JP5862039B2 - 塗装用樹脂組成物及びそれを使用した成形品 - Google Patents
塗装用樹脂組成物及びそれを使用した成形品 Download PDFInfo
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- JP5862039B2 JP5862039B2 JP2011083039A JP2011083039A JP5862039B2 JP 5862039 B2 JP5862039 B2 JP 5862039B2 JP 2011083039 A JP2011083039 A JP 2011083039A JP 2011083039 A JP2011083039 A JP 2011083039A JP 5862039 B2 JP5862039 B2 JP 5862039B2
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- Prior art keywords
- resin
- rubber
- mass
- coating
- vinyl
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- 238000000576 coating method Methods 0.000 title claims description 84
- 239000011248 coating agent Substances 0.000 title claims description 82
- 239000011342 resin composition Substances 0.000 title claims description 39
- -1 aromatic vinyl compound Chemical class 0.000 claims description 94
- 229920001577 copolymer Polymers 0.000 claims description 88
- 229920002554 vinyl polymer Polymers 0.000 claims description 70
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 54
- 239000000178 monomer Substances 0.000 claims description 53
- 229920001971 elastomer Polymers 0.000 claims description 49
- 229920005989 resin Polymers 0.000 claims description 46
- 239000011347 resin Substances 0.000 claims description 46
- 229920006026 co-polymeric resin Polymers 0.000 claims description 42
- 229920000642 polymer Polymers 0.000 claims description 36
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 33
- 239000005977 Ethylene Substances 0.000 claims description 33
- 239000005060 rubber Substances 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 22
- 230000000379 polymerizing effect Effects 0.000 claims description 19
- 229920001225 polyester resin Polymers 0.000 claims description 17
- 239000004645 polyester resin Substances 0.000 claims description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 16
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 16
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 15
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 12
- 238000001746 injection moulding Methods 0.000 claims description 12
- 150000003923 2,5-pyrrolediones Chemical class 0.000 claims description 9
- 150000001993 dienes Chemical class 0.000 claims description 7
- 150000008360 acrylonitriles Chemical class 0.000 claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 40
- 239000000203 mixture Substances 0.000 description 27
- 239000003973 paint Substances 0.000 description 27
- 238000012360 testing method Methods 0.000 description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 25
- 238000006116 polymerization reaction Methods 0.000 description 25
- 239000002253 acid Substances 0.000 description 22
- 239000000047 product Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 238000006068 polycondensation reaction Methods 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 15
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 14
- 239000002245 particle Substances 0.000 description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 13
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 13
- 238000005886 esterification reaction Methods 0.000 description 12
- 238000000465 moulding Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 11
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000004711 α-olefin Substances 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000007809 chemical reaction catalyst Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 229920000800 acrylic rubber Polymers 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 229920000058 polyacrylate Polymers 0.000 description 8
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- 229920000126 latex Polymers 0.000 description 7
- 239000003505 polymerization initiator Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 239000004816 latex Substances 0.000 description 6
- CLNYHERYALISIR-UHFFFAOYSA-N nona-1,3-diene Chemical compound CCCCCC=CC=C CLNYHERYALISIR-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 238000010422 painting Methods 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 150000008065 acid anhydrides Chemical class 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 4
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 125000005907 alkyl ester group Chemical group 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 229920003244 diene elastomer Polymers 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 4
- 235000021189 garnishes Nutrition 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 239000000057 synthetic resin Substances 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 3
- 229920001634 Copolyester Polymers 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Natural products CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 3
- 239000004640 Melamine resin Substances 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 238000000071 blow moulding Methods 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 239000002320 enamel (paints) Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 2
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- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
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- 230000000996 additive effect Effects 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
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- 229920006127 amorphous resin Polymers 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
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- 229920001400 block copolymer Polymers 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
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- 239000000701 coagulant Substances 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
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- 229920006037 cross link polymer Polymers 0.000 description 2
- 229920006038 crystalline resin Polymers 0.000 description 2
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 2
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 2
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 2
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
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- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 238000004018 waxing Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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Description
ゴム質重合体〔a〕の存在下にビニル系単量体〔b1〕を重合して得られたゴム強化共重合樹脂〔A1〕、または、ゴム質重合体〔a〕の存在下にビニル系単量体〔b1〕を重合して得られたゴム強化共重合樹脂〔A1〕とビニル系単量体〔b2〕の(共)重合体〔A2〕を含有するゴム強化ビニル系樹脂。
但し、ゴム質重合体〔a〕としてジエン系重合体を使用し、ビニル系単量体〔b1〕及びビニル系単量体〔b2〕として以下の組み合わせの化合物を使用するが、[b1]が(1)又は(2)、かつ、[b2]が(1)又は(2)である。
(1)芳香族ビニル化合物及びシアン化ビニル化合物。
(2)芳香族ビニル化合物、シアン化ビニル化合物及びマレイミド系化合物。
本発明の塗装用樹脂組成物は、特定のゴム強化ビニル系樹脂〔A〕、ポリエステル樹脂〔B〕及びエチレン・(メタ)アクリル酸エステル・一酸化炭素共重合体〔C〕から成る。以下、上記の各成分について、それぞれ、成分〔A〕、成分〔B〕、成分〔C〕と略記することがある。
ゴム強化ビニル系樹脂〔A〕は、ゴム質重合体〔a〕の存在下にビニル系単量体〔b1〕を重合して得られたゴム強化共重合樹脂〔A1〕、または、ゴム質重合体〔a〕の存在下にビニル系単量体〔b1〕を重合して得られたゴム強化共重合樹脂〔A1〕とビニル系単量体〔b2〕の(共)重合体〔A2〕を含有するゴム強化ビニル系樹脂である。
(2)芳香族ビニル化合物、シアン化ビニル化合物及びマレイミド系化合物。
(4)(メタ)アクリル酸エステル化合物のみを重合して得られた(共)重合体の1種以上。
(5)芳香族ビニル化合物及びシアン化ビニル化合物を重合して得られた共重合体の1種以上。
(6)芳香族ビニル化合物及び(メタ)アクリル酸エステル化合物を重合して得られた共重合体の1種以上。
(7)芳香族ビニル化合物、シアン化ビニル化合物及び(メタ)アクリル酸エステル化合物を重合して得られた共重合体の1種以上。
(8)芳香族ビニル化合物及びマレイミド系化合物を重合して得られた共重合体の1種以上。
(9)芳香族ビニル化合物、シアン化ビニル化合物及びマレイミド系化合物を重合して得られた共重合体の1種以上。
[数1]
グラフト率(質量%)={(y−x)/x}×100
本発明で使用するポリエステル樹脂〔B〕は、分子の主鎖中にエステル結合を有する樹脂であれば、特に限定されず、飽和ポリエステル樹脂であってよいし、不飽和ポリエステル樹脂であってもよい。これらのうち、特に飽和ポリエステル樹脂が好ましい。また、ホモ型ポリエステルであってよいし、共重合ポリエステルであってもよい。更に、結晶性樹脂であってよいし、非晶性樹脂であってもよい。
本発明で使用するエチレン・(メタ)アクリル酸エステル・一酸化炭素共重合体〔C〕は、エチレン単位(以下、「単位〔t1〕」という)と、(メタ)アクリル酸エステルから成る単位(以下、「単位〔t2〕」という)と、一酸化炭素から成る単位(以下、「単位〔t3〕」という)とを含む共重合体である。
本発明の塗装用樹脂組成物は、本発明の目的を損なわない限り、難撚剤、充填剤、着色剤、金属粉末、補強剤、可塑剤、相容化剤、熱安定剤、光安定剤、酸化防止剤、紫外線吸収剤、帯電防止剤、滑剤、耐候剤、老化防止剤、防曇剤、抗菌剤、防かび剤、粘着付与剤、可塑剤などの添加剤を適宜添加することが出来る。着色剤としては、有機顔料、有機染料、無機顔料などが挙げられる。
本発明の塗装用樹脂組成物において、成分〔A〕/成分〔B〕/成分〔C〕の配合量は、上記成分〔A〕、〔B〕及び〔C〕の合計を100質量部として、84.9〜98.9/1〜8/0.1〜7.1質量部、好ましくは87〜97/2〜7/1〜6質量部、更に好ましくは89〜95/3〜6/2〜5質量部、特に好ましくは91〜95/3〜5/2〜4質量部である。
本発明の塗装用樹脂組成物は、射出成形、射出圧縮成形、プレス成形、押出成形、共押出成形、シート押出成形、異形押出成形、発泡成形、真空成形、ブロー成形、圧縮成形、キャスト成形、ロール成形などの公知の成形法により、所定形状の成形品とすることが出来る。
ISO179に準じて、室温におけるシャルピー衝撃強さ(Edgewise Impact、ノッチ付き)を測定した。測定条件は、次の通りである。
試験片タイプ : Type 1
ノッチタイプ : Type A
荷重 : 2J
ISO1133に準じ、測定温度240℃、荷重98Nの条件で測定を行った。
ISO75に準じ、荷重1.80MPaの条件で測定を行った。
FANAC株式会社製の射出成形機「α−150」(型式名)を用い、表1に記載の塗装用樹脂組成物からなる、150mm×70mm×3mmの試験片を射出成形した。射出成形時の樹脂温度は260℃、金型温度は5℃、射出速度は5mm/sであった。得られた試験片を以下の手順(i)〜(vi)に従って塗装し、その判定を行った。
射出成形した試験片を、0℃にコントロールした恒温層内に12時間以上放置して状態調節を行った。
<(ii)ベース塗装>
合成樹脂エナメル塗料53部及び合成樹脂塗料用シンナー47部(但し、これら成分の合計は100部)からなるベース塗装用塗料を調製し、吹き付け塗装を行った。塗膜厚さは20〜30μmであった。
<(iii)1分間放置>
(ii)の試験片を、1分間放置した。
<(iv)クリア塗装>
合成樹脂クリア塗料56部、合成樹脂塗料用シンナー22部、及び、硬化剤22部(但し、これら成分の合計は100部)からなるクリア塗装用塗料を調製し、吹き付け塗装を行った。塗膜厚さは30〜40μmであった。
<(v)10分間放置>
クリア塗装後の試験片を、10分間放置した。
<(vi)乾燥>
(v)の試験片を、温度80℃、30分間の条件で乾燥を行った。
乾燥後の試験片の塗装表面を観察し、塗装不良(ワキ)の発生を、以下の評価基準に基づいて判定を行った。
○:試験片表面にワキ不良は発生しなかった。
△:試験片表面にワキ不良が1〜10個発生した。
×:試験片表面にワキ不良が11個以上発生した。
塗装評価(ワキ)の評価で準備した試験片について、ワキ以外の塗装不良の発生を、以下の基準に基づいて判定を行った。
○:試験片全体に塗装不良の発生はなく、美麗な塗装外観が得られた。
△:試験片の一部に塗装不良が発生した。
×:試験片全体にわたって塗装不良が発生し、美麗は塗装外観が得られなかった。
FANAC株式会社製の射出成形機「α−150」(型式名)を用い、表1に記載の塗装用樹脂組成物からなる試験片を射出成形した。射出成形時の樹脂温度は260℃、金型温度は50℃、射出速度は5mm/sであった。
○:ゲート近傍に剥離は発生しなかった。
△:ゲートから成形品に向かって剥離が発生した。剥離の長さはゲートから5mm以下であった。
×:ゲートから成形品に向かって剥離が発生した。剥離の長さはゲートから5mmを超えた。
フラスコ内に、ポリブタジエンゴムラテックス(平均粒子径270nm)を固形分換算で54部、スチレン−ブタジエン系共重合体ゴムラテックス(スチレン含率25%、平均粒子径550nm)を固形分換算で6部加え、イオン交換水150部、スチレン7部、アクリロニトリル3部、t−ドデシルメルカプタン0.2部を更に加えてフラスコ内温度を60℃に昇温した後、ピロリン酸ナトリウム0.2部、硫酸第一鉄7水和物0.01部、ブドウ糖0.4部をイオン交換水20部に溶解した溶液を加え、クメンハイドロパーオキサイド0.1部を更に加えて重合を開始し、温浴温度を70℃に保った。1時間重合させた後、スチレン22部、アクリロニトリル8部、t−ドデシルメルカプタン0.5部、クメンハイドロパーオキサイド0.2部を2時間かけて連続的に添加し、更に、1時間重合させて反応を完結させた。得られた共重合体ラテックスに硫酸を加えて凝固し、水洗、乾燥し、パウダー状の樹脂組成物を得た。得られた樹脂組成物のグラフト率は33%、アセトン可溶分の極限粘度[η](MEK溶液、30℃)は0.21dl/gであった。
撹拌機付き重合容器に、水250部およびパルミチン酸ナトリウム1.0部を投入し、脱酸素後、窒素気流中で撹拌しながら70℃まで加熱した。さらにナトリウムホルムアルデヒドスルホキシレート0.4部、硫酸第一鉄0.0025部、エチレンジアミン四酢酸二ナトリウム0.01部を仕込み後、α−メチルスチレン70部、アクリロニトリル25部、スチレン5部、t−ドデシルメルカプタン0.5部、クメンハイドロパーオキサイド0.2部から成る単量体混合物を、重合温度70℃で連続的に7時間かけて滴下した。滴下終了後、重合温度を75℃にし、1時間撹拌を続けて重合を終了させ、共重合体のラテックスを得た。重合転化率は99%であった。その後、得られたラテックスを塩化カルシウムを添加して凝固し、洗浄、濾過および乾燥工程を経てパウダー状の共重合体を得た。得られた共重合体のアセトン可溶分の極限粘度[η]は0.40dl/gであった。
電気化学工業株式会社製「デンカIP MX037(商品名)」(N−フェニルマレイミド−アクリロニトリル−スチレン共重合体、N−フェニルマレイミド単位含有率38.5%)
リボン型攪拌機翼、助剤連続添加装置、温度計などを装備した容積20リットルのステンレス製オートクレーブに、スチレン63質量部、アクリロニトリル質量37部、t−ドデシルメルカプタン0.5質量部、トルエン40質量部、及び、ジクミルパーオキサイド0.05質量部を仕込み、攪拌回転数100rpmで攪拌を行いながら、内温を145℃に昇温した。内温が110℃に達した時を重合開始とし、その後3.5時間の重合反応を行った。尚、内温が145℃に到達した後は、内温を145℃に保持し、攪拌回転数100rpmで攪拌を行った。上記3.5時間の重合反応の終了後、内温を100℃まで冷却し、反応混合物をオートクレーブより抜き出し、水蒸気蒸留により未反応物と溶媒を留去した。更に、40mmφベント付き押出機(シリンダー温度220℃、真空度760mmHg)を使用して揮発分を実質的に脱気させ、ペレット化した。重合終了時の重合転化率は82%であった。得られたスチレン・アクリルニトリル共重合体の極限粘度[η](メチルエチルケトン中、30℃)は0.42dl/g、重量平均分子量は80,000、アクリロニトリル単位の含有量は32質量%であった。
ウィンテックポリマー株式会社製「ジュラネックス200FP(商品名)」(PBT)
エチレン・(メタ)アクリル酸エステル・一酸化炭素共重合体(商品名「エルバロイHP−4051」、三井・デュポンポリケミカル社製)を使用した。JIS K7210に準ずるMFR(温度;200℃、荷重;19.6N)は、12g/10分である。
エチレン・(メタ)アクリル酸エステル・一酸化炭素共重合体(商品名「エルバロイ HP−771」、三井・デュポンポリケミカル社製)を使用した。JISK7210に準ずるMFR(温度;200℃、荷重;19.6N)は、100g/10分である。
エチレンビスステアリン酸アマイド(商品名「カオーワックス EB−P」、花王社製)を使用した。
3−(3’,5’−ジ−tert−ブチル−4’−ヒドロキシフェニル)−N−オクタデシルプロピオネート(商品名「アデカスタブ AO−50」、アデカ社製)を使用した。
ビス(2,6−ジ−tert−ブチル−4−メチルフェニル)ペンタエリスリトールジホスファイト(商品名「アデカスタブPEP−36」、アデカ社製)を使用した。
表1に記載の配合割合で、上記成分〔A〕〜〔D〕をヘンシェルミキサーにより混合した後、二軸押出機(日本製鋼所製、TEX44、バレル設定温度240℃)で混練し、塗装用樹脂組成物をペレット化した。得られたペレットで評価用の各試験片を成形し、前記の評価を行い、その結果を表1及び表2に示した。
実施例1の塗装用樹脂組成物を用い、1200mm×150mm、平均肉厚3mmの車両用スポイラーを射出成形し、塗装を行ったところ、塗装不良のない美麗な外観をもつ車両用スポイラーを得ることが出来た。
比較例1の塗装用樹脂組成物を用い、1200mm×150mm、平均肉厚3mmの車両用スポイラーを射出成形し、塗装を行ったところ、ワキが発生し、美麗な外観をもつ車両用スポイラーを得ることが出来なかった。
実施例1の塗装用樹脂組成物を用い、500mm×200mm、平均肉厚3mmの車両用リアガーニッシュを射出成形し、塗装を行ったところ、塗装不良のない美麗な外観をもつ車両用リアガーニッシュを得ることが出来た。
比較例1の塗装用樹脂組成物を用い、500mm×200mm、平均肉厚3mmの車両用リアガーニッシュを射出成形し、塗装を行ったところ、ワキが発生し、美麗な外観をもつ車両用リアガーニッシュを得ることが出来なかった。
比較例1は、成分〔B〕及び成分〔C〕の含有量が本発明の範囲外に少ない例であるが、塗装不良(ワキ)が生じた。
比較例2は、成分〔B〕の含有量が本発明の範囲外に少ない例であるが、塗装外観が悪かった。
比較例3は、成分〔C〕の含有量が本発明の範囲外に少ない例であるが、塗装不良(ワキ)が生じた。
比較例4は、成分〔B〕の含有量が本発明の範囲外に多い例であるが、成形品に剥離が生じた。
比較例5は、成分〔C〕の含有量が本発明の範囲外に多い例であるが、塗装外観が悪く、剥離が生じた。
2:ゲート
3:切り込み
Claims (10)
- 以下に記載のゴム強化ビニル系樹脂〔A〕84.9〜98.9質量部、ポリエステル樹脂〔B〕1〜8質量部およびエチレン・(メタ)アクリル酸エステル・一酸化炭素共重合体〔C〕0.1〜7.1質量部(ただし、〔A〕+〔B〕+〔C〕=100質量部)から成ることを特徴とする塗装用樹脂組成物。
[ゴム強化ビニル系樹脂〔A〕]
ゴム質重合体〔a〕の存在下にビニル系単量体〔b1〕を重合して得られたゴム強化共重合樹脂〔A1〕、または、ゴム質重合体〔a〕の存在下にビニル系単量体〔b1〕を重合して得られたゴム強化共重合樹脂〔A1〕とビニル系単量体〔b2〕の(共)重合体〔A2〕を含有するゴム強化ビニル系樹脂。
但し、ゴム質重合体〔a〕としてジエン系重合体を使用し、ビニル系単量体〔b1〕及びビニル系単量体〔b2〕は、以下の組み合わせの化合物を使用するが、[b1]が(1)又は(2)、かつ、[b2]が(1)又は(2)である。
(1)芳香族ビニル化合物及びシアン化ビニル化合物。
(2)芳香族ビニル化合物、シアン化ビニル化合物及びマレイミド系化合物。 - ゴム質重合体〔a〕の含有量が、ゴム強化ビニル系樹脂〔A〕100質量%に対し、5〜40質量%である請求項1に記載の塗装用樹脂組成物。
- ゴム強化ビニル系樹脂〔A〕が、α−メチルスチレンに由来する構造単位、及び/又は、マレイミド系化合物に由来する構造単位を含有し、且つ、α−メチルスチレンに由来する構造単位、及び/又は、マレイミド系化合物に由来する構造単位の合計量が、該ゴム強化ビニル系樹脂100質量%に対し、10〜50質量%である請求項1又は2に記載の塗装用樹脂組成物。
- ポリエステル樹脂〔B〕がポリブチレンテレフタレートである請求項1〜3の何れか1項に記載の塗装用樹脂組成物。
- 請求項1〜4の何れかに記載の塗装用樹脂組成物から成ることを特徴とする成形品。
- 射出成形により得られる請求項5に記載の成形品。
- 請求項1〜4の何れかに記載の塗装用樹脂組成物から成ることを特徴とする自動車外装部品。
- 射出成形により得られる請求項7に記載の自動車外装部品。
- 請求項1〜4の何れかに記載の塗装用樹脂組成物から成ることを特徴とするスポイラー。
- 射出成形により得られる請求項9に記載のスポイラー。
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