CA1219693A - In-mold coating composition - Google Patents
In-mold coating compositionInfo
- Publication number
- CA1219693A CA1219693A CA000466081A CA466081A CA1219693A CA 1219693 A CA1219693 A CA 1219693A CA 000466081 A CA000466081 A CA 000466081A CA 466081 A CA466081 A CA 466081A CA 1219693 A CA1219693 A CA 1219693A
- Authority
- CA
- Canada
- Prior art keywords
- weight
- parts
- copolymerizable
- mold coating
- coating composition
- 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.)
- Expired
Links
- 239000008199 coating composition Substances 0.000 title claims description 33
- 239000000203 mixture Substances 0.000 claims abstract description 48
- -1 free radical peroxide Chemical class 0.000 claims abstract description 31
- 239000004593 Epoxy Substances 0.000 claims abstract description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 22
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 19
- 239000000194 fatty acid Substances 0.000 claims abstract description 19
- 229930195729 fatty acid Natural products 0.000 claims abstract description 19
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 239000000945 filler Substances 0.000 claims abstract description 15
- 150000002978 peroxides Chemical class 0.000 claims abstract description 14
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 13
- 229920002689 polyvinyl acetate Polymers 0.000 claims abstract description 12
- 239000011118 polyvinyl acetate Substances 0.000 claims abstract description 12
- 150000003751 zinc Chemical class 0.000 claims abstract description 12
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 239000000454 talc Substances 0.000 claims abstract description 10
- 229910052623 talc Inorganic materials 0.000 claims abstract description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims description 26
- 239000011248 coating agent Substances 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 19
- 239000003365 glass fiber Substances 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 9
- 229920001567 vinyl ester resin Polymers 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 6
- 229920001225 polyester resin Polymers 0.000 claims description 5
- 239000004645 polyester resin Substances 0.000 claims description 5
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 4
- 230000001464 adherent effect Effects 0.000 claims description 4
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims 5
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims 3
- 239000008116 calcium stearate Substances 0.000 claims 3
- 235000013539 calcium stearate Nutrition 0.000 claims 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims 3
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 claims 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical group CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims 1
- 239000004634 thermosetting polymer Substances 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract description 13
- 239000000758 substrate Substances 0.000 description 9
- 229920003023 plastic Polymers 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- 150000003440 styrenes Chemical class 0.000 description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000006082 mold release agent Substances 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical group CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 2
- CWPKTBMRVATCBL-UHFFFAOYSA-N 3-[1-[1-[(2-methylphenyl)methyl]piperidin-4-yl]piperidin-4-yl]-1h-benzimidazol-2-one Chemical group CC1=CC=CC=C1CN1CCC(N2CCC(CC2)N2C(NC3=CC=CC=C32)=O)CC1 CWPKTBMRVATCBL-UHFFFAOYSA-N 0.000 description 2
- 239000004412 Bulk moulding compound Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229920002176 Pluracol® Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- QVZZPLDJERFENQ-NKTUOASPSA-N bassianolide Chemical compound CC(C)C[C@@H]1N(C)C(=O)[C@@H](C(C)C)OC(=O)[C@H](CC(C)C)N(C)C(=O)[C@@H](C(C)C)OC(=O)[C@H](CC(C)C)N(C)C(=O)[C@@H](C(C)C)OC(=O)[C@H](CC(C)C)N(C)C(=O)[C@@H](C(C)C)OC1=O QVZZPLDJERFENQ-NKTUOASPSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002990 reinforced plastic Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- OXYKVVLTXXXVRT-UHFFFAOYSA-N (4-chlorobenzoyl) 4-chlorobenzenecarboperoxoate Chemical compound C1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1 OXYKVVLTXXXVRT-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical class C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 description 1
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 description 1
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- AHWAAQOJHMFNIV-UHFFFAOYSA-N 2-tert-butylperoxy-2-ethylhexanoic acid Chemical compound CCCCC(CC)(C(O)=O)OOC(C)(C)C AHWAAQOJHMFNIV-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical class CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- JYSUEYYBKTVYJR-UHFFFAOYSA-N 3,4-dimethyldioxolane-3,5-diol Chemical compound CC1C(O)OOC1(C)O JYSUEYYBKTVYJR-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004923 Acrylic lacquer Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 238000006430 Cargill rearrangement reaction Methods 0.000 description 1
- 206010011416 Croup infectious Diseases 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 244000228367 Lewisia rediviva Species 0.000 description 1
- 235000007279 Lewisia rediviva Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000003677 Sheet moulding compound Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical group OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 201000010549 croup Diseases 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000010423 industrial mineral Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- BQJCRHHNABKAKU-KBQPJGBKSA-N morphine Chemical compound O([C@H]1[C@H](C=C[C@H]23)O)C4=C5[C@@]12CCN(C)[C@@H]3CC5=CC=C4O BQJCRHHNABKAKU-KBQPJGBKSA-N 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 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
- 235000021317 phosphate Nutrition 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005650 polypropylene glycol diacrylate Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 229960004029 silicic acid Drugs 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- ZFDIRQKJPRINOQ-UHFFFAOYSA-N transbutenic acid ethyl ester Natural products CCOC(=O)C=CC ZFDIRQKJPRINOQ-UHFFFAOYSA-N 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- GAWWVVGZMLGEIW-GNNYBVKZSA-L zinc ricinoleate Chemical compound [Zn+2].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O.CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O GAWWVVGZMLGEIW-GNNYBVKZSA-L 0.000 description 1
- 229940100530 zinc ricinoleate Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/022—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations
- C08F299/024—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations the unsaturation being in acrylic or methacrylic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/026—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight
-
- 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
- C09D163/10—Epoxy resins modified by unsaturated compounds
-
- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
Abstract
Abstract Of The Disclosure An FRP molding can be in-mold coated using a free radical peroxide initiated thermosetting composition of at least one polymerizable epoxy based oligomer having at least two acrylate groups, at least one copolymerizable ethylenically unsaturated monomer, at least one copolymerizable monoethylenically unsaturated compound having a -CO- group and a -NH2, -NH-and/or -OH group, carboxylated polyvinyl acetate, at least one zinc salt of a fatty acid, at least one calcium salt of a fatty acid, at least one copolymerizable tri or tetra acrylate, at least one accelerator for a peroxide initiator, conductive carbon black, a filler such as talc and at least one polyoxyalkylene glycol oligomer having two acrylate groups.
Description
Lo This invention relates to a thermosetting in-mold coating composition useful for in-mold coating a molded fiberglass reinforced thermoses plastic such as a polyester resin or a vinyl ester resin (FRY) molding or part that usually does not require the combining of two or more components immediately prior to use.
A major deficiency of compression molded thermoses glass fiber reinforced polyester (FRY) moldings is surface imperfections such as pits, pores, surface cracks, waviness and sink marks. The in-mold coating process of U.S. Patent 4,081,578 generally overcomes these imperfections by molding a low viscosity thermoses on top of the FRY in a second molding operation. The composition described in U.S. Patent 4,081,578 contains free hydroxyl as well as isn't groups that erupt at room temperature, resulting in a limited (about one-half hour) pot life. In practice, the reactive ingredients are kept apart, and combined only immediately prior to application. This necessitates dual pumping equipment and an accurate metering device, which increase the cost and complexity of the system. A single component coating would thus offer a significant advantage. Moreover, conductive carbon black does not dispense well in isn't based in-mold coating compositions, and it is difficult to obtain after in-mold coating and subsequent electrostatic painting, a paint layer which is even.
Therefore, it is an object of this invention to avoid the difficulties alluded to and to provide a process for in-mold coating an FRY molding with a one-eomponent coating composition.
., . I
I
Another object of this invention is to provide a composition suitable for in-mold coating an FRY molding.
A further object of this invention is to provide d cleared mulled FRY molding or part with an arrant coating infold '; kowtow with a one componer1t in-mol(l costing composition.
These end other objects and advantages of the present invention will become more apparent to those skilled in the art -from the following detailed description and working examples.
Summary Of The Invention lo According to the present invention a FRY molding can be in-rnold coated using a one-component free radical initiated thermosetting composition of (a) loo parts by weight of at least one polymerizdble epoxy based oligomer having at least two acrylate groups and a weight average molecular weight of from about 500 to 1,500, (b) from about 80 to 160 parts by weight o-f at least one copolymerizable ethylenically unsaturated monomer, (c) from about lo to 120 parts by weight of at least one copolymerizable monoethylenically unsaturated compound having a -CO- group and a -NH2, -NH- and/or -OH
group, (d) from about 20 to 90 parts by weight of carboxylated polyvinyl acetate having an acid number of from about lo to 4, (e) from about 0.2 to 5 parts by weight of at least one zinc salt of a fatty acid having at least lo carbon atoms, (F) from about Oily to lo part by weight of at least one accelerator -for a peroxide initiator, (g) -from about S to 30 parts by weigh-t of conductive carbon black, (h) from about 50 to l55 parts by weight of a filler, s .
'`' i93 (i) a copolymerizable or cocurable diacrylate compound having a weight average molecular weight of from about 250 to 5,000 and being at least one polyoxyalkylene glycol based oliyomer having two acryla.te croups, (j) at least one copolymerizable in or twitter acrylate having an average molecular weight of from about 250 to 1,000, the total of (i) and (j) being from about 5 to 120 parts by weight and the weight ratio of (i) to (j) being from about 10:1 to 1:10 and (k) at least one calcium salt of a fatty acid having at least 10 carbon atoms in an amount of from about 0.2 to 5 parts by weight.
Another aspect of the invention provides a method which comprises in-mold coating a molded thermoses polyester resin or thermoses vinyl ester resin glass fiber composition containing from about 10 to 75% by weight of glass fibers with the thermosetting in-mold coating composition under pressure, at a temperature and for a period of time sufficient to cure said in-mold coating composition to form an adherent thermoses coating on said molded thermoses resin glass fiber composition, said in-mold coating composition further comprising at least one organic free radical peroxide initiator in an amount of up to about 5% by weight based on the weight of the polymerizable ethylenically unsaturated materials.
Still a further aspect of the invention provides a laminate comprising an adherent, thermoses in-mold coating composition in-mold coated onto a molded thermoses polyester . ,~, r, I
-pa-resin or thermoses vinyl ester resin glass fiber composition containing from about 10 to 75~ by weight o-f glass fibers, said in-mold coating composition comprising the reaction product owe 100 parts by weight of at least one polymerizable epoxy based oligomer having at least two acrylate groups and a weight average molecular weight of from about 500 to 1,500, from about 80 to 160 parts by weight of at least one copolymerizable ethylenically unsaturated monomer, from about 10 to 120 parts by weight of at least one copolymerizable monoethylenically unsaturated compound having a -CO- group and a -NH2, -NH- and/or -OH group, (I) a copolymerizable or cocurable diacrylate compound having a weight average molecular weight of from about 250 to 5,000 and being at least one polyoxyalkylene glycol oligomer having two acrylate groups, (II) at least one copolymerizable in or twitter acrylate having an average molecular weight of from about 250 to 1,000, the total of (I) and (II) being from about 5 to 120 parts by weight and the weight ratio of (I) to (II) being from about 10:1 to 1:10, in admixture with from about 20 to 90 parts by weight of carboxylated polyvinyl acetate having an acid number of from about 1.5 to 4, from about 0.2 to 5 parts by weight of at least one zinc salt of a fatty acid having at least lo carbon atoms, at least one calcium salt of a fatty acid having at least 10 carbon atoms in an amount of from about 0.2 to 5 parts by weight, from about 5 to 30 parts by weight of conductive carbon black and from about 50 to 155 parts by weight of a filler.
.
3b~ 93 An organic free radical peroxide initiator is used in the composition in an amount of up to about 5%, preferably up to I
by weight based on the weight of the polymerizable ethylenically unsaturated materials.
The composition flows well and is stable for about a week even when containing the peroxide. It can be molded in a short period of time. The resulting thermoses coating exhibits good adhesion to different FRY substrates and will accept many paint finishes obviating the need for a primer.
Also, the carbon black disperses well throughout the composition to provide on curing an in-mold coating which can be spray painted electrostatically to provide an even paint coating or film. The present coating, moreover, thus generally eliminates any subsequent step of priming the in-mold coating with a conductive primer before electrostatic painting.
The present in-mold coating composition gives improved hardness and resistance to solvents as compared to that shown in U.S. Patent No. 4,414,173 mentioned swooper.
Discussion of Details And Preferred Embodiments (a) The polymerizable epoxy based oligomer having at least two acrylate (or methacrylate or ethacrylate) groups is pro-pared by reacting acrylic acid, methacrylic acid or ethacrylic acid and L9~93 so forth with an epoxy based oligomer or resin such as a Bisphenol A epoxy, a tetrdbromo Bisphenol A epoxy, finlike novolak epoxy, tetraphenylolethane epoxy, dicycloaliphatic epoxy and so forth. Mixtures of` these epoxy based oligomers may be used. Of these materials it is preferred to use a diacrylate terminated Bisphenol A epoxy oligomer. They have weight average molecular weights of from about 500 to 1,500. These materials are well known. For more information on these materials see "Heat Resistant Vinyl Ester Resin," M. I. Linctus, Technical Bulletin, SKYE, Shell Chemical Company, June, 1976 and Shell Chemical Company Technical Bulletins SKYE and SKYE.
(b) A copolymerizable ethylenically unsaturated monomer is used to copolymerize with and to cross link the polymerizable oligomers and includes styrenes (preferred), alpha methyl styrenes vinyl Tulane, t-butyl styrenes chlorostyrene, methyl methacrylate, Delilah ph-thalate (with styrenes or methyl methacrylate and the like), triallyl sonority, triallyl isocyanurate, divinely Bunsen, methyl acrylate and so forth and mixtures thereof. The unsaturated monomer is used in an amount of from about 80 to 1~0 parts by weight per 100 parts by weight of the polymerizable epoxy based oligomer.
(c) For further copolymerization and cross linking and to improve hardness of the resulting coating there is used in the in-mold coating composition a monoethylenically unsaturated compound having a -C- group and having a -NH2, -NH- and/or -OH
group. Examples of such monomeric compounds are hydroxyl propel methacrylate (preferred), hydroxyethyl methacrylate, hydroxy ethyl acrylate, hydroxy ethyl crotonate, hydroxypropyl acrylate, hydroxy polyoxypropylene acrylate, hydroxy polyoxypropylene methacrylate~ hydroxy polyoxyethylene methacrylate, acrylamide, methacrylamide, N-hydroxymethyl acrylamide, N-hydroxymethyl methacrylamide and so forth and mixtures of the same. These compounds are used in an amount of from about 10 to 120 parts by weight per 100 parts by weight of the polymerizable epoxy based of i goner .
(d) Carboxylated polyvinyl acetate is employed in the in-mol(l composition to improve print adhesion and hardness of the in-molcl coating to the substrate. The carboxylate(l polyvinyl acetate has an acid number of from about 1.5 to Thea carboxylated polyvinyl acetate is employed in an amount of from about 20 to 90 parts by weight per 100 parts by weight of the epoxy based polymerizable oligomer.
(e) A zinc salt of a fatty acid having at least 10 carbon atoms, also, is employed in the in-mold coating composition and appears to function as a mold release agent and as a secondary accelerator for the cure. Fatty acids are well known. See "Organic Chemistry," Fuzzier and Fuzzier, DO Heath and Company, lo Boston, 19~, pages 88, 381-390, 398 and ~01 and "Hocus Chemical Dictionary," Grant, McGraw Hill Book Company, New York, 1969, page 261. Mixtures of zinc salts of the fatty acids can be used. Examples of some zinc salts are zinc palpitate, zinc Stewart, zinc ricinoleate and the like. It is preferred to use the zinc salt of a saturated fatty acid such as zinc Stewart.
See, also, "Whittington's Dictionary Of Plastics," Whittington, Technomic Publishing Co., Inc., Stamford, Corn., 1968, pages 35, 102 and 261. The zinc salt is used in an amount from about 0.2 to 5 parts by weight per 100 parts by weight of the polymerizable epoxy based oligomer.
(f) An accelerator is used for the peroxide initiator and is a material such as a drier, e.g., cobalt octet (preferred).
Other materials which may be used are zinc naphthenate, lead naphthenate, cobalt naphthenate and manganese naphthenate.
30 Soluble Co, My and Pub salts of linoleic acid, also, may be used. I
Mixtures of accelerators may be used. The accelerator is used in an amount of from about 0.01 to 1 part by weight per 100 parts by weigh-t of the polymerizable epoxy based oligomer.
~Z~69~3 (g) Conductive carbon black is used in the in-mold coating composition in an amount o-f from about 5 to 30 parts by weight per lo parts by weight of the polylnerizable epoxy based oligomer.
(h) A filler is used in the in-mold coating composition in an amount of from about 50 to loss parts by weight per 100 parts by weight of the polymerizable epoxy based oligomer. Examples of fillers are clay, Moo, Mg(0~l)27 Cook, silica, calcium silicate, mica, aluminum hydroxide, barium sulfate, talc, hydrated silica, magnesium carbonate and mixtures of the same.
The fillers should be finely divided. Of these fillers it is preferred to use talc. Fillers can afford the desired viscosity and flow to the in-mold composition for molding and contribute to the desired physical properties in the resulting thermoses in-mold coating. Fillers, also, may improve adhesion. However, care should be exercised in the use of high filler contents as this may give high viscosities and result in flow and handling difficulties.
(i) Inhere further is employed in the in-mold coating composition a copolymerizable or cocurdble diacryldte compound hiving a weight average molecular weight of from about 250 to 5,000 and being at least one polyoxyalkylene glycol based oligomer having two acrylate groups. Examples of said diacryldte compounds include triethylene glycol diacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacryldte, polypropylene glycol diacrylate, polyethylene glycol dimethacrylate or polyoxyethylene glycol dimethacryldte (preferred), polypropylene glycol dimethacryldte, polyethylene propylene glycol diacryldte, and so forth and mixtures thereof. These acryldtes are made by reacting polyoxyalkylene glycols such do polypropylene ether glycol with acrylic acid, methacrylic acid and the like or by ester interchange.
(j) There, also, is employed in the in-mold composition to improve hardness without adversely affecting paint adhesion a copolymerizable in or twitter acrylate such as the reaction r 6~33 product of acrylic and/or methdcrylic acids with trios or petrols like glycerol, trinlethylnl propane Hun trio pentaerythritoi and the like. These materials also, may he obtailled by ester interch(lntJe, for example, by reaction of ethyl acrylate and the polyols. Other polyols may be use like the ethylene oxide and/or propylene oxide adduces of these ~olyols ` such as try (2-hydroxy-propoxy) propane ("CP-2fiQ~' my of to about 260, Dow Chemical Co.), "Pluracol~ PEP 650 (propylene oxide adduce of pentaerythritol, equivalent weight of about 148.1, BASS
Wyandotte, "Pluracol" TO 340 (propylene oxide adduce of trimethylol propane, equivalent weight of about 101.1, BASS
Wyandotte) and so forth and mixtures thereof. Examples of some of these acrylates are trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylol propane trimethacrylate (preferred) and so forth.
Mixtures of these in and twitter acrylates can be used. These acrylates have average molecular weights of from about 250 to 1 ,000.
The total of (i) and (j) is from about S to 120 parts by weight per 100 parts by weight of the polymerizable epoxy based oligomer and the weight ratio of (i) to (j) is from about 10:1 to 1 : 1 0 .
Since some of these reactive polyacrylates may be made by reacting unsaturated acids and alcohols, they may contain some OH
and/or COO groups.
The acrylate compounds above, appear to improve the hardness of and reduce the brittleness of the in-mold coating.
(k) A calcium salt of a fatty acid having at least 10 carbon atoms in an amount of from about 0.2 to 5 parts by weight of calcium salt per 100 parts by weight of the polymerizable epoxy based oligomer is used in the in-mold coating composition as a mold release agent and to control the rate of the cure.
Fatty acids are well known, see above. Mixtures of calcium salts of the fatty acids can be used. Examples of some calcium salts try I
Lo 3 are calcium Stewart, calciunl palpitate, calcium owlet and the like It is preferred to use the calciunl salt of a saturdtecl fatty acid like calciuln Stewart.
An organic free-radicdl or free radical generating initiator (catalyst) such as a peroxide is used to catalyze the polymerization, copolymerization and/or cross linking of the ethylenically unsaturated oligomers and the other ethylenically unsaturated materials. Examples of free-radical initiators include tertiary bottle perbenzoate, tertiary bottle peroctoate in Delilah phthalate, dustily peroxide in dim ethyl phthalate, dibenzoyl peroxide, di(p-chlorobenzoyl) peroxide in dibutyl phthalate, di(2,4-dichlorobenzoyl) peroxide with dibutyl phthalate, dilauroyl peroxide, methyl ethyl kitten peroxide, cyclohexanone peroxide in dibutyl phthalate, 3,5-dihydroxy-3,4-dimethyl-1,2-dioxacyclopentane, t-butylperoxy(2-ethyl hexanoate), caprylyl peroxide, 2,5-dimethyl-2,5-di(benzoyl proxy) hexane, l-hydroxy cyclohexyl hydroperoxide~l, t-butyl proxy (2-ethyl bitterroot), 2,5-dimethyl-2,5-bis(t-butyl proxy) hexane, cumuli hydroperoxide, dustily peroxide, t-butyl hydroperoxide, ditertiary bottle peroxide, 3,5-dihydroxy-3,5-dimethyl-1,2-oxacyclopentane, and l,l-bis(t-butyl peroxy)-3,3,5-trimethyl cyclohexane and the like and mixtures thereof. It is desirable sometimes to use mixtures of initiators to take advantage of their different decomposition rates and times at different temperatures and so forth. A preferred initiator to use is tertiary bottle perbenzoate. The peroxide initiator should be used in an amount sufficient to overcome the effect of the inhibitor and to cause cross linking or curing of the ethylenically unsaturated materials. In general the peroxide initiator is used in an amount of up to about 5%, preferably up to about 2%, by weight based on the weight of the ethylenically unsaturated materials employed in the in-mold coating composition.
The unsaturated materials mentioned above, thus, are used in an amount sufficient to provide on cure (e.g., polymerization, copolymerization and/or cross linking) a thermoses composition.
To prevent premature gelatin of the ethylenically unsaturated materials and to provide for improved shelf lo or storage ability inhibitors are added in the desired amount to the composition or are provided in the raw materials before use.
S Exan1ples of inhibitors are hydroquinone, benzoquinone, p-t-butyl catcall and the like and mixture thereof.
The in-mold composition additionally optionally may be compounded with other mold release agents, antidegradants, U-V
absorbers, paraffin wax, solid glass or resin micro-spheres, thickening agents, low shrink additives and the like. These compounding ingredients should be used in amounts sufficient to provide satisfactory results. It is not desirable to use in the in-mold composition of this invention materials like buta(liene-s-tyrene block copolymers or fatty alcohol phosphates.
lo For ease in handling, materials like carboxylated polyvinyl acetate may be dissolved in a reactive monomer like styrenes The viscosity of the oligomers may be reduced by dilution with styrenes and the like. The ingredients of the in-mold composition should be readily mixed and handled at ambient or room temperature or temperatures below the polymerization temperature so that they may be readily pumped to the mold and injected into the same. The ingredients may be warmed or heated before or during mixing and mixed in steps to facilitate -thorough mixing, dispersion and solution of the same.
Also, the bulk of the ingredients can be thoroughly mixed and the remainder including the catalyst separately mixed and then both can be pumped to a mixing head to be mixed together and then injected into the mold.
With the peroxide initiator or catalyst the in-mold composition exhibits a shelf-life at room temperature (about 25C) of about a week, and without the initiator it exhibits a shelf life of several months at room temperature. The initiator is preferably added to the composition and thoroughly mixed therewith just before molding.
All of the ingredients of the in-mold coating composition should be kept dry or have a minimal amount of moisture or the ~LZ~9~93 water content should be controlled to obtain reprodllcible results and to prevent pore Formation.
Mixing of the ingredients of the in-nlold composition should he thorough. Injection or compression transfer molding, or oiler molcl-illg apparatlls or machines can be used for the in-mold coating. lolling apparatus and methods may be found in lJ.S~
Patents Nos. 4,076,780; 4,076,7~; 4,081,578; 4,082,4S6;
4,1B9,517; 4,222,929; 4,245,006; 4,239,796; 4,239,~308 and 4,331,735. Please see, also, "Proceedings of the Thirty-Second Annual Conference Reinforced Plastics/Composites Institute," SPIT
Washington, February, 1977, Griffith et at, Section 2-C, pages 1-3 and "33rd Annual Technical Conference, 1978 Reinforced Plastics/Composites Institute The Society of the Plastics Industry, Inc.," SPIT Ongena, Section 14-B, pages 1-7. The in-mold coating composition can be applied to the substrate and cured at a temperature of from about 290 to 310F. and at a pressure of about 1000 pi For from about 0.5 to 3 minutes.
The processes and products of the present invention can be used in the manufacture of automobile parts such as grille and headlamp assemblies, deck hoods, fenders, door panels and roofs as well as in the manufacture of food trays, appliance and electrical components, furniture, machine covers and guards, bathroom components, structural panels and so forth. The glass fiber reinforced thermoses plastic (FRY) such as the polyester resin or vinyl ester resin and glass fiber composition substrate to which the in-mold composition is applied can be a sheet molding compound (SAC) or a bulk molding compound (BMC), or other thermosetting FRY material as well as a high strength molding compound (HMC) or a thick molding compound. The FRY substrate can have from about 10 to 75% by weight of glass fibers. The SAC
compound usually contains from about 25 to 30% by weight of glass fibers while the HMC compound may contain from about 55 to 60% by weight of glass fibers. The glass fiber reinforced thermoses plastic (FRY) substrate can be rigid or semirigid (may contain a flexibilizing moiety such as an adipate group in the polyester).
The substrate, also, may contain other flexibilizing polymers the elastoll1ers and plaston1ers, such do the styrene-butd-liene block copolymers. Unsatllrated plaster glass fiber thermoses are known as shown by Modern Plastics Encyclopedia," 1975-1976, October, 1975, Vol. 52, No. loan McGra\~-Hill, Inc., New York, pages 61, 62 and 105 to 107; "Modern Plastics Encyclopedia,"
1979-1980, October, 1979, Volume 56, Number loan pages 55, I
58, 147 and 148 and "Modern Plastics Encyclopedia," 19~0-81, October, 1930, Volume 57, Number loan pages 59, 60, and 151 to 153, McGraw-Hill, Inc., New York, NAY. For information on vinyl ester resins see the Shell Chemical Company Technical Bulletins mentioned above.
The compositions of the present invention can exhibit good pump ability and flow in the mold. They can give rapid cures as low as 50 to 90 seconds at 300F. They, also, show good adhesion to paints and can be used not only as an in-mold coating to cover blemishes but as a good conductive coating for electrostatic painting and as a primer for most paint finish systems such as soluble acrylic lacquers, acrylic dispersion lacquers, water borne acrylic enamels, high solids solution acrylic enamels, acrylic non-aqueous dispersions and urethanes.
The following example will serve to illustrate the present invention with more particularity to those skilled in the art.
In the example, the parts are parts by weight unless otherwise indicated.
Example In-Mold Coating Composition Parts By Mdteridl Weight __ __ ___ . _ LP-40A 75.0 Styrenes 32.0 Hydroxypropylmethacrylate 30.0 Trimethylolpropane trimethacrylate 12.0 Polyoxyethylene glycol 600 dimeth- 3.0 acrylate, molecular weight of about 770~ C36H6617
A major deficiency of compression molded thermoses glass fiber reinforced polyester (FRY) moldings is surface imperfections such as pits, pores, surface cracks, waviness and sink marks. The in-mold coating process of U.S. Patent 4,081,578 generally overcomes these imperfections by molding a low viscosity thermoses on top of the FRY in a second molding operation. The composition described in U.S. Patent 4,081,578 contains free hydroxyl as well as isn't groups that erupt at room temperature, resulting in a limited (about one-half hour) pot life. In practice, the reactive ingredients are kept apart, and combined only immediately prior to application. This necessitates dual pumping equipment and an accurate metering device, which increase the cost and complexity of the system. A single component coating would thus offer a significant advantage. Moreover, conductive carbon black does not dispense well in isn't based in-mold coating compositions, and it is difficult to obtain after in-mold coating and subsequent electrostatic painting, a paint layer which is even.
Therefore, it is an object of this invention to avoid the difficulties alluded to and to provide a process for in-mold coating an FRY molding with a one-eomponent coating composition.
., . I
I
Another object of this invention is to provide a composition suitable for in-mold coating an FRY molding.
A further object of this invention is to provide d cleared mulled FRY molding or part with an arrant coating infold '; kowtow with a one componer1t in-mol(l costing composition.
These end other objects and advantages of the present invention will become more apparent to those skilled in the art -from the following detailed description and working examples.
Summary Of The Invention lo According to the present invention a FRY molding can be in-rnold coated using a one-component free radical initiated thermosetting composition of (a) loo parts by weight of at least one polymerizdble epoxy based oligomer having at least two acrylate groups and a weight average molecular weight of from about 500 to 1,500, (b) from about 80 to 160 parts by weight o-f at least one copolymerizable ethylenically unsaturated monomer, (c) from about lo to 120 parts by weight of at least one copolymerizable monoethylenically unsaturated compound having a -CO- group and a -NH2, -NH- and/or -OH
group, (d) from about 20 to 90 parts by weight of carboxylated polyvinyl acetate having an acid number of from about lo to 4, (e) from about 0.2 to 5 parts by weight of at least one zinc salt of a fatty acid having at least lo carbon atoms, (F) from about Oily to lo part by weight of at least one accelerator -for a peroxide initiator, (g) -from about S to 30 parts by weigh-t of conductive carbon black, (h) from about 50 to l55 parts by weight of a filler, s .
'`' i93 (i) a copolymerizable or cocurable diacrylate compound having a weight average molecular weight of from about 250 to 5,000 and being at least one polyoxyalkylene glycol based oliyomer having two acryla.te croups, (j) at least one copolymerizable in or twitter acrylate having an average molecular weight of from about 250 to 1,000, the total of (i) and (j) being from about 5 to 120 parts by weight and the weight ratio of (i) to (j) being from about 10:1 to 1:10 and (k) at least one calcium salt of a fatty acid having at least 10 carbon atoms in an amount of from about 0.2 to 5 parts by weight.
Another aspect of the invention provides a method which comprises in-mold coating a molded thermoses polyester resin or thermoses vinyl ester resin glass fiber composition containing from about 10 to 75% by weight of glass fibers with the thermosetting in-mold coating composition under pressure, at a temperature and for a period of time sufficient to cure said in-mold coating composition to form an adherent thermoses coating on said molded thermoses resin glass fiber composition, said in-mold coating composition further comprising at least one organic free radical peroxide initiator in an amount of up to about 5% by weight based on the weight of the polymerizable ethylenically unsaturated materials.
Still a further aspect of the invention provides a laminate comprising an adherent, thermoses in-mold coating composition in-mold coated onto a molded thermoses polyester . ,~, r, I
-pa-resin or thermoses vinyl ester resin glass fiber composition containing from about 10 to 75~ by weight o-f glass fibers, said in-mold coating composition comprising the reaction product owe 100 parts by weight of at least one polymerizable epoxy based oligomer having at least two acrylate groups and a weight average molecular weight of from about 500 to 1,500, from about 80 to 160 parts by weight of at least one copolymerizable ethylenically unsaturated monomer, from about 10 to 120 parts by weight of at least one copolymerizable monoethylenically unsaturated compound having a -CO- group and a -NH2, -NH- and/or -OH group, (I) a copolymerizable or cocurable diacrylate compound having a weight average molecular weight of from about 250 to 5,000 and being at least one polyoxyalkylene glycol oligomer having two acrylate groups, (II) at least one copolymerizable in or twitter acrylate having an average molecular weight of from about 250 to 1,000, the total of (I) and (II) being from about 5 to 120 parts by weight and the weight ratio of (I) to (II) being from about 10:1 to 1:10, in admixture with from about 20 to 90 parts by weight of carboxylated polyvinyl acetate having an acid number of from about 1.5 to 4, from about 0.2 to 5 parts by weight of at least one zinc salt of a fatty acid having at least lo carbon atoms, at least one calcium salt of a fatty acid having at least 10 carbon atoms in an amount of from about 0.2 to 5 parts by weight, from about 5 to 30 parts by weight of conductive carbon black and from about 50 to 155 parts by weight of a filler.
.
3b~ 93 An organic free radical peroxide initiator is used in the composition in an amount of up to about 5%, preferably up to I
by weight based on the weight of the polymerizable ethylenically unsaturated materials.
The composition flows well and is stable for about a week even when containing the peroxide. It can be molded in a short period of time. The resulting thermoses coating exhibits good adhesion to different FRY substrates and will accept many paint finishes obviating the need for a primer.
Also, the carbon black disperses well throughout the composition to provide on curing an in-mold coating which can be spray painted electrostatically to provide an even paint coating or film. The present coating, moreover, thus generally eliminates any subsequent step of priming the in-mold coating with a conductive primer before electrostatic painting.
The present in-mold coating composition gives improved hardness and resistance to solvents as compared to that shown in U.S. Patent No. 4,414,173 mentioned swooper.
Discussion of Details And Preferred Embodiments (a) The polymerizable epoxy based oligomer having at least two acrylate (or methacrylate or ethacrylate) groups is pro-pared by reacting acrylic acid, methacrylic acid or ethacrylic acid and L9~93 so forth with an epoxy based oligomer or resin such as a Bisphenol A epoxy, a tetrdbromo Bisphenol A epoxy, finlike novolak epoxy, tetraphenylolethane epoxy, dicycloaliphatic epoxy and so forth. Mixtures of` these epoxy based oligomers may be used. Of these materials it is preferred to use a diacrylate terminated Bisphenol A epoxy oligomer. They have weight average molecular weights of from about 500 to 1,500. These materials are well known. For more information on these materials see "Heat Resistant Vinyl Ester Resin," M. I. Linctus, Technical Bulletin, SKYE, Shell Chemical Company, June, 1976 and Shell Chemical Company Technical Bulletins SKYE and SKYE.
(b) A copolymerizable ethylenically unsaturated monomer is used to copolymerize with and to cross link the polymerizable oligomers and includes styrenes (preferred), alpha methyl styrenes vinyl Tulane, t-butyl styrenes chlorostyrene, methyl methacrylate, Delilah ph-thalate (with styrenes or methyl methacrylate and the like), triallyl sonority, triallyl isocyanurate, divinely Bunsen, methyl acrylate and so forth and mixtures thereof. The unsaturated monomer is used in an amount of from about 80 to 1~0 parts by weight per 100 parts by weight of the polymerizable epoxy based oligomer.
(c) For further copolymerization and cross linking and to improve hardness of the resulting coating there is used in the in-mold coating composition a monoethylenically unsaturated compound having a -C- group and having a -NH2, -NH- and/or -OH
group. Examples of such monomeric compounds are hydroxyl propel methacrylate (preferred), hydroxyethyl methacrylate, hydroxy ethyl acrylate, hydroxy ethyl crotonate, hydroxypropyl acrylate, hydroxy polyoxypropylene acrylate, hydroxy polyoxypropylene methacrylate~ hydroxy polyoxyethylene methacrylate, acrylamide, methacrylamide, N-hydroxymethyl acrylamide, N-hydroxymethyl methacrylamide and so forth and mixtures of the same. These compounds are used in an amount of from about 10 to 120 parts by weight per 100 parts by weight of the polymerizable epoxy based of i goner .
(d) Carboxylated polyvinyl acetate is employed in the in-mol(l composition to improve print adhesion and hardness of the in-molcl coating to the substrate. The carboxylate(l polyvinyl acetate has an acid number of from about 1.5 to Thea carboxylated polyvinyl acetate is employed in an amount of from about 20 to 90 parts by weight per 100 parts by weight of the epoxy based polymerizable oligomer.
(e) A zinc salt of a fatty acid having at least 10 carbon atoms, also, is employed in the in-mold coating composition and appears to function as a mold release agent and as a secondary accelerator for the cure. Fatty acids are well known. See "Organic Chemistry," Fuzzier and Fuzzier, DO Heath and Company, lo Boston, 19~, pages 88, 381-390, 398 and ~01 and "Hocus Chemical Dictionary," Grant, McGraw Hill Book Company, New York, 1969, page 261. Mixtures of zinc salts of the fatty acids can be used. Examples of some zinc salts are zinc palpitate, zinc Stewart, zinc ricinoleate and the like. It is preferred to use the zinc salt of a saturated fatty acid such as zinc Stewart.
See, also, "Whittington's Dictionary Of Plastics," Whittington, Technomic Publishing Co., Inc., Stamford, Corn., 1968, pages 35, 102 and 261. The zinc salt is used in an amount from about 0.2 to 5 parts by weight per 100 parts by weight of the polymerizable epoxy based oligomer.
(f) An accelerator is used for the peroxide initiator and is a material such as a drier, e.g., cobalt octet (preferred).
Other materials which may be used are zinc naphthenate, lead naphthenate, cobalt naphthenate and manganese naphthenate.
30 Soluble Co, My and Pub salts of linoleic acid, also, may be used. I
Mixtures of accelerators may be used. The accelerator is used in an amount of from about 0.01 to 1 part by weight per 100 parts by weigh-t of the polymerizable epoxy based oligomer.
~Z~69~3 (g) Conductive carbon black is used in the in-mold coating composition in an amount o-f from about 5 to 30 parts by weight per lo parts by weight of the polylnerizable epoxy based oligomer.
(h) A filler is used in the in-mold coating composition in an amount of from about 50 to loss parts by weight per 100 parts by weight of the polymerizable epoxy based oligomer. Examples of fillers are clay, Moo, Mg(0~l)27 Cook, silica, calcium silicate, mica, aluminum hydroxide, barium sulfate, talc, hydrated silica, magnesium carbonate and mixtures of the same.
The fillers should be finely divided. Of these fillers it is preferred to use talc. Fillers can afford the desired viscosity and flow to the in-mold composition for molding and contribute to the desired physical properties in the resulting thermoses in-mold coating. Fillers, also, may improve adhesion. However, care should be exercised in the use of high filler contents as this may give high viscosities and result in flow and handling difficulties.
(i) Inhere further is employed in the in-mold coating composition a copolymerizable or cocurdble diacryldte compound hiving a weight average molecular weight of from about 250 to 5,000 and being at least one polyoxyalkylene glycol based oligomer having two acrylate groups. Examples of said diacryldte compounds include triethylene glycol diacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacryldte, polypropylene glycol diacrylate, polyethylene glycol dimethacrylate or polyoxyethylene glycol dimethacryldte (preferred), polypropylene glycol dimethacryldte, polyethylene propylene glycol diacryldte, and so forth and mixtures thereof. These acryldtes are made by reacting polyoxyalkylene glycols such do polypropylene ether glycol with acrylic acid, methacrylic acid and the like or by ester interchange.
(j) There, also, is employed in the in-mold composition to improve hardness without adversely affecting paint adhesion a copolymerizable in or twitter acrylate such as the reaction r 6~33 product of acrylic and/or methdcrylic acids with trios or petrols like glycerol, trinlethylnl propane Hun trio pentaerythritoi and the like. These materials also, may he obtailled by ester interch(lntJe, for example, by reaction of ethyl acrylate and the polyols. Other polyols may be use like the ethylene oxide and/or propylene oxide adduces of these ~olyols ` such as try (2-hydroxy-propoxy) propane ("CP-2fiQ~' my of to about 260, Dow Chemical Co.), "Pluracol~ PEP 650 (propylene oxide adduce of pentaerythritol, equivalent weight of about 148.1, BASS
Wyandotte, "Pluracol" TO 340 (propylene oxide adduce of trimethylol propane, equivalent weight of about 101.1, BASS
Wyandotte) and so forth and mixtures thereof. Examples of some of these acrylates are trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylol propane trimethacrylate (preferred) and so forth.
Mixtures of these in and twitter acrylates can be used. These acrylates have average molecular weights of from about 250 to 1 ,000.
The total of (i) and (j) is from about S to 120 parts by weight per 100 parts by weight of the polymerizable epoxy based oligomer and the weight ratio of (i) to (j) is from about 10:1 to 1 : 1 0 .
Since some of these reactive polyacrylates may be made by reacting unsaturated acids and alcohols, they may contain some OH
and/or COO groups.
The acrylate compounds above, appear to improve the hardness of and reduce the brittleness of the in-mold coating.
(k) A calcium salt of a fatty acid having at least 10 carbon atoms in an amount of from about 0.2 to 5 parts by weight of calcium salt per 100 parts by weight of the polymerizable epoxy based oligomer is used in the in-mold coating composition as a mold release agent and to control the rate of the cure.
Fatty acids are well known, see above. Mixtures of calcium salts of the fatty acids can be used. Examples of some calcium salts try I
Lo 3 are calcium Stewart, calciunl palpitate, calcium owlet and the like It is preferred to use the calciunl salt of a saturdtecl fatty acid like calciuln Stewart.
An organic free-radicdl or free radical generating initiator (catalyst) such as a peroxide is used to catalyze the polymerization, copolymerization and/or cross linking of the ethylenically unsaturated oligomers and the other ethylenically unsaturated materials. Examples of free-radical initiators include tertiary bottle perbenzoate, tertiary bottle peroctoate in Delilah phthalate, dustily peroxide in dim ethyl phthalate, dibenzoyl peroxide, di(p-chlorobenzoyl) peroxide in dibutyl phthalate, di(2,4-dichlorobenzoyl) peroxide with dibutyl phthalate, dilauroyl peroxide, methyl ethyl kitten peroxide, cyclohexanone peroxide in dibutyl phthalate, 3,5-dihydroxy-3,4-dimethyl-1,2-dioxacyclopentane, t-butylperoxy(2-ethyl hexanoate), caprylyl peroxide, 2,5-dimethyl-2,5-di(benzoyl proxy) hexane, l-hydroxy cyclohexyl hydroperoxide~l, t-butyl proxy (2-ethyl bitterroot), 2,5-dimethyl-2,5-bis(t-butyl proxy) hexane, cumuli hydroperoxide, dustily peroxide, t-butyl hydroperoxide, ditertiary bottle peroxide, 3,5-dihydroxy-3,5-dimethyl-1,2-oxacyclopentane, and l,l-bis(t-butyl peroxy)-3,3,5-trimethyl cyclohexane and the like and mixtures thereof. It is desirable sometimes to use mixtures of initiators to take advantage of their different decomposition rates and times at different temperatures and so forth. A preferred initiator to use is tertiary bottle perbenzoate. The peroxide initiator should be used in an amount sufficient to overcome the effect of the inhibitor and to cause cross linking or curing of the ethylenically unsaturated materials. In general the peroxide initiator is used in an amount of up to about 5%, preferably up to about 2%, by weight based on the weight of the ethylenically unsaturated materials employed in the in-mold coating composition.
The unsaturated materials mentioned above, thus, are used in an amount sufficient to provide on cure (e.g., polymerization, copolymerization and/or cross linking) a thermoses composition.
To prevent premature gelatin of the ethylenically unsaturated materials and to provide for improved shelf lo or storage ability inhibitors are added in the desired amount to the composition or are provided in the raw materials before use.
S Exan1ples of inhibitors are hydroquinone, benzoquinone, p-t-butyl catcall and the like and mixture thereof.
The in-mold composition additionally optionally may be compounded with other mold release agents, antidegradants, U-V
absorbers, paraffin wax, solid glass or resin micro-spheres, thickening agents, low shrink additives and the like. These compounding ingredients should be used in amounts sufficient to provide satisfactory results. It is not desirable to use in the in-mold composition of this invention materials like buta(liene-s-tyrene block copolymers or fatty alcohol phosphates.
lo For ease in handling, materials like carboxylated polyvinyl acetate may be dissolved in a reactive monomer like styrenes The viscosity of the oligomers may be reduced by dilution with styrenes and the like. The ingredients of the in-mold composition should be readily mixed and handled at ambient or room temperature or temperatures below the polymerization temperature so that they may be readily pumped to the mold and injected into the same. The ingredients may be warmed or heated before or during mixing and mixed in steps to facilitate -thorough mixing, dispersion and solution of the same.
Also, the bulk of the ingredients can be thoroughly mixed and the remainder including the catalyst separately mixed and then both can be pumped to a mixing head to be mixed together and then injected into the mold.
With the peroxide initiator or catalyst the in-mold composition exhibits a shelf-life at room temperature (about 25C) of about a week, and without the initiator it exhibits a shelf life of several months at room temperature. The initiator is preferably added to the composition and thoroughly mixed therewith just before molding.
All of the ingredients of the in-mold coating composition should be kept dry or have a minimal amount of moisture or the ~LZ~9~93 water content should be controlled to obtain reprodllcible results and to prevent pore Formation.
Mixing of the ingredients of the in-nlold composition should he thorough. Injection or compression transfer molding, or oiler molcl-illg apparatlls or machines can be used for the in-mold coating. lolling apparatus and methods may be found in lJ.S~
Patents Nos. 4,076,780; 4,076,7~; 4,081,578; 4,082,4S6;
4,1B9,517; 4,222,929; 4,245,006; 4,239,796; 4,239,~308 and 4,331,735. Please see, also, "Proceedings of the Thirty-Second Annual Conference Reinforced Plastics/Composites Institute," SPIT
Washington, February, 1977, Griffith et at, Section 2-C, pages 1-3 and "33rd Annual Technical Conference, 1978 Reinforced Plastics/Composites Institute The Society of the Plastics Industry, Inc.," SPIT Ongena, Section 14-B, pages 1-7. The in-mold coating composition can be applied to the substrate and cured at a temperature of from about 290 to 310F. and at a pressure of about 1000 pi For from about 0.5 to 3 minutes.
The processes and products of the present invention can be used in the manufacture of automobile parts such as grille and headlamp assemblies, deck hoods, fenders, door panels and roofs as well as in the manufacture of food trays, appliance and electrical components, furniture, machine covers and guards, bathroom components, structural panels and so forth. The glass fiber reinforced thermoses plastic (FRY) such as the polyester resin or vinyl ester resin and glass fiber composition substrate to which the in-mold composition is applied can be a sheet molding compound (SAC) or a bulk molding compound (BMC), or other thermosetting FRY material as well as a high strength molding compound (HMC) or a thick molding compound. The FRY substrate can have from about 10 to 75% by weight of glass fibers. The SAC
compound usually contains from about 25 to 30% by weight of glass fibers while the HMC compound may contain from about 55 to 60% by weight of glass fibers. The glass fiber reinforced thermoses plastic (FRY) substrate can be rigid or semirigid (may contain a flexibilizing moiety such as an adipate group in the polyester).
The substrate, also, may contain other flexibilizing polymers the elastoll1ers and plaston1ers, such do the styrene-butd-liene block copolymers. Unsatllrated plaster glass fiber thermoses are known as shown by Modern Plastics Encyclopedia," 1975-1976, October, 1975, Vol. 52, No. loan McGra\~-Hill, Inc., New York, pages 61, 62 and 105 to 107; "Modern Plastics Encyclopedia,"
1979-1980, October, 1979, Volume 56, Number loan pages 55, I
58, 147 and 148 and "Modern Plastics Encyclopedia," 19~0-81, October, 1930, Volume 57, Number loan pages 59, 60, and 151 to 153, McGraw-Hill, Inc., New York, NAY. For information on vinyl ester resins see the Shell Chemical Company Technical Bulletins mentioned above.
The compositions of the present invention can exhibit good pump ability and flow in the mold. They can give rapid cures as low as 50 to 90 seconds at 300F. They, also, show good adhesion to paints and can be used not only as an in-mold coating to cover blemishes but as a good conductive coating for electrostatic painting and as a primer for most paint finish systems such as soluble acrylic lacquers, acrylic dispersion lacquers, water borne acrylic enamels, high solids solution acrylic enamels, acrylic non-aqueous dispersions and urethanes.
The following example will serve to illustrate the present invention with more particularity to those skilled in the art.
In the example, the parts are parts by weight unless otherwise indicated.
Example In-Mold Coating Composition Parts By Mdteridl Weight __ __ ___ . _ LP-40A 75.0 Styrenes 32.0 Hydroxypropylmethacrylate 30.0 Trimethylolpropane trimethacrylate 12.0 Polyoxyethylene glycol 600 dimeth- 3.0 acrylate, molecular weight of about 770~ C36H6617
2% benzoquinone in styrenes 8.0 A. All of the above were mixed well Zinc Stewart 0.90 15 Calcium Stewart 1.35 Cobalt octet (12% as Co in 0.12 mineral oil) B. The Zen, Cay and Co materials were aided Jo A. and mixed well 20 CargiIl Resin 1570 (non-volatile diacrylate 85.0 ester of a liquid Bisphenol A epoxy resin, Car gill Corp.) C. Added 1570 to A. and B. and mixed well D. Blended with A. B. and C were 25 VULCAN CRY (N472, Conductive furnace 10 carbon black, Cabot Corp.) and MIX I ~RSC Talc (Hydrous magnesium 80 silicate, Cyprus Industrial Minerals Corp.) Brook field Viscosity of the in-mold coating composition at 86F, #7 spindle 100 rum was 14,800 cups.
Gel times on total in-mold coating composition at 230F, minutes/peak temp. DO
e I
i 1 part TBPB/100 parts in-mold coating composition 13.1/374F
1.5 parts TBPB/100 parts in-mold coating composition 8.3/358F
IBPB (Tertiary bottle perbenzoate) LP-40A - BOOKLET -okay% by weight carboxylated polyvinyl I acetate, acid No. 2.3-2.7, in styrenes viscosity of 5,000 centipoises at 25C, specific gravity at 25/25C of 0.997, solidification temperature of -30C, storage stability of ~30 days at 120F, Union Carbide Corp.
When the in-mold composition was cured on an SAC (FRY) substrate in a mold for 60 seconds at 300F and 1000 psi, the following properties were obtained on testing the coating (1.5 mix thickness):
Hardness pencil* at cay 75F F to H
Hardness pencil* at 290-300F 3B
Solvent Resistance (rub test, to rub off coating) methyl ethyl kitten good ethylene chloride good Ransberg meter reading (top of scale) 165~
In comparison a similar in-mold coating composition in which polyvinyl acetate was used in place of the carboxylated polyvinyl acetate and in which all of the trimethylol propane trimethacrylate was replaced with an equal amount of polyoxyethylene glycol 600 dimethacrylate gave after in-mold coating on an SAC (FRY) substrate the following results:
25 Hardness pencil* at cay 75F F
Hardness pencil* at 290-300F 6B
Solvent resistance (rub test) methyl ethyl kitten Fair ethylene chloride Poor 30 Ransberg meter reading (conductivity) 165+
*ASTM D3363-74 (Reproved 1980) Softer Harder or Jo
Gel times on total in-mold coating composition at 230F, minutes/peak temp. DO
e I
i 1 part TBPB/100 parts in-mold coating composition 13.1/374F
1.5 parts TBPB/100 parts in-mold coating composition 8.3/358F
IBPB (Tertiary bottle perbenzoate) LP-40A - BOOKLET -okay% by weight carboxylated polyvinyl I acetate, acid No. 2.3-2.7, in styrenes viscosity of 5,000 centipoises at 25C, specific gravity at 25/25C of 0.997, solidification temperature of -30C, storage stability of ~30 days at 120F, Union Carbide Corp.
When the in-mold composition was cured on an SAC (FRY) substrate in a mold for 60 seconds at 300F and 1000 psi, the following properties were obtained on testing the coating (1.5 mix thickness):
Hardness pencil* at cay 75F F to H
Hardness pencil* at 290-300F 3B
Solvent Resistance (rub test, to rub off coating) methyl ethyl kitten good ethylene chloride good Ransberg meter reading (top of scale) 165~
In comparison a similar in-mold coating composition in which polyvinyl acetate was used in place of the carboxylated polyvinyl acetate and in which all of the trimethylol propane trimethacrylate was replaced with an equal amount of polyoxyethylene glycol 600 dimethacrylate gave after in-mold coating on an SAC (FRY) substrate the following results:
25 Hardness pencil* at cay 75F F
Hardness pencil* at 290-300F 6B
Solvent resistance (rub test) methyl ethyl kitten Fair ethylene chloride Poor 30 Ransberg meter reading (conductivity) 165+
*ASTM D3363-74 (Reproved 1980) Softer Harder or Jo
Claims (10)
1. A composition useful as a thermosetting coating composition comprising (a) 100 parts by weight of at least one polymerizable epoxy based oligomer having at least two acrylate groups and a weight average molecular weight of from about 500 to 1,500, (b) from about 80 to 160 parts by weight of at least one copolymerizable ethylenically unsaturated monomer, (c) from about 10 to 120 parts by weight of at least one copolymerizable monoethylenically unsaturated compound having a -CO- group and a -NH2, -NH- and/or -OH
group, (d) from about 20 to 90 parts by weight of carboxylated polyvinyl acetate having an acid number of from about 1.5 to 4, (e) from about 0.2 to 5 parts by weight of at least one zinc salt of a fatty acid having at least 10 carbon atoms, (f) from about 0.01 to 1.0 part by weight of at least one accelerator for a peroxide initiator, (g) from about 5 to 30 parts by weight of conductive carbon black, (h) from about 50 to 155 parts by weight of a filler, (i) a copolymerizable or cocurable diacrylate compound having a weight average molecular weight of from about 250 to 5,000 and being at least one polyoxyalkylene glycol oligomer having two acrylate groups and (j) at least one copolymerizable tri or tetra acrylate having an average molecular weight of from about 250 to 1,000, the total of (i) and (j) being from about 5 to 120 parts by weight and the weight ratio of (i) to (j) being from about 10:1 to 1:10 and (k) at least one calcium salt of a fatty acid having at least 10 carbon atoms in an amount of from about 0.2 to 5 parts by weight.
group, (d) from about 20 to 90 parts by weight of carboxylated polyvinyl acetate having an acid number of from about 1.5 to 4, (e) from about 0.2 to 5 parts by weight of at least one zinc salt of a fatty acid having at least 10 carbon atoms, (f) from about 0.01 to 1.0 part by weight of at least one accelerator for a peroxide initiator, (g) from about 5 to 30 parts by weight of conductive carbon black, (h) from about 50 to 155 parts by weight of a filler, (i) a copolymerizable or cocurable diacrylate compound having a weight average molecular weight of from about 250 to 5,000 and being at least one polyoxyalkylene glycol oligomer having two acrylate groups and (j) at least one copolymerizable tri or tetra acrylate having an average molecular weight of from about 250 to 1,000, the total of (i) and (j) being from about 5 to 120 parts by weight and the weight ratio of (i) to (j) being from about 10:1 to 1:10 and (k) at least one calcium salt of a fatty acid having at least 10 carbon atoms in an amount of from about 0.2 to 5 parts by weight.
2. A composition according to claim 1 containing additionally at least one organic free radical peroxide initiator in an amount of up to about 5% by weight based on the weight of the polymerizable ethylenically unsaturated materials.
3. A composition according to claim 1 where (h) comprises talc.
4. A composition according to claim 1 where (a) is a diacrylate ester of a liquid Bisphenol A
epoxy resin, (b) is styrene, (c) is hydroxypropyl methacrylate, (e) is zinc stearate, (f) is cobalt octoate, (h) is talc, (i) is polyoxyethylene glycol dimethacrylate having a molecular weight of about 770, (j) is trimethylol propane trimethacrylate and (k) is calcium stearate.
epoxy resin, (b) is styrene, (c) is hydroxypropyl methacrylate, (e) is zinc stearate, (f) is cobalt octoate, (h) is talc, (i) is polyoxyethylene glycol dimethacrylate having a molecular weight of about 770, (j) is trimethylol propane trimethacrylate and (k) is calcium stearate.
5. A method which comprises in-mold coating a molded thermoset polyester resin or thermoset vinyl ester resin glass fiber composition containing from about 10 to 75% by weight of glass fibers with a thermosetting in-mold coating composition under pressure, at a temperature and for a period of time sufficient to cure said in-mold coating composition to form an adherent thermoset coating on said molded thermoset resin glass fiber composition, said in-mold coating composition comprising (a) 100 parts by weight of at least one polymerizable epoxy based oligomer having at least two acrylate groups and a weight average molecular weight of from about 500 to 1,500, (b) from about 80 to 160 parts by weight of at least one copolymerizable ethylenically unsaturated monomer, (c) From about 10 to 120 parts by weight of at least one copolymerizable monoethylenically unsaturated compound having a -CO- group and a -NH2, -NH- and/or -OH
group, (d) from about 20 to 90 parts by weight of carboxylated polyvinyl acetate having an acid number of from about 1.5 to 4, (e) from about 0.2 to 5 parts by weight of at least one zinc salt of a fatty acid having at least 10 carbon atoms, (f) from about 0.01 to 1.0 part by weight of at least one accelerator for a peroxide initiator, (g) from about 5 to 30 parts by weight of conductive carbon black, (h) from about 50 to 155 parts by weight of a filler, (i) a copolymerizable or cocurable diacrylate compound having a weight average molecular weight of from about 250 to 5,000 and being at least one polyoxyalkylene glycol oligomer having two acrylate groups, (j) at least one copolymerizable tri or tetra acrylate having an average molecular weight of from about 250 to 1,000, the total of (i) and (j) being from about 5 to 120 parts by weight and the weight ratio of (i) to (j) being from about 10:1 to 1:10, (k) at least one calcium salt of a fatty acid having at least 10 carbon atoms in an amount of from about 0.2 to 5 parts by weight and at least one organic free radical peroxide initiator in an amount of up to about 5% by weight based on the weight of the polymerizable ethylenically unsaturated materials.
group, (d) from about 20 to 90 parts by weight of carboxylated polyvinyl acetate having an acid number of from about 1.5 to 4, (e) from about 0.2 to 5 parts by weight of at least one zinc salt of a fatty acid having at least 10 carbon atoms, (f) from about 0.01 to 1.0 part by weight of at least one accelerator for a peroxide initiator, (g) from about 5 to 30 parts by weight of conductive carbon black, (h) from about 50 to 155 parts by weight of a filler, (i) a copolymerizable or cocurable diacrylate compound having a weight average molecular weight of from about 250 to 5,000 and being at least one polyoxyalkylene glycol oligomer having two acrylate groups, (j) at least one copolymerizable tri or tetra acrylate having an average molecular weight of from about 250 to 1,000, the total of (i) and (j) being from about 5 to 120 parts by weight and the weight ratio of (i) to (j) being from about 10:1 to 1:10, (k) at least one calcium salt of a fatty acid having at least 10 carbon atoms in an amount of from about 0.2 to 5 parts by weight and at least one organic free radical peroxide initiator in an amount of up to about 5% by weight based on the weight of the polymerizable ethylenically unsaturated materials.
6. A method according to claim 5 where (h) comprises talc.
7. A method according to claim 5 where (a) is a diacrylate ester of a liquid Bisphenol A
epoxy resin, (b) is styrene, (c) is hydroxypropyl methacrylate, (e) is zinc stearate, (f) is cobalt octoate, (h) is talc, (i) is polyoxyethylene glycol dimethacrylate having a molecular weight of about 770 (j) is trimethylol propane trimethacrylate, (k) is calcium stearate and said initiator is tertiary butyl perbenzoate.
epoxy resin, (b) is styrene, (c) is hydroxypropyl methacrylate, (e) is zinc stearate, (f) is cobalt octoate, (h) is talc, (i) is polyoxyethylene glycol dimethacrylate having a molecular weight of about 770 (j) is trimethylol propane trimethacrylate, (k) is calcium stearate and said initiator is tertiary butyl perbenzoate.
8. A laminate comprising an adherent, thermoset in-mold coating composition in-mold coated onto a molded thermoset polyester resin or thermoset vinyl ester resin glass fiber composition containing from about 10 to 75% by weight of glass fibers, said in-mold coating composition comprising the reaction product of 100 parts by weight of at least one polymerizable epoxy based oligomer having at least two acrylate groups and a weight average molecular weight of from about 500 to 1,500, from about 80 to 160 parts by weight of at least one copolymerizable ethylenically unsaturated monomer, from about 10 to 120 parts by weight of at least one copolymerizable monoethylenically unsaturated compound having a -CO- group and a -NH2, -NH-and/or -OH group, (I) a copolymerizable or cocurable diacrylate compound having a weight average molecular weight of from about 250 to 5,000 and being at least one polyoxyalkylene glycol oligomer having two acrylate groups, (II) at least one copolymerizable tri or tetra acrylate having an average molecular weight of from about 250 to 1,000, the total of (I) and (II) being from about 5 to 120 parts by weight and the weight ratio of (I) to (II) being from about 10:1 to 1:10, in admixture with from about 20 to 90 parts by weight of carboxylated polyvinyl acetate having an acid number of from about 1.5 to 4, from about 0.2 to 5 parts by weight of at least one zinc salt of a fatty acid having at least 10 carbon atoms, at least one calcium salt of a fatty acid having at least 10 carbon atoms in an amount of from about 0.2 to 5 parts by weight, from about 5 to 30 parts by weight of conductive carbon black and from about 50 to 155 parts by weight of a filler.
9. A laminate according to claim 8 in which in said in-mold coating composition said filler comprises talc.
10. A laminate according to claim 8 in which in said in-mold coating composition said epoxy based oligomer is a diacrylate ester of a liquid Bisphenol A epoxy resin, said ethylenically unsaturated monomer is styrene, said monoethylenically unsaturated compound is hydroxy propyl methacrylate, said (I) copolymerizable or cocurable diacrylate compound is polyoxyethylene glycol dimethacrylate having a molecular weight of about 770, said (II) tri or tetra acrylate is trimethylol propane trimethacrylate, said filler comprises talc, said zinc salt is zinc stearate and said calcium salt is calcium stearate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US597,149 | 1984-04-05 | ||
| US06/597,149 US4515710A (en) | 1983-07-18 | 1984-04-05 | In-mold coating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1219693A true CA1219693A (en) | 1987-03-24 |
Family
ID=24390309
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000466081A Expired CA1219693A (en) | 1984-04-05 | 1984-10-23 | In-mold coating composition |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4515710A (en) |
| JP (1) | JPS60212467A (en) |
| CA (1) | CA1219693A (en) |
| DE (1) | DE3441073A1 (en) |
| FR (1) | FR2562551B1 (en) |
| GB (1) | GB2156835B (en) |
| IT (1) | IT1177332B (en) |
| SE (1) | SE456503B (en) |
Families Citing this family (37)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4774035A (en) * | 1986-01-14 | 1988-09-27 | Camelot Industries Corporation | Process of coating an ophthalmic lens |
| US4873274A (en) * | 1987-09-24 | 1989-10-10 | Morton Thiokol, Inc. | In-mold coating powders with two initiators or 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane as a single initiator |
| US5084353A (en) * | 1989-05-12 | 1992-01-28 | Gencorp Inc. | Thermosetting in-mold coating compositions |
| US5132052A (en) * | 1991-03-20 | 1992-07-21 | Gencorp Inc. | Fast cure in-mold coating |
| US5428068A (en) * | 1992-01-30 | 1995-06-27 | Gencorp Inc. | Unsaturated polyester-modified flexible polymers for use in molding composition |
| US5362819A (en) * | 1992-01-30 | 1994-11-08 | Gencorp Inc. | Polyester-flexible polymer block copolymers and mixtures thereof |
| US5385963A (en) * | 1992-01-30 | 1995-01-31 | Gencorp Inc. | Unsaturated polyester-modified flexible copolymers for use in sheet molding compositions |
| US5334441A (en) * | 1992-01-30 | 1994-08-02 | Gencorp Inc. | Composite comprising unsaturated polyester-flexible polymer block copolymer coated fiber structures in a polyester or vinyl ester resin matrix |
| US5342554A (en) * | 1993-01-07 | 1994-08-30 | Gencorp Inc. | Vinyl-terminated polyesters and polycarbonates for flexibilizing and improving the toughness of compositions from unsaturated polyesters and fiber reinforced plastics made from them |
| US5376721A (en) * | 1993-01-29 | 1994-12-27 | Gencorp Inc. | Low-profile additives for thermosetting polyester compositions |
| EP0622386B1 (en) * | 1993-04-26 | 1998-01-28 | Gencorp Inc. | Conductive in-mold coatings |
| DE4317302A1 (en) * | 1993-05-25 | 1994-12-01 | Degussa | Conductive floor coating |
| EP0662501A1 (en) * | 1994-01-07 | 1995-07-12 | Gencorp Inc. | Polymeric compositions, their preparation and use |
| WO1997034709A1 (en) * | 1996-03-21 | 1997-09-25 | The Dow Chemical Company | Process for the preparation of electrostatically coated, thermoset articles containing fillers |
| US5849168A (en) * | 1996-06-14 | 1998-12-15 | Acushnet Company | Method of in-mold coating golf balls |
| US5777053A (en) * | 1997-01-17 | 1998-07-07 | Gencorp Inc. | In-mold coating compositions suitable as is for an end use application |
| ZA994919B (en) * | 1998-08-21 | 2000-02-07 | Sartomer Co Inc | Unsaturated polyester resin compositions comprising metallic monomers. |
| US6174427B1 (en) | 1998-09-24 | 2001-01-16 | The Dow Chemical Company | Process for the preparation of electromotively coated filled thermoset articles |
| WO2001081065A1 (en) * | 2000-04-20 | 2001-11-01 | Decoma Exterior Trim Inc. | Method of molding a panel |
| US20040071980A1 (en) * | 2000-07-12 | 2004-04-15 | Mcbain Douglas S. | Method for in-mold coating a polyolefin article |
| US6617033B1 (en) | 2000-07-12 | 2003-09-09 | Omnova Solutions Inc. | Method for in-mold coating a polyolefin article |
| US6793861B2 (en) | 2000-07-12 | 2004-09-21 | Omnova Solutions Inc. | Optimization of in-mold coating injection molded thermoplastic substrates |
| US6887550B2 (en) * | 2001-10-22 | 2005-05-03 | Omnova Solutions Inc. | Removable defined flange for in-mold coating containment |
| US7105231B2 (en) * | 2001-10-22 | 2006-09-12 | Omnova Solutions Inc. | In-mold coating barrier for a substrate injection orifice |
| US6890469B2 (en) | 2001-10-22 | 2005-05-10 | Omnova Solutions Inc. | Selectively controlling in-mold coating flow |
| US7045213B2 (en) * | 2001-10-22 | 2006-05-16 | Omnova Solutions Inc. | In-mold coating injection inlet flow control |
| JP4230692B2 (en) | 2001-11-22 | 2009-02-25 | 大日本塗料株式会社 | Manufacturing method for in-mold coating |
| US6676877B2 (en) | 2002-04-03 | 2004-01-13 | Omnova Solutions Inc. | Mold runner for prevention of in-mold coating flow |
| US6720076B2 (en) * | 2002-05-31 | 2004-04-13 | Omnova Solutions Inc. | In-mold primer coating for thermoplastic substrates |
| CA2496490C (en) * | 2002-08-23 | 2009-08-18 | Mitsui Chemicals, Inc. | In-mold coating molded article and process for preparing the same |
| US20040121034A1 (en) * | 2002-12-10 | 2004-06-24 | Mcbain Douglas S. | Integral injection molding and in-mold coating apparatus |
| WO2005010106A2 (en) * | 2003-07-22 | 2005-02-03 | Omnova Solutions Inc. | Base-coat in-mold coating |
| GB0408480D0 (en) * | 2004-04-16 | 2004-05-19 | Koninkl Philips Electronics Nv | Variable focus lens having two liquids and electronic device |
| JP4590473B2 (en) * | 2008-12-10 | 2010-12-01 | 大日本塗料株式会社 | In-mold coating composition and in-mold coated molded body |
| ES2363429B1 (en) * | 2010-01-20 | 2012-06-13 | Fco. Ramon Sanchez Lopez | COMPOSITE MATERIAL WITH SLATE AND CARBON REINFORCEMENT AND ITS PROCESSING PROCEDURE. |
| WO2015107903A1 (en) * | 2014-01-17 | 2015-07-23 | 東レ株式会社 | Coated fiber-reinforced resin molding and process for producing same |
| JP7205280B2 (en) * | 2019-02-18 | 2023-01-17 | Dic株式会社 | Thermosetting resin composition, bulk molding compound, and molded article |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4367192A (en) * | 1977-07-11 | 1983-01-04 | The General Tire & Rubber Company | In-mold coating of sheet molding compound moldings |
| US4329134A (en) * | 1977-07-11 | 1982-05-11 | The General Tire & Rubber Company | In-the-mold coating apparatus and method |
| US4239808A (en) * | 1979-06-13 | 1980-12-16 | The General Tire & Rubber Company | In-mold coating of sheet molding compound moldings |
| US4414173A (en) * | 1981-11-02 | 1983-11-08 | The General Tire & Rubber Company | In-mold coating |
| MX173523B (en) * | 1981-11-02 | 1994-03-11 | Gencorp Inc | IMPROVEMENTS IN THERMOSURING COATING COMPOSITION AND METHOD |
-
1984
- 1984-04-05 US US06/597,149 patent/US4515710A/en not_active Expired - Lifetime
- 1984-10-23 CA CA000466081A patent/CA1219693A/en not_active Expired
- 1984-10-24 SE SE8405324A patent/SE456503B/en not_active IP Right Cessation
- 1984-10-31 FR FR8416659A patent/FR2562551B1/en not_active Expired
- 1984-11-07 JP JP59233366A patent/JPS60212467A/en active Granted
- 1984-11-09 DE DE19843441073 patent/DE3441073A1/en not_active Ceased
- 1984-11-22 GB GB08429472A patent/GB2156835B/en not_active Expired
- 1984-11-27 IT IT23752/84A patent/IT1177332B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| IT1177332B (en) | 1987-08-26 |
| GB8429472D0 (en) | 1985-01-03 |
| SE456503B (en) | 1988-10-10 |
| FR2562551A1 (en) | 1985-10-11 |
| JPH0139690B2 (en) | 1989-08-23 |
| SE8405324D0 (en) | 1984-10-24 |
| US4515710A (en) | 1985-05-07 |
| IT8423752A1 (en) | 1986-05-27 |
| GB2156835B (en) | 1987-07-15 |
| JPS60212467A (en) | 1985-10-24 |
| IT8423752A0 (en) | 1984-11-27 |
| DE3441073A1 (en) | 1985-10-24 |
| FR2562551B1 (en) | 1986-12-26 |
| SE8405324L (en) | 1985-10-06 |
| GB2156835A (en) | 1985-10-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1219693A (en) | In-mold coating composition | |
| US5359002A (en) | Epoxy polyacrylate with OH or amide-containing monomer | |
| US4414173A (en) | In-mold coating | |
| JP3548229B2 (en) | Conductive gray mold inner coating | |
| CA2049895C (en) | Fast cure in-mold coating | |
| CA1192453A (en) | Method for repairing glass fiber reinforced plastic parts | |
| US4534888A (en) | In-mold coating | |
| US5371117A (en) | Sprayable filler composition | |
| CA1186429A (en) | In-mold coating | |
| US4508785A (en) | In-mold coating | |
| EP1532214A2 (en) | In-mold primer coating for thermoplastic substrates | |
| EP0461320B1 (en) | In mold coating compositions | |
| JPH07100729B2 (en) | Thermosetting resin composition for gel coat |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |