing curable composition is significantly improved, however, has superior physical properties, especially the solidify material of very good mechanical properties can be by using based on component (A), (B) and (C) one or more polymkeric substance or the multipolymer of maximum 2wt% of total amount obtain as component (B), described polymkeric substance or multipolymer have the oxirane value of at least 3 equivalent/kilograms and the molecular weight (number average of 800-20 000 separately, and the structural repeat unit of the identical or different formula of having mentioned above containing (I) Mn).
Therefore the present invention relates to curable compositions, comprising:
(A) based on component (A), (B) and (C) the 80-97.9wt% polyester components of total amount, it has the acid number of 10-40mg KOH/g component altogether and is made up of one or more polyester that contain free carboxy;
(B) based on component (A), (B) and (C) component of forming by one or more polymkeric substance or multipolymer of the 0.2-2wt% of total amount, the structural repeat unit that described polymkeric substance or multipolymer have the oxirane value of at least 3 equivalent/kilograms and the molecular weight of 800-20 000 (number average Mn) separately and contain identical or different formula (I):
R wherein
1And R
2Be hydrogen atom or methyl independently of one another; With
(C) component of forming by one or more monomer multi-shrinking glyceryl compounds of the highest weight of the oxirane value with at least 3.5 equivalent/kilograms and 600, based on component (A), (B) and (C) amount (wt%) of the component of total amount (C) corresponding to 100 with based on component (A), (B) and (C) difference between the component of total amount (A) and the percentage consumption summation (B); With
(D) be used for the promotor of epoxy group(ing) and carboxyl reaction,
In addition, wherein component (B) account for component (B) and (C) gross weight 5-95% and in composition the mol ratio of glycidyl and carboxyl be 1.3: 1-1: 1.3.
Especially have outstanding performance with extraordinary flow characteristics and the solidify material that generation has high crosslink density and very good mechanical properties according to curable compositions of the present invention.
For example be suitable for as tackiness agent, curtain coating resin or compression moulding composition according to curable compositions of the present invention, as required, may be blended in other component commonly used in the described Application Areas therein.
Particularly preferably be and contain the powder paint compositions of with good grounds composition of the present invention as the curable components system.Therefore the present invention also relates to based on the powder paint compositions according to curable compositions of the present invention.
Polyester components (A) preferably accounts for the 85-96wt% of thing combined according to the invention, and 88-95wt% especially is based on component (A), (B) and total amount (C).
Therefore the acid number of 10-40mg KOH/g is applicable to whole polyester components, when several different polyester of use, corresponding to the average acid number of these polyester summations.Preferably wherein polyester components (A) has 20-40mg altogether, and preferably the acid number of 22-38mg KOH/kg component is a kind of according to composition of the present invention.
The polyester of component (A) at room temperature (15-35 ℃) is desirably solid, for example has the molecular weight (number average Mn) of 1000-10000.The Mw of those polyester (weight-average molecular weight) generally is 2-10 with the ratio of Mn.For example, have 4000-15 000, the especially molecular weight of 6500-11 000 (using the weight average Mw of polystyrene calibration) and 35-120 ℃ by gpc measurement, preferably the polyester that contains free carboxy of 50-90 ℃ second-order transition temperature (Tg) is particularly suitable for the present invention.
For example in US-A-3 397 254 and EP-A-0 600 546, described as above-mentioned those polyester.Be suitable for polyester of the present invention and be two senses, trifunctional and/or polyfunctional alcohol (polyvalent alcohol) and dicarboxylic acid and trifunctional as required and/or polyfunctional carboxylic acids, perhaps with the condensation product of corresponding carboxylic acid acid anhydride.Employed polyvalent alcohol for example comprises ethylene glycol, glycol ether, propylene glycol, butyleneglycol, 1,3 butylene glycol, 1, the 4-butyleneglycol, neopentyl glycol, isoamyl glycol, 1, the 6-hexylene glycol, glycerine, hexanetriol, trimethylolethane, TriMethylolPropane(TMP), tetrahydroxybutane, tetramethylolmethane, cyclohexanediol and 1,4-hydroxymethyl-cyclohexane.The dicarboxylic acid that is fit to for example comprises m-phthalic acid, terephthalic acid and phthalic acid, the methyl substituted derivative of described acid, tetrahydrophthalic acid, methyl tetrahydrophthalic acid, for example 4-methyl tetrahydrophthalic acid, hexanaphthene-dicarboxylic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, dodecanedicarboxylic acid, fumaric acid, toxilic acid and 4,4'-diphenyldicarboxylic acids etc.The tricarboxylic acid that is fit to comprises for example aliphatic tricarboxylic acid, as 1,2, and the 3-tricarballylic acid, the aromatic tricarboxylic acid, as 1,3, the 5-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid and benzene-1,2,3-tricarboxylic acid, and cycloaliphatic tricarboxylic acid are as 6-methyl cyclohexane-4-alkene-1,2,3-tricarboxylic acid.The tetracarboxylic acid that is fit to for example comprises 1,2,4,5-pyromellitic acid and benzophenone-3,3 ', 4,4 '-tetracarboxylic acid.Be purchased polyester especially very generally with as the neopentyl glycol of main alcohols monomer component and/or TriMethylolPropane(TMP) and as mainly hexanodioic acid and/or terephthalic acid and/or m-phthalic acid and/or 1,2 of acid mono component, the 4-benzenetricarboxylic acid is basic.
Component (B) preferably accounts for the 0.7-2wt% of thing combined according to the invention, and 0.7-1.8wt% especially is based on component (A), (B) and gross weight (C).In addition, preferred ingredient (B) accounts for many glycidyls component (B) and (C) 5-50% of gross weight, especially 7.5-25%.
Constitute the polymkeric substance of component (B) of thing combined according to the invention and the molecular weight (number average Mn) that multipolymer preferably has 1000-10000.For example by being selected from the monomer of vinylformic acid glycidyl esters, glycidyl methacrylate, vinylformic acid Beta-methyl glycidyl ester and methacrylic acid Beta-methyl glycidyl ester, as required can also be in the presence of an amount of polymerisable comonomer of free radical, carry out common radical polymerization, can prepare this polymkeric substance and multipolymer.For example can be by monomer being dissolved in suitable organic solvent, as toluene, 1-methoxyl group-2-propyl alcohol, acetate 1-methoxyl group-2-propyl ester, or in the methyl iso-butyl ketone (MIBK), perhaps in the mixture of described solvent, and the initiator that is being fit to, α for example, under the existence of α '-azo isobutyronitrile or dicumyl peroxide, when needing at chain terminator, for example gained solution is heated in the existence of glycidyl allyl ether down, carries out polyreaction.The comonomer that is fit to for example comprises (methyl) acrylate, as ethyl propenoate, and butyl acrylate, 2-EHA, and especially also have methacrylic acid C
1-C
4Alkyl ester, as methyl methacrylate, Jia Jibingxisuanyizhi and butyl methacrylate, in addition, for example vinyl cyanide and methacrylonitrile, (methyl) acrylamide and vinyl compound, for example aromatic vinyl compound, especially vinylbenzene and styrene derivatives.
Yet, also may be according to one of common method, for example by polymkeric substance or multipolymer and excessive Epicholorohydrin are reacted in the presence of the catalyzer that is fit to, after this poly-halo alcohol ester of gained uses hydrogenchloride wedding agent (binding agent) to carry out dehydrochlorination, makes poly-(methyl) acrylate copolymer or poly-(methyl) acrylic copolymer carry out Racemic glycidolizations.
Component (B) preferably is made up of the polymkeric substance or the multipolymer of the oxirane value that has 5 equivalent/kilograms separately at least.
More specifically preferably, component (B) constitutes by the polymkeric substance of being made up of the structural repeat unit of identical or different formula (I) substantially:
R wherein
1And R
2Be hydrogen atom or methyl independently of one another, especially work as the R in the formula (I)
2When being hydrogen atom.At last, many glycidyls component (C) preferably accounts for the 0.1-38wt% of thing combined according to the invention, and 5-15wt% especially is based on component (A), (B) and total amount (C).
Component (C) is made up of one or more many glycidyls that have 3.5 equivalents/kilogram oxirane value separately or many (Beta-methyl) glycidyl compound at least.Compare with the multi-shrinking glyceryl compound of the component (B) that constitutes thing combined according to the invention, these compounds are to have highest weight 600 (in this case, molecular weight is understood that to refer to the summation of the nucleidic mass of molecule, the calculated value of each compound) monomeric compound, for example at room temperature be preferably corresponding diglycidyl of solid or triglycidyl group compound, perhaps have even the corresponding multi-shrinking glyceryl compound of the glycidyl/molecule of high number more.
Preferably, the component of composition (C) is by having at least 4 equivalents, and especially one or more glycidyl compounds of the oxirane value of at least 5 equivalent/kilograms are formed.
The example of glycidyl compound that is suitable as the component (C) of thing combined according to the invention especially comprises 1,2,4-benzenetricarboxylic acid triglycidyl group ester, the three-glycidyl isocyanuric acid ester, six hydrogen terephthalic acid diglycidyl esters, especially trans six hydrogen terephthalic acid diglycidyl esters, six hydrogen m-phthalic acid 2-glycidyl esters, six hydrogen 1,2,4-benzenetricarboxylic acid three-glycidyl ester, terephthalic acid diglycidyl ester, m-phthalic acid 2-glycidyl ester and cyclohexanedimethanodiglycidyl diglycidyl ether.
For composition according to the present invention, in addition preferably, component (B) and oxirane value (C) are at least 3.5 equivalents together equally, the mixture of this two component of preferred at least 5 equivalent/kilograms.
Preferably has the epoxy group(ing) of crossing molar weight slightly according to composition of the present invention.In composition, the mol ratio of glycidyl and carboxyl therefore preferably 1.3: 1-1: 1, for example about 1.2: 1-1.1: 1.
For curing reaction can carry out fully fast, also contain the catalyzer that is used for epoxy group(ing) and carboxylic acid reaction as component (D) according to composition of the present invention.This catalyzer is the derivative of organic amine or amine normally, especially tertiary amine or nitrogen-containing heterocycle compound.The preferred catalyst that is used for the reaction of epoxy group(ing) and carboxyl is a phenylimidazole, N-benzyl dimethyl amine and 1,8-diazabicyclo [5.4.0]-7-undecylene, as required, can also be on silicate carrier or triphenylphosphine, Actiron NXJ-60 (2-propyl imidazole), Actiron NXJ-60P (the 60wt% 2-propyl imidazole on the 40wt% solid carrier), Beschleuniger DT 3126 ([C
16H
33N (CH
3)
3] Br
-).Preferred so that the mixture of catalyzer or catalyst mixture is about 70-400 second at 180 ℃ gel time (measuring according to DIN 55990), and the amount of preferred 90-300 second is added.Generally, will need about 0.1-10wt%, especially the catalyzer of 0.5-5wt% is used for this purpose.Certainly, some are purchased polyester and have contained one of one of a certain amount of above-mentioned catalyzer or comparable catalyzer as the composition of the component (A) of thing combined according to the invention, and this amount should be counted in the above weight percentage numeral of catalyzer; Above-mentioned preferred gel time can be used in provides the indication that also needs to add how many catalyzer.
Except the component of having mentioned, certainly contain other component according to composition of the present invention, this can change according to the Application Areas of composition, and is known to the skilled person in described field.
Powder paint compositions based on thing combined according to the invention for example also can contain the additive that is customarily used in top coat industry with common consumption, especially as photostabilizer, and curing catalyst, dyestuff, pigment, for example TiO 2 pigment, air release agent, for example bitter almond oil camphor also has other flowing agent.The flowing agent that is fit to for example comprises polyvinyl acetal, as polyvinyl butyral acetal, and polyoxyethylene glycol, Polyvinylpyrolidone (PVP), glycerine and vinylformic acid mixed polymer, for example those that buy under one's name at Modaflow and Acrylron .
Can prepare according to powder paint compositions of the present invention simply by for example in ball mill, being mixed together each composition.In addition, preferred possibility comprises together fusing, and each composition of blend and homogenizing preferably uses forcing machine, as Buss kneader altogether, cools off and pulverizes the gained material.In this schedule of operation, after extruding, immediately, perhaps placed several hours at them at least, for example approximately after 24-48 hour, powder paint compositions according to the present invention becomes so hard and crisp so that they can be easy to be ground, and such fact is verified to be special ideal.Powder paint compositions preferably has the m at 0.015-500 μ, especially the granularity in the 10-75 mu m range.In some cases, also advantageously, at first by binding agent, Resins, epoxy and the part of other component when needing prepare masterbatch (masterbatch), then in second step remainder of masterbatch and binding agent and remaining component mixes with homogenizing with acquisition finished product powder paint compositions.
After the goods that coating will apply, powder paint compositions solidifies under preferred 150-220 ℃ the temperature at about at least 100 ℃.Solidify general cost about 5-60 minute.Need solidified stable all material under this temperature, especially pottery and metal are suitable for applying.Base material can have the one layer or more bottom covering compatible with this powder paint compositions.
This powder paint compositions has showed combining of good flow characteristics and favorable mechanical performance, good weathering resistance and good chemical-resistant.
Embodiment 1: the glycidyl methacrylate (=GMA) preparation of homopolymer
Use AIBN (α, α '-azo isobutyronitrile) to carry out radical polymerization as initiator.Required lower molecular weight (Mw or Mn) is by selecting the amount of initiator, and the amount and the polymerization temperature of chain terminator (being glycidyl allyl ether in this case) obtain.In the present example in the polymerization process of Shi Yonging, the monomer mixture of major portion (90%), the initiator of full dose and the solvent of major portion are metered in during two hours in the initial charging in the reactor, and this initial charging is made up of the remainder (10%) and the solvent remainder of monomer mixture.This makes controlled polymerization heat release well and help obtain reproducible molecular weight.Certainly, many variations of response procedures are possible; Those skilled in the art will find that the condition that decision is fit to is very simple.
Poly-unit is made up of the heated 3000ml double-walled jacketed reactor with agitator, reflux exchanger, thermometer, nitrogen sparge tube, reinforced receptor and Jia Ke pump (" Masterflex " peristaltic pump).The monomer mixture that preparation is made up of 1300.50g glycidyl methacrylate and 144.50g glycidyl allyl ether.Add 144.50g monomer mixture and 867.00g acetate methoxyl group propyl ester (MPA, solvent) in the reactor.Pack into the remainder (1300.50g) of monomer mixture of reinforced receptor, the MPA of 96.50g and 72.25g AIBN.AIBN should be by uniform dissolution.Whole device (comprising reinforced receptor) becomes inertia with nitrogen, and reactor is heated to 100 ℃ internal temperature (105 ℃ jacket temperatures), begins then to feed in raw material.Select about 2 hours of the feasible reinforced cost of reinforced speed.Stirring velocity is 100 rev/mins.When finishing when reinforced, be aggregated in 100 ℃ and nitrogen and continued other 2 hours down.In hexane, precipitate viscous soln, decant solvent again.The grease-like residue is dissolved in the acetone neutralization and is precipitated out from water.The precipitation residue is redeposition from acetone once more.The elimination solid polymer is also dry in a vacuum.Remained the colourless polymer of 1200.00g powder type with following analytical data:
Tg passes through dsc measurement: 31 ℃
GPC (polystyrene calibration): Mw=7147; Mn=2986
Oxirane value, volumetry: 6.44 equivalents/kg
Embodiment 2: the preparation of other GMA homopolymer
The following material of operation polymerization according to description in embodiment 1:
The glycidyl methacrylate of monomer mixture: 144.50g+25.50g glycidyl allyl ether
Initial reactor charge: 17.00g monomer mixture+102.00g MPA
Reinforced: 153.00g monomer mixture+11.30g MPA+8.50g AIBN
Obtain the colourless polymer of 158.30g powder type, had following analytical data:
Tg：42℃
GPC (polystyrene calibration): Mw=6099; Mn=1304
Oxirane value, volumetry: 6.39 equivalents/kg
The preparation of embodiment 3:GMA multipolymer (Rt 2549/1)
The following material of operation polymerization according to description in embodiment 1:
Monomer mixture: 25.50g butyl methacrylate+127.50g glycidyl methacrylate+17.00g glycidyl allyl ether
Initial reactor charge: 17.00g monomer mixture and 102.00g MPA
Reinforced: 153.00g monomer mixture+11.30g MPA+8.50g AIBN
Revise the separation of solid polymer a little: use Rotary Evaporators that polymers soln is concentrated to drying, residue is dissolved in the acetone, is precipitated out from ice-water then.Obtained to have the colourless polymer of the 157.00g powder type of following analytical data:
GPC (polystyrene calibration): Mw=7182; Mn=1926
Oxirane value, volumetry: 5.47 equivalents/kg
The radical polymerization of embodiment 4:GMA in terephthalic acid diglycidyl ester (DGT)
200g terephthalic acid diglycidyl ester (DGT) is incorporated in 1 flask of the peaceful end.With 40g glycidyl methacrylate (GMA) and 4g 1, two (t-butyl peroxy)-3,3 of 1-, 5-trimethyl-cyclohexane (50% solution=, C50) be incorporated in the 250ml taper neck flask available from the Trigonox 29 of AKZO.Two flasks interconnect.Florence flask heats by oil bath, till the DGT fusing.When all DGT had melted, 1 flask of the peaceful end of finding time was supplied with flask with the 250ml that is connected it, again with 5 times nitrogen filling altogether.In then during 20 minutes, under agitation, with GMA and 1, two (t-butyl peroxy)-3,3 of 1-, the mixture of 5-trimethyl-cyclohexane is supplied with flask from 250ml and is joined the fused DGT, and this batch of material reacted 3.5 hours under further stirring.With postcooling the time, liquid substance solidifies.
Yield: 236g (98%)
GPC (polystyrene calibration): Mw=15 700; Mn=8921
Oxirane value, volumetry: 6.86 equivalents/kg
Embodiment 5:
The use forcing machine (available from the laboratory forcing machine of PRISM, The Old Stable, England), the powder paint compositions of representing in following table 1a and 1b is homogenizing under 60-80 ℃ temperature.The total amount of powder paint compositions is about 100-200 gram in all cases.Grind the refrigerative extrudate, the finished product powder paint compositions that has obtained to have about 40 μ m granularities.Table 1a: according to powder paint compositions prescription A-C of the present invention and contrast coating composition E-G
| Prescription/amount [wt%] | The present invention | Comparison | ||||
| ??A | ??B | ??C | ??E | ??F | ??G | |
| ????Uralac?P ????3485 1) | ??58.98 | ??59.96 | ??90.77 | ??59.08 | ??59.81 | ??59.95 |
| ????DGT | ??4.69 | ??3.97 | ??6.01 | ??4.89 | ??--- | ??--- |
| The GMA polymkeric substance of embodiment 1 | ??--- | ??1.03 | ??--- | ??--- | ??5.16 | ??--- |
| The GMA polymkeric substance of embodiment 2 | ??--- | ??--- | ??1.52 | ??--- | ??--- | ??5.02 |
| GMA polymkeric substance (6.7eq/kg) | ??0.80 | |||||
| ????DT?3126-1 2) | ??0.50 | ??--- | ??--- | ??1.00 | ??--- | ??--- |
| Bitter almond oil camphor | ??0.20 | ??0.20 | ??0.20 | ??0.20 | ??0.20 | ??0.20 |
| ????Acrylron 3) | ??1.50 | ??1.50 | ??1.50 | ??1.50 | ??1.50 | ??1.50 |
| ????TiO 2Pigment | ??33.33 | ??33.33 | ??--- | ??33.33 | ??33.33 | ??33.33 |
1)Based on the polyester of terephthalic acid, m-phthalic acid and neopentyl glycol, it has 28 acid number and 71 ℃ glass transition temperature Tg;
2)Alkylammonium salt in polyester;
3)Vinylformic acid mixed polymer as flowing agent.
Table 1b: according to powder paint compositions H-K of the present invention and P
| Prescription [wt%] | The present invention | ||||
| ?H | ???I | ??J | ????K | ????P | |
| Polyester 4) | ?Uralac ?P-3485 ?58.71 | ???Crylcoat ???801 ???57.61 | ??Crylcoat ??D-6210 ??59.66 | ????Alftalat ????9952 ????58.90 | ????Uralac ????P-3485 ????59.09 |
| The DGT/GMA mixed polymer | ?5.76 5) | ???6.86 5) | ??4.81 5) | ????5.57 5) | ????5.38 6) |
| Bitter almond oil camphor | ?0.20 | ???0.20 | ??0.20 | ????0.20 | ????0.50 |
| Acrylon | ?1.50 | ???1.50 | ??1.50 | ????1.50 | ????0.20 |
| XB?3126 | ?0.50 | ???0.50 | ??0.50 | ????0.50 | ????1.50 |
| TiO 2Pigment | ?33.33 | ???33.33 | ??33.33 | ????33.33 | ????33.33 |
4)Based on the polyester of terephthalic acid, m-phthalic acid and neopentyl glycol, it has according to the acid number of following table and second-order transition temperature:
| Polyester | Crylcoat?801 | ?CrylcoatD-6210 | ?Alftalat9952 |
| Acid number | ????34 | ???????23 | ??????27 |
| ??Tg(℃) | ????73 | ???????72 | ??????64 |
* DSC test for the first time.
5)Have the about 86wt%DGT of oxirane value of 6.37 equivalents/kilogram mixture and the mixture of 14wt%GMA homopolymer.
6)According to the DGT of embodiment 4 and the mixture of GMA homopolymer.
Use electrostatic spraying gun, on the Q plate of powder paint compositions paint as base material.Then coating plate is put into baking oven so that fusing and completely solidified powder paint compositions.Listed the thickness of gel time, solidification value and set time and gained powdex coating in following table 2a and 2b, also had the performance of gained coating, it is important from process for surface coating.
Table 2a: use composition A, B, C and E, F, G to obtain
Coating be important performance from process for surface coating
| The present invention | Comparison | |||||
| ??A | ??B | ??C | ??E | ??F | ??G | |
| Gel time at 180 ℃ 6)[s] | ??220 | ??170 | ??90 | ??205 | ??25 | ??20 |
| Condition of cure | ??15min/ ??180℃ | ??15min/ ??180℃ | ??15min/ ??180℃ | ??15min/ ??180℃ | ??15min/ ??180℃ | ??15min/ ??180℃ |
| Bed thickness [μ m] | ??60 | ??53 | ??59 | ??60 | ??59 | ??60 |
| 60 ° of glossiness | ??94 | ??96 | ??124 | ??87 | ??18 | ??21 |
| 20 ° of glossiness | ??85 | ??77 | ??117 | ??95 | ??60 | ??65 |
| Yellowness factor value Yi 7) | ??0.2 | ??-0.8 | ??--- | ??-1.2 | ??-1.1 | ??-0.8 |
| Flow 8)[grading] | ??10 | ??10 | ??12 | ??12 | Tangerine peel is peeled off | Tangerine peel is peeled off |
| Shock-produced deformation, reverse side 9)[kg?cm] | ??160 | ??160 | ??160 | ??160 | ??＜5 | ??＜5 |
| Shock-produced deformation, positive [kg cm] | ??160 | ??160 | ??140 | ??160 | ??80 | ??80 |
| Acetone test 10), the 1min[grading] | ??3 | ??3 | ??3 | 5 do not solidify | ??3 | ??3 |
| Outward appearance | Satisfied | Satisfied | Satisfied | Satisfied | Coarse | Coarse |
8)Experience standard from 0 (very good) to 18 (tangerine peel is peeled off)
9)By with weight of impact 2kg, have the ball of 20mm diameter with its downside (wherein downside is preceding) from certain height, from coating back (or reverse side) or drop to coatingsurface from the coating front and measure shock-produced deformation.Institute's indicating value is the product of weight of impact (kg) and test height (cm), under this height, does not still detect the destruction to coating.
10)According to DIN 53320.Sample remained in the acetone 1 minute.The result estimates according to the standard of following 5 grades: 0=does not change; 1=has resistibility, can not scratch with fingernail; 2=is difficult to scratch, and can stain cotton wool pad; 3=is softening, is scratched easily; 4=begins to separate or dissolving; 5=dissolves fully.
Table 2b: use H-K, the process for surface coating performance of the coating of the composition of P
| The present invention | |||||
| ????H | ????I | ????J | ????K | ????P | |
| At 180 ℃ gel times [s] | ????225 | ????275 | ????180 | ????170 | ????260 |
| Condition of cure | ????15min/ ????200℃ | ????15min/ ????200℃ | ????15min/ ????200℃ | ????15min/ ????200℃ | ????15min/ ????180℃ |
| Bed thickness [μ m] | ????60 | ????55 | ????50 | ????47 | ????46 |
| 60 ° of glossiness | ????89 | ????95 | ????94 | ????96 | ????95 |
| 20 ° of glossiness | ????76 | ????88 | ????84 | ????83 | ????85 |
| Yellowness factor value Yi 7) | ????-0.4 | ????0.0 | ????-1.0 | ????-1.8 | ????-1.5 |
| Flow 8)[grading] | ????8 | ????8 | ????10 | ????10 | ????10 |
| Shock-produced deformation, reverse side 9)????[kg?cm] | ????＞160 | ????120 | ????＞160 | ????＞160 | ????＞160 |
| Shock-produced deformation, positive [kg cm] | ????＞160 | ????＞160 | ????＞160 | ????＞160 | ????＞160 |
| Acetone test 10), the 1min[grading] | ????3 | ????3 | ????3 | ????3 | ????3 |
| Outward appearance | Satisfied | Satisfied | Satisfied | Satisfied | Satisfied |
Claims (17)
1, a kind of curable compositions comprises:
(A) based on component (A), (B) and (C) the 80-97.9wt% polyester components of total amount, it has the acid number of 10-40mg KOH/g component altogether and is made up of one or more polyester that contain free carboxy;
(B) based on component (A), (B) and (C) component of forming by one or more polymkeric substance or multipolymer of the 0.2-2wt% of total amount, described polymkeric substance or multipolymer have separately the oxirane value of at least 3 equivalent/kilograms and the molecular weight of 800-20 000 (number average, Mn) and the structural repeat unit that contains identical or different formula (I):
R wherein
1And R
2Be hydrogen atom or methyl independently of one another; With
(C) component of forming by one or more monomer multi-shrinking glyceryl compounds of the highest weight of the oxirane value with at least 3.5 equivalent/kilograms and 600, based on component (A), (B) and (C) amount (wt%) of the component of total amount (C) corresponding to 100 with based on component (A), (B) and (C) difference between the component of total amount (A) and the percentage consumption summation (B); With
(D) be used for the promotor of epoxy group(ing) and carboxyl reaction.
2, according to the composition of claim 1, contain 85-96wt%, the component of 88-95wt% (A) especially is based on component (A), (B) and total amount (C).
3, according to the composition of claim 1 or claim 2, wherein polyester components (A) has the acid number of 22-38mg KOH/g component altogether.
4, according to each composition among the claim 1-3, the polyester that wherein constitutes polyester components (A) has 4000-15 000, especially the molecular weight of 6500-11 000 (using the weight average Mw of the gpc measurement of polystyrene calibration) and 35-120 ℃, preferably 50-90 ℃ glass glass transition temperature (Tg).
5, according to each composition among the claim 1-4, the polyester that wherein constitutes polyester components (A) is with as the neopentyl glycol of main alcohols monomer component and/or TriMethylolPropane(TMP) with as mainly hexanodioic acid and/or terephthalic acid and/or m-phthalic acid and/or 1 of acid mono component, 2, the 4-benzenetricarboxylic acid is the basis.
6, according to each composition among the claim 1-5, it contains 0.7-2wt%, and the component of 0.7-1.8wt% (B) especially is based on component (A), (B) and total amount (C).
7, according to each composition among the claim 1-6, wherein component (B) accounts for component (B) and (C) 5-50% of gross weight, especially 7.5-25%.
8, according to each composition among the claim 1-7, wherein component (B) is made up of one or more polymkeric substance or the multipolymer of the oxirane value that has 5 equivalent/kilograms separately at least.
9, according to each composition among the claim 1-8, wherein constitute the polymkeric substance of component (B) and the molecular weight (number average Mn) that multipolymer has 1000-10 000.
10, according to each composition among the claim 1-9, the polymkeric substance formation of component (B) wherein by forming by the structural repeat unit of identical or different formula (I) substantially:
Radicals R wherein
1And R
2Be hydrogen atom or methyl independently of one another.
11, according to each composition among the claim 1-10, R in its Chinese style (I)
2It is hydrogen atom.
12, according to each composition among the claim 1-11, it contains 0.1-38wt%, and the component (C) of preferred 5-15wt% is based on component (A), (B) and total amount (C).
13, according to each composition among the claim 1-12, wherein component (C) is made up of one or more multi-shrinking glyceryl compounds of the oxirane value with at least 5 equivalent/kilograms.
14, according to each composition among the claim 1-13, wherein component (C) is formed by being selected from one or more following monomer multi-shrinking glyceryl compounds: 1,2,4-benzenetricarboxylic acid triglycidyl group ester, triglycidyl isocyanurate, six hydrogen terephthalic acid diglycidyl esters, especially trans six hydrogen terephthalic acid diglycidyl esters, six hydrogen m-phthalic acid 2-glycidyl esters, six hydrogen 1,2,4-benzenetricarboxylic acid three-glycidyl ester, terephthalic acid diglycidyl ester, m-phthalic acid 2-glycidyl ester and cyclohexanedimethanodiglycidyl diglycidyl ether.
15, according to each composition among the claim 1-14, wherein component (B) and (C) together oxirane value be at least 3.5 equivalent/kilograms, preferred at least 5 equivalent/kilograms.
16, according to each composition among the claim 1-15, wherein the mol ratio of glycidyl and carboxyl is 1.3 in composition: 1-1: 1.
17, a kind of powder paint compositions, this powder paint compositions is based on according to each curable compositions among the claim 1-16.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1304/99 | 1999-07-14 | ||
| CH130499 | 1999-07-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1360619A true CN1360619A (en) | 2002-07-24 |
Family
ID=4207317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00810254A Pending CN1360619A (en) | 1999-07-14 | 2000-07-06 | Curable composition |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP1196508A1 (en) |
| JP (1) | JP2003505531A (en) |
| KR (1) | KR20020018685A (en) |
| CN (1) | CN1360619A (en) |
| AU (1) | AU6689800A (en) |
| BR (1) | BR0013164A (en) |
| CA (1) | CA2378191A1 (en) |
| HU (1) | HUP0201962A2 (en) |
| MX (1) | MXPA02000341A (en) |
| PL (1) | PL352938A1 (en) |
| TR (1) | TR200200040T2 (en) |
| WO (1) | WO2001005901A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101506302B (en) * | 2006-08-24 | 2011-11-16 | 巴斯福涂料股份有限公司 | Resin compositions for coatings and coating compositions wherein these are used |
| CN105176169A (en) * | 2015-10-31 | 2015-12-23 | 安徽神剑新材料股份有限公司 | Epoxy-terminated powder paint curing agent and synthesis method thereof |
| CN107434926A (en) * | 2011-02-07 | 2017-12-05 | 威士伯采购公司 | Container and other product coating compositions and coating method |
| US10745514B2 (en) | 2014-04-14 | 2020-08-18 | Swimc Llc | Methods of preparing compositions for containers and other articles and methods of using same |
| US10894632B2 (en) | 2012-08-09 | 2021-01-19 | Swimc Llc | Compositions for containers and other articles and methods of using same |
| US11130881B2 (en) | 2010-04-16 | 2021-09-28 | Swimc Llc | Coating compositions for packaging articles and methods of coating |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4242253A (en) * | 1979-06-04 | 1980-12-30 | E. I. Du Pont De Nemours And Company | Low gloss powder coating compositions |
| JPS57108166A (en) * | 1980-12-25 | 1982-07-06 | Dainippon Ink & Chem Inc | Resin composition for powder paint |
| JPH01313573A (en) * | 1988-06-10 | 1989-12-19 | Nippon Oil & Fats Co Ltd | Powder coating composition |
| JPH037757A (en) * | 1989-11-07 | 1991-01-14 | Toray Ind Inc | Polyester resin composition for molding |
| TW312701B (en) * | 1992-12-01 | 1997-08-11 | Dsm Nv |
-
2000
- 2000-07-06 WO PCT/EP2000/006423 patent/WO2001005901A1/en not_active Application Discontinuation
- 2000-07-06 CA CA002378191A patent/CA2378191A1/en not_active Abandoned
- 2000-07-06 TR TR2002/00040T patent/TR200200040T2/en unknown
- 2000-07-06 KR KR1020017016787A patent/KR20020018685A/en not_active Application Discontinuation
- 2000-07-06 BR BR0013164-4A patent/BR0013164A/en not_active IP Right Cessation
- 2000-07-06 PL PL00352938A patent/PL352938A1/en not_active Application Discontinuation
- 2000-07-06 MX MXPA02000341A patent/MXPA02000341A/en unknown
- 2000-07-06 EP EP00954442A patent/EP1196508A1/en not_active Withdrawn
- 2000-07-06 CN CN00810254A patent/CN1360619A/en active Pending
- 2000-07-06 JP JP2001511122A patent/JP2003505531A/en active Pending
- 2000-07-06 AU AU66898/00A patent/AU6689800A/en not_active Abandoned
- 2000-07-06 HU HU0201962A patent/HUP0201962A2/en unknown
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101506302B (en) * | 2006-08-24 | 2011-11-16 | 巴斯福涂料股份有限公司 | Resin compositions for coatings and coating compositions wherein these are used |
| US11130881B2 (en) | 2010-04-16 | 2021-09-28 | Swimc Llc | Coating compositions for packaging articles and methods of coating |
| CN107434926A (en) * | 2011-02-07 | 2017-12-05 | 威士伯采购公司 | Container and other product coating compositions and coating method |
| US11634607B2 (en) | 2011-02-07 | 2023-04-25 | Swimc Llc | Compositions for containers and other articles and methods of using same |
| US10894632B2 (en) | 2012-08-09 | 2021-01-19 | Swimc Llc | Compositions for containers and other articles and methods of using same |
| US11628974B2 (en) | 2012-08-09 | 2023-04-18 | Swimc Llc | Compositions for containers and other articles and methods of using same |
| US12043448B2 (en) | 2012-08-09 | 2024-07-23 | Swimc Llc | Compositions for containers and other articles and methods of using same |
| US10745514B2 (en) | 2014-04-14 | 2020-08-18 | Swimc Llc | Methods of preparing compositions for containers and other articles and methods of using same |
| US11525018B2 (en) | 2014-04-14 | 2022-12-13 | Swimc Llc | Methods of preparing compositions for containers and other articles and methods of using same |
| CN105176169A (en) * | 2015-10-31 | 2015-12-23 | 安徽神剑新材料股份有限公司 | Epoxy-terminated powder paint curing agent and synthesis method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20020018685A (en) | 2002-03-08 |
| BR0013164A (en) | 2002-04-09 |
| JP2003505531A (en) | 2003-02-12 |
| PL352938A1 (en) | 2003-09-22 |
| EP1196508A1 (en) | 2002-04-17 |
| CA2378191A1 (en) | 2001-01-25 |
| AU6689800A (en) | 2001-02-05 |
| MXPA02000341A (en) | 2002-07-02 |
| HUP0201962A2 (en) | 2002-09-28 |
| TR200200040T2 (en) | 2002-12-23 |
| WO2001005901A1 (en) | 2001-01-25 |
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