JP3926343B2 - 塩化ビニル系樹脂組成物 - Google Patents
塩化ビニル系樹脂組成物 Download PDFInfo
- Publication number
- JP3926343B2 JP3926343B2 JP2004078473A JP2004078473A JP3926343B2 JP 3926343 B2 JP3926343 B2 JP 3926343B2 JP 2004078473 A JP2004078473 A JP 2004078473A JP 2004078473 A JP2004078473 A JP 2004078473A JP 3926343 B2 JP3926343 B2 JP 3926343B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl
- mass
- copolymer
- monomer
- vinyl chloride
- 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 - Lifetime
Links
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims description 43
- 239000011342 resin composition Substances 0.000 title claims description 30
- 239000000178 monomer Substances 0.000 claims description 58
- 229920002554 vinyl polymer Polymers 0.000 claims description 32
- 229920001577 copolymer Polymers 0.000 claims description 30
- 229920000642 polymer Polymers 0.000 claims description 24
- 229920006163 vinyl copolymer Polymers 0.000 claims description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 13
- 150000003949 imides Chemical class 0.000 claims description 9
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 claims description 7
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical group O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 2
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- -1 rate Chemical class 0.000 description 8
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical group CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000012760 heat stabilizer Substances 0.000 description 4
- 238000006358 imidation reaction Methods 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 4
- 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 3
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 3
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 3
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 3
- 239000012744 reinforcing agent Substances 0.000 description 3
- 150000003440 styrenes Chemical class 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 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
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 150000008360 acrylonitriles Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011437 continuous method Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 125000005498 phthalate group Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- XXCVIFJHBFNFBO-UHFFFAOYSA-N 1-ethenoxyoctane Chemical compound CCCCCCCCOC=C XXCVIFJHBFNFBO-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- BAWHYOHVWHQWFQ-UHFFFAOYSA-N 1-naphthalen-1-ylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC2=CC=CC=C12 BAWHYOHVWHQWFQ-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical class OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 description 1
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 229940091181 aconitic acid Drugs 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- KRGNPJFAKZHQPS-UHFFFAOYSA-N chloroethene;ethene Chemical group C=C.ClC=C KRGNPJFAKZHQPS-UHFFFAOYSA-N 0.000 description 1
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000950 dibromo group Chemical group Br* 0.000 description 1
- ZTXLZPNGKWQASW-UHFFFAOYSA-L dicalcium octadecanoate Chemical compound C(CCCCCCCCCCCCCCCCC)(=O)[O-].[Ca+2].C(CCCCCCCCCCCCCCCCC)(=O)[O-].[Ca+2] ZTXLZPNGKWQASW-UHFFFAOYSA-L 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- DADSZOFTIIETSV-UHFFFAOYSA-N n,n-dichloroaniline Chemical compound ClN(Cl)C1=CC=CC=C1 DADSZOFTIIETSV-UHFFFAOYSA-N 0.000 description 1
- ILCQYORZHHFLNL-UHFFFAOYSA-N n-bromoaniline Chemical compound BrNC1=CC=CC=C1 ILCQYORZHHFLNL-UHFFFAOYSA-N 0.000 description 1
- KUDPGZONDFORKU-UHFFFAOYSA-N n-chloroaniline Chemical compound ClNC1=CC=CC=C1 KUDPGZONDFORKU-UHFFFAOYSA-N 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000036316 preload Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000045 pyrolysis gas chromatography Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明に用いられる(A)塩化ビニル系重合体は、塩化ビニル単量体単独または塩化ビニル単量体とこれと共重合可能な1種以上の単量体との混合物を重合して得られたものである。共重合可能な単量体としては、酢酸ビニルやプロピオン酸ビニル等のビニルエステル類、メチルアクリレートやブチルアクリレート等のアクリル酸エステル類、メチルメタクリレートやエチルメタクリレート等のメタクリル酸エステル類、ブチルマレートやジエチルマレート等のフマル酸エステル類、ビニルメチルエーテル、ビニルブチルエーテル及びビニルオクチルエーテル等のビニルエーテル類、アクリロニトリルやメタアクリロニトリル等のシアン化ビニル類、エチレン、プロピレン等のα−オレフィン類、スチレン、α−メチルスチレン、ビニルトルエン、t−ブチルスチレン、クロロスチレン等のスチレン類及びその置換体、塩化ビニリデンや臭化ビニル等の塩化ビニル以外のハロゲン化ビニリデンやハロゲン化ビニル類、ジアリルフタレート等のフタル酸エステル類が挙げられる。
また、(C)ビニル共重合体の樹脂組成物における配合割合は2.5〜21.0質量%である。(C)ビニル共重合体が2.5質量%未満であるか、もしくは21.0質量部を超えると(A)塩化ビニル系重合体及び(B)マレイミド系共重合体との相溶性が悪くなり、衝撃強度低下を来たす。
(1)(A)成分の塩化ビニル系重合体
・塩化ビニル樹脂 TH1000(平均重合度1000)大洋塩ビ株式会社社製
・塩化ビニル−エチレン共重合体 TE650(平均重合度650)大洋塩ビ(株)社製
・塩化ビニル樹脂 TH2000(平均重合度2000)大洋塩ビ(株)社製
(2)(B)成分のマレイミド系共重合体
後述の参考例1に従い得た(b−1〜6)を使用した。
(3)(C)成分のビニル共重合体
後述の参考例2に従い得た(c−1〜5)を使用した。
(4)熱安定剤
・ハイドロタルサイト 日産化学(株)社製
・ステアリン酸カルシウム カルシウムステアレート 日本油脂(株)社製
・ステアリン酸亜鉛 ジンクステアレートGP 日本油脂(株)社製
・アデカスタブ1500(4,4‘−イソプロピリデン−ジフェノールアルキル(C12〜C15)ホスファイト)旭電化工業(株)社製
(5)滑剤
・特殊脂肪酸エステル リケスターEW−100(アジピン酸ペンタエリスリトールポリマーのステアレート) 理研ビタミン(株)社製
・ポリエチレンワックス Hiwax400 三井化学(株)社製
(6)酸化防止剤
・イルガノックス1010(テトラキス−[メチレン−3−(3‘,5’−ジ−t−ブチル−4‘−ヒドロキシフェニル)プロピオネート]メタン) チバスペシャリティケミカル社製
(B)マレイミド系共重合体の製造
攪拌機付きオートクレーブにスチレン10.0kg、メチルエチルケトン15.0kg、α−メチルスチレンダイマー21gを仕込み、系内を窒素ガスで置換した後温度を80℃に昇温し、無水マレイン酸を6.2kgとベンゾイルパーオキサイド40gをメチルエチルケトン9.0kgに溶解した溶液を8時間で連続的に添加した。添加後、更に3時間温度を80℃に保った。ここで得られた共重合溶液にアニリン5.8kg、トリエチルアミン0.1kgを加え温度140℃で7時間反応させた。反応液をベント付き二軸押出機に供給し、脱揮してマレイミド系共重合体(b−1)を得た。他のマレイミド系共重合体(b−2〜6)も仕込み組成を表1のように変えた他はほぼ同様の条件で作成した。最終重合体組成と重量平均分子量も表1に示す。
(C)ビニル共重合体の製造
攪拌機付きオートクレーブに純水50kg、過硫酸カリウム83g、第三リン酸カルシウム400g、t−ドデシルメルカプタン400g、スチレン49.6kg、アクリロニトリル16kg及びベンゾイルパーオキサイド105gを仕込み、系内を窒素ガスで置換した後温度を100℃に保ち、その後スチレン14.4kgを温度100℃で2時間、温度103℃で3時間の計5時間をかけて連続添加した。添加終了後、110℃で1時間、120℃で1時間昇温して重合を完了させ、冷却後重合液に塩酸を加え中和、脱水、乾燥してビニル共重合体(c−1)のビーズを得た。他のビニル共重合体(c−2〜5)も仕込み組成を表2のように変えた他はほぼ同様の条件で作成した。最終重合体組成と重量平均分子量も表2に示す。
上記参考例1及び2における共重合体の最終組成はスチレン成分及びアクリロニトリル成分は熱分解ガスクロマトグラフィーを用いて測定した。また、不飽和ジカルボン酸イミド誘導体成分はC13NMR分析を用いて測定した。
上記参考例1及び2における共重合体の重量平均分子量はGPC(ゲルパーミエーションクロマトグラフィー)を用いて測定した。Polymer Labolatory社のPL gel MIXED−Bのカラム、装置はSYSTEM−21(Shodex)を用い、移動相:THF、流量:1.0ml/分、検出器:RI、標準ポリマー:ポリスチレンの条件下で行った。
(B)成分と(C)成分の溶融混練
上記参考例1、2にて得られたマレイミド系共重合体(b−1〜6)及びビニル共重合体(c−1〜5)を表3に示す配合によりヘンシェルミキサー(三井鉱山(株)社製、20リットル)にて混合した後、35mmφ脱揮装置付き同方向回転二軸押出機(東芝機械(株)社製、TEM35B)を用いて、シリンダー温度280℃にて押出しペレット化した。得られたペレットを遠心式回転粉砕機(三井鉱山(株)社製、ウルトラセントリミルUCM150)にて平均粒子径100〜200μm(d50)に粉砕処理して、(B)成分と(C)成分の溶融混練樹脂(d−1〜50)を得た。
表4〜表10に示す配合によりヘンシェルミキサー(同上)にて混合した後、6インチロール混練機(東京実業(株)社製、TJ−TP6×15UD)を用いて、前ロール180〜200℃、後ロール170〜190℃にてシートサンプルを得た。このシートサンプルを複数枚重ねて40トンプレス成形機(東京実業(株)社製、TJ−P4030SA)を用いて、温度185℃、予圧5MPa×5分、本圧20MPa×5分にて4mm厚の樹脂組成物板サンプルを得た。尚、(A)塩化ビニル系重合体、(B)マレイミド系共重合体、(C)ビニル共重合体の3成分を一度に溶融混練した例、更には(A)成分と(B)成分及び(A)成分と(C)成分を溶融混練したの後、残りの成分を配合して上述の方法により樹脂組成物を作成した例について、表11の実施例37〜42に示す。
(2) 耐熱性(荷重たわみ温度):上記板サンプルより試験片を切り出し、JIS K 7191に準拠し、荷重1.8MPaでの荷重たわみ温度を測定した。
(3)耐熱性(ビカット軟化温度):上記板サンプルより試験片を切り出し、JIS K 7206に準拠し、荷重50N、昇温温度50℃/hrでのビカット軟化温度を測定した。
(4)引張特性:上記板サンプルより試験片を切り出し、JIS K 7161、7162に準拠し、相対湿度50%、雰囲気温度23℃での引張降伏応力、引張破壊応力、引張破壊呼び歪みを測定した。
(5)流動性:ペレット形状の樹脂サンプルをフローテスター(島津製作所(株)社製、CFT−500)にて温度180℃、荷重10MPa、ノズル径1mm、ランド長10mmの条件にて測定した。
(6)色相:上記板サンプルより試験片を切り出し(9cm×5cm)、この試験片を160℃、3時間ギアオーブン内に放置した前後の黄色度YIを色差計(日本電色工業(株)社製、Σ−90)で測定した。
Claims (3)
- 平均重合度が700〜1700である(A)塩化ビニル系重合体70〜95質量%、(B)芳香族ビニル単量体15〜70質量%、不飽和ジカルボン酸イミド誘導体25〜65質量%、不飽和ジカルボン酸無水物単量体0〜25質量%からなり、かつ重量平均分子量が60000〜140000であるマレイミド系共重合体1.5〜15.0質量%、(C)芳香族ビニル単量体40〜85質量%、シアン化ビニル単量体15〜40質量%及びこれらと共重合可能なビニル単量体0〜40質量%からなり、重量平均分子量が50000〜110000であるビニル共重合体2.5〜21.0質量%を配合してなる塩化ビニル系樹脂組成物。(ただし、(A)塩化ビニル系重合体と(B)マレイミド系共重合体と(C)ビニル共重合体の合計は100質量%とする)
- (B)マレイミド系共重合体の芳香族ビニル単量体がスチレン、不飽和ジカルボン酸イミド誘導体がN−フェニルマレイミド、不飽和ジカルボン酸無水物単量体が無水マレイン酸である請求項1記載の塩化ビニル系樹脂組成物。
- (C)ビニル共重合体の芳香族ビニル単量体がスチレン、シアン化ビニル単量体がアクリロニトリルである請求項1記載の塩化ビニル系樹脂組成物。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004078473A JP3926343B2 (ja) | 2004-03-18 | 2004-03-18 | 塩化ビニル系樹脂組成物 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004078473A JP3926343B2 (ja) | 2004-03-18 | 2004-03-18 | 塩化ビニル系樹脂組成物 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2005263976A JP2005263976A (ja) | 2005-09-29 |
JP3926343B2 true JP3926343B2 (ja) | 2007-06-06 |
Family
ID=35088852
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2004078473A Expired - Lifetime JP3926343B2 (ja) | 2004-03-18 | 2004-03-18 | 塩化ビニル系樹脂組成物 |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3926343B2 (ja) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102131864B (zh) * | 2008-06-23 | 2013-08-14 | 可乐丽股份有限公司 | 聚氯乙烯树脂组合物及其制造方法 |
WO2022039098A1 (ja) * | 2020-08-19 | 2022-02-24 | デンカ株式会社 | マレイミド系共重合体、及びマレイミド系共重合体と塩素含有ポリマーを含む塩素含有ポリマー系樹脂組成物 |
-
2004
- 2004-03-18 JP JP2004078473A patent/JP3926343B2/ja not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JP2005263976A (ja) | 2005-09-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JPWO2016186133A1 (ja) | 耐熱性樹脂組成物及びその製造方法 | |
JPS6023438A (ja) | 熱可塑性樹脂組成物 | |
WO2022039098A1 (ja) | マレイミド系共重合体、及びマレイミド系共重合体と塩素含有ポリマーを含む塩素含有ポリマー系樹脂組成物 | |
JP2006265373A (ja) | マレイミド系共重合体及び塩化ビニル系重合体を有する塩化ビニル系樹脂組成物 | |
KR20150074099A (ko) | 방향족 비닐-시안화비닐계 수지 내열성 향상용의 공중합체 | |
CN115427468A (zh) | 马来酰亚胺类共聚物、以及含有马来酰亚胺类共聚物和含氯聚合物的含氯聚合物类树脂组合物 | |
JPWO2016186142A1 (ja) | ポリマーブレンド相容化剤用共重合体および樹脂組成物 | |
AU596724B2 (en) | Heat and impact resistant resin composition | |
JP7245334B2 (ja) | マレイミド系共重合体、その製造方法及びそれを用いた樹脂組成物 | |
US20230250270A1 (en) | Resin composition and molded resin articles | |
JP3926343B2 (ja) | 塩化ビニル系樹脂組成物 | |
US20230183480A1 (en) | Maleimide-based copolymer, maleimide-based copolymer composition, resin composition, and injection molded body | |
JP6266984B2 (ja) | Pc/abs系樹脂の伸び及び耐衝撃性向上用の共重合体、この共重合体とpc/abs系樹脂と樹脂組成物 | |
WO2020217687A1 (ja) | 熱可塑性樹脂組成物及びその成形品 | |
JP2009019083A (ja) | 熱可塑性樹脂組成物 | |
WO2023191064A1 (ja) | 塩素含有ポリマー用耐熱付与剤、樹脂組成物、ならびに当該樹脂組成物から成形される成形体 | |
JP2003041080A (ja) | マレイミド系耐熱付与材 | |
WO2022234816A1 (ja) | マレイミド系共重合体と塩素含有ポリマーを含む樹脂組成物、ならびに当該樹脂組成物から成形される雨どい及び雨どい部品、建具用形材、ならびにパイプ及び継手 | |
JP2009007528A (ja) | 熱可塑性樹脂組成物 | |
JPS61148267A (ja) | 耐熱性耐衝撃性樹脂組成物 | |
JP2009132776A (ja) | 熱可塑性樹脂組成物 | |
JP2009132778A (ja) | 熱可塑性樹脂組成物 | |
JP2016138197A (ja) | ブロー成形用スチレン系樹脂組成物及びそのブロー成形品 | |
CN117460788A (zh) | 含有马来酰亚胺系共聚物和含氯聚合物的树脂组合物、以及由该树脂组合物成型的檐槽和檐槽部件、门窗扇用型材以及管道和接头 | |
US3600461A (en) | Vinyl halide polymeric blends |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20060731 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20060829 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20061027 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20070227 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20070227 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 3926343 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110309 Year of fee payment: 4 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110309 Year of fee payment: 4 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120309 Year of fee payment: 5 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130309 Year of fee payment: 6 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130309 Year of fee payment: 6 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140309 Year of fee payment: 7 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
EXPY | Cancellation because of completion of term |