JP2005281570A - Vinyl chloride resin composition for injection-molded article - Google Patents
Vinyl chloride resin composition for injection-molded article Download PDFInfo
- Publication number
- JP2005281570A JP2005281570A JP2004099121A JP2004099121A JP2005281570A JP 2005281570 A JP2005281570 A JP 2005281570A JP 2004099121 A JP2004099121 A JP 2004099121A JP 2004099121 A JP2004099121 A JP 2004099121A JP 2005281570 A JP2005281570 A JP 2005281570A
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- JP
- Japan
- Prior art keywords
- vinyl chloride
- chloride resin
- macromonomer
- injection
- resin
- 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.)
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- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 239000011342 resin composition Substances 0.000 title claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 87
- 229920005989 resin Polymers 0.000 claims abstract description 74
- 239000011347 resin Substances 0.000 claims abstract description 74
- 229920000642 polymer Polymers 0.000 claims abstract description 43
- 238000002347 injection Methods 0.000 claims abstract description 23
- 239000007924 injection Substances 0.000 claims abstract description 23
- 229920006026 co-polymeric resin Polymers 0.000 claims description 43
- 239000000203 mixture Substances 0.000 claims description 33
- 229920002554 vinyl polymer Polymers 0.000 abstract description 14
- 238000000465 moulding Methods 0.000 abstract description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 12
- 239000000243 solution Substances 0.000 abstract description 5
- 230000006866 deterioration Effects 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 62
- 238000006116 polymerization reaction Methods 0.000 description 40
- 238000004519 manufacturing process Methods 0.000 description 36
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 27
- 238000002156 mixing Methods 0.000 description 23
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 20
- 238000010526 radical polymerization reaction Methods 0.000 description 18
- 239000004800 polyvinyl chloride Substances 0.000 description 16
- 229920000915 polyvinyl chloride Polymers 0.000 description 16
- -1 vinylsilyl group Chemical group 0.000 description 15
- 125000000524 functional group Chemical group 0.000 description 14
- 239000002002 slurry Substances 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 12
- 229920000578 graft copolymer Polymers 0.000 description 12
- 239000000314 lubricant Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000654 additive Substances 0.000 description 9
- 230000001771 impaired effect Effects 0.000 description 9
- 239000004014 plasticizer Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000001746 injection moulding Methods 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000006057 Non-nutritive feed additive Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 239000004816 latex Substances 0.000 description 6
- 229920000126 latex Polymers 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000004611 light stabiliser Substances 0.000 description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 4
- 239000012986 chain transfer agent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- CRJIYMRJTJWVLU-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-yl 3-(5,5-dimethylhexyl)dioxirane-3-carboxylate Chemical compound CC(C)(C)CCCCC1(C(=O)OC(C)(C)CC(C)(C)C)OO1 CRJIYMRJTJWVLU-UHFFFAOYSA-N 0.000 description 3
- 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 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000004709 Chlorinated polyethylene Substances 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000012760 heat stabilizer Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229940049920 malate Drugs 0.000 description 3
- 229920002689 polyvinyl acetate Polymers 0.000 description 3
- 239000011118 polyvinyl acetate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010558 suspension polymerization method Methods 0.000 description 3
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical group CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 2
- 239000003623 enhancer Substances 0.000 description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- OWXJKYNZGFSVRC-IHWYPQMZSA-N (z)-1-chloroprop-1-ene Chemical group C\C=C/Cl OWXJKYNZGFSVRC-IHWYPQMZSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- GGSRTHRSSCWGGK-UHFFFAOYSA-L 2,2-dibutyl-5-hydroxy-1,3,2-dioxastannepane-4,7-dione Chemical compound CCCC[Sn]1(CCCC)OC(=O)CC(O)C(=O)O1 GGSRTHRSSCWGGK-UHFFFAOYSA-L 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- USICVVZOKTZACS-UHFFFAOYSA-N 3-butylpyrrole-2,5-dione Chemical compound CCCCC1=CC(=O)NC1=O USICVVZOKTZACS-UHFFFAOYSA-N 0.000 description 1
- UJTRCPVECIHPBG-UHFFFAOYSA-N 3-cyclohexylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C2CCCCC2)=C1 UJTRCPVECIHPBG-UHFFFAOYSA-N 0.000 description 1
- UIZDKHDPZRCOBN-UHFFFAOYSA-N 3-dodecylpyrrole-2,5-dione Chemical compound CCCCCCCCCCCCC1=CC(=O)NC1=O UIZDKHDPZRCOBN-UHFFFAOYSA-N 0.000 description 1
- MXVZVCCKUVRGQC-UHFFFAOYSA-N 3-hexylpyrrole-2,5-dione Chemical compound CCCCCCC1=CC(=O)NC1=O MXVZVCCKUVRGQC-UHFFFAOYSA-N 0.000 description 1
- ZLPORNPZJNRGCO-UHFFFAOYSA-N 3-methylpyrrole-2,5-dione Chemical compound CC1=CC(=O)NC1=O ZLPORNPZJNRGCO-UHFFFAOYSA-N 0.000 description 1
- BLHDYAXSQWGYSM-UHFFFAOYSA-N 3-octadecylpyrrole-2,5-dione Chemical compound CCCCCCCCCCCCCCCCCCC1=CC(=O)NC1=O BLHDYAXSQWGYSM-UHFFFAOYSA-N 0.000 description 1
- VOYQCFMGTRPFKT-UHFFFAOYSA-N 3-octylpyrrole-2,5-dione Chemical compound CCCCCCCCC1=CC(=O)NC1=O VOYQCFMGTRPFKT-UHFFFAOYSA-N 0.000 description 1
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 description 1
- MDXKEHHAIMNCSW-UHFFFAOYSA-N 3-propylpyrrole-2,5-dione Chemical compound CCCC1=CC(=O)NC1=O MDXKEHHAIMNCSW-UHFFFAOYSA-N 0.000 description 1
- IZSHZLKNFQAAKX-UHFFFAOYSA-N 5-cyclopenta-2,4-dien-1-ylcyclopenta-1,3-diene Chemical group C1=CC=CC1C1C=CC=C1 IZSHZLKNFQAAKX-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PXFRBTZJEFMJBP-UHFFFAOYSA-N FC(C(C(C(C(F)(F)F)(C(=C(F)F)F)F)(F)F)(F)F)(F)F Chemical group FC(C(C(C(C(F)(F)F)(C(=C(F)F)F)F)(F)F)(F)F)(F)F PXFRBTZJEFMJBP-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-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
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- FUIBVSHMELLXFV-UHFFFAOYSA-K S[Sn](CCCC)CCCC.S[Sn](CCCCCCCC)CCCCCCCC.S[Sn](CCCC)CCCC.C[Sn]C Chemical compound S[Sn](CCCC)CCCC.S[Sn](CCCCCCCC)CCCCCCCC.S[Sn](CCCC)CCCC.C[Sn]C FUIBVSHMELLXFV-UHFFFAOYSA-K 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 1
- PMSNFNRNIGPRQJ-UHFFFAOYSA-N [Cr](=O)(=O)([O-])[O-].[Mo+4].[Cr](=O)(=O)([O-])[O-] Chemical class [Cr](=O)(=O)([O-])[O-].[Mo+4].[Cr](=O)(=O)([O-])[O-] PMSNFNRNIGPRQJ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- MGFRKBRDZIMZGO-UHFFFAOYSA-N barium cadmium Chemical compound [Cd].[Ba] MGFRKBRDZIMZGO-UHFFFAOYSA-N 0.000 description 1
- SHLNMHIRQGRGOL-UHFFFAOYSA-N barium zinc Chemical compound [Zn].[Ba] SHLNMHIRQGRGOL-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- BPOZNMOEPOHHSC-UHFFFAOYSA-N butyl prop-2-enoate;prop-2-enoic acid Chemical group OC(=O)C=C.CCCCOC(=O)C=C BPOZNMOEPOHHSC-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 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
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- WGXGKXTZIQFQFO-CMDGGOBGSA-N ethenyl (e)-3-phenylprop-2-enoate Chemical compound C=COC(=O)\C=C\C1=CC=CC=C1 WGXGKXTZIQFQFO-CMDGGOBGSA-N 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 description 1
- UMKARVFXJJITLN-UHFFFAOYSA-N lead;phosphorous acid Chemical compound [Pb].OP(O)O UMKARVFXJJITLN-UHFFFAOYSA-N 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate 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
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- ACEONLNNWKIPTM-UHFFFAOYSA-N methyl 2-bromopropanoate Chemical compound COC(=O)C(C)Br ACEONLNNWKIPTM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-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
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- IWAAYHVSKLLSAM-UHFFFAOYSA-N phosphoric acid;triphenyl phosphate Chemical compound OP(O)(O)=O.C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 IWAAYHVSKLLSAM-UHFFFAOYSA-N 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
- JQCXWCOOWVGKMT-UHFFFAOYSA-N phthalic acid diheptyl ester Natural products CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical group CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Landscapes
- Injection Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
本発明は、射出成形品用塩化ビニル系樹脂組成物に関する。さらに詳しくは、射出成形品用途に通常使用される範囲の平均重合度または平均分子量を有する塩化ビニル系樹脂を用いて射出成形する際において、強度物性の低下がなく成形加工時の流動性に優れた射出成形品を得るために有用な塩化ビニル系樹脂組成物に関する。 The present invention relates to a vinyl chloride resin composition for injection molded articles. More specifically, when injection molding is performed using a vinyl chloride resin having an average degree of polymerization or average molecular weight in the range normally used for injection molded product applications, there is no decrease in strength properties and excellent fluidity during molding. The present invention relates to a vinyl chloride resin composition useful for obtaining an injection molded product.
塩化ビニル樹脂は種々の成形品に汎用されているが、特に継手、バルブ製品等の射出成形品用途においては、充分に満足し得る程度の流動性、強度物性が発現しにくいという欠点がある。この塩化ビニル樹脂の成形加工時の流動性や二次加工性を向上させることを目的として、例えばメタクリル酸メチルを主成分とする共重合体を加工性改良剤として配合する方法（特許文献１）が提案されている。しかしこの方法では、カレンダー成形加工時には流動性が良好でエアーマークに優れた成形品を得ることができるものの、射出成形品用途に対してはその効果は不明瞭であった。また、流動性改善のために可塑剤を添加する方法もよく知られているが、この方法では強度物性の低下を招く。さらに、強度物性の一つとしての耐衝撃性向上のために、例えば塩化ビニル系樹脂にメタクリル酸メチル−ブタジエン−スチレン共重合体（以下ＭＢＳ樹脂と略す）または塩素化ポリエチレン（以下ＣＰＥと略す）を耐衝撃強化剤として添加する方法（特許文献２）が開示されている。しかしながら塩化ビニル樹脂にこれら強化剤を配合する場合、成形加工時の流動性は改善されず、製造条件面での問題も生じていた。
本発明は、多種多量の添加剤を配合することなく、成形加工時の流動性が良好で且つ強度物性の低下がない、射出成形品用塩化ビニル系樹脂組成物を提供することを目的とする。 It is an object of the present invention to provide a vinyl chloride resin composition for injection molded articles, which does not contain a large amount of various additives, has good fluidity during molding and does not deteriorate strength properties. .
本発明者らは鋭意研究の結果、塩化ビニル系モノマーと二重結合を含有するエチレン性不飽和モノマーからなる重合体を主鎖に有するマクロモノマーとを共重合してなる塩化ビニル系共重合樹脂を塩化ビニル系樹脂に添加することにより、上記課題を達成できることを見出し、本発明を完成した。
すなわち本発明は、
（１）塩化ビニル系モノマーと、二重結合を含有するエチレン性不飽和モノマーからなる重合体を主鎖に有するマクロモノマーとを共重合してなる塩化ビニル系共重合樹脂を、塩化ビニル系樹脂に添加することを特徴とする、射出成形品用塩化ビニル系樹脂組成物（請求項１）、
（２）塩化ビニル系樹脂１００重量部を基準として、塩化ビニル系共重合樹脂中の二重結合を含有するエチレン性不飽和モノマーからなる重合体を主鎖に有するマクロモノマー成分の含量が、０．１重量部以上１重量部以下であることを特徴とする、請求項１に記載の射出成形品用塩化ビニル系樹脂組成物（請求項２）、
（３）塩化ビニル系共重合樹脂全体に占める、二重結合を含有するエチレン性不飽和モノマーからなる重合体を主鎖に有するマクロモノマー成分の分率が、５重量％以上５０重量％以下であることを特徴とする、請求項１〜２のいずれかに記載の射出成形品用塩化ビニル系樹脂組成物（請求項３）、
に関する。
As a result of intensive studies, the present inventors have found that a vinyl chloride copolymer resin obtained by copolymerizing a vinyl chloride monomer and a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain. It was found that the above-mentioned problems can be achieved by adding to a vinyl chloride resin, and the present invention was completed.
That is, the present invention
(1) A vinyl chloride copolymer resin obtained by copolymerizing a vinyl chloride monomer and a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain. A vinyl chloride resin composition for injection-molded articles (claim 1),
(2) Based on 100 parts by weight of the vinyl chloride resin, the content of the macromonomer component having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the vinyl chloride copolymer resin in the main chain is 0. The vinyl chloride resin composition for injection-molded articles according to claim 1, wherein the composition is 1 part by weight or more and 1 part by weight or less (Claim 2).
(3) The fraction of the macromonomer component having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain of the vinyl chloride copolymer resin is 5% by weight or more and 50% by weight or less. A vinyl chloride resin composition for injection-molded articles according to any one of claims 1 to 2, wherein the vinyl chloride-based resin composition (claim 3),
About.
本発明の射出成形品用塩化ビニル系樹脂組成物によれば、成形加工時の流動性が良好で且つ強度物性の低下がない、継手やバルブ製品等の射出塩化ビニル系樹脂成形品が得られる。 According to the vinyl chloride resin composition for injection molded articles of the present invention, injection vinyl chloride resin molded articles such as joints and valve products can be obtained that have good fluidity during molding and have no deterioration in strength properties. .
本発明の射出成形品用塩化ビニル系樹脂組成物は、塩化ビニル系モノマーと二重結合を含有するエチレン性不飽和モノマーからなる重合体を主鎖に有するマクロモノマーとを共重合してなる塩化ビニル系共重合樹脂を、塩化ビニル系樹脂に添加することを特徴とする塩化ビニル系樹脂組成物であり、特に射出成形用に好適な塩化ビニル系樹脂組成物である。本発明における、塩化ビニル系樹脂を用いる射出成形加工法とは、樹脂組成物等をスクリューを用いて加熱シリンダー内へ送り込み、シリンダーの熱とスクリューによる剪断によって該組成物等を加熱溶融して流動化させ、該溶融樹脂組成物等を金型内に射出注入し、冷却固化して成形品を得る成形加工法のことであり、用いる塩化ビニル系樹脂としては、ＪＩＳ Ｋ ７３６７−２に従って測定したＫ値が５５〜６１の範囲の平均重合度を有することが好適である。また平均粒径としては特に限定されないが、通常５０〜３００μｍの範囲である。 The vinyl chloride resin composition for injection-molded articles of the present invention is obtained by copolymerizing a vinyl chloride monomer and a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain. It is a vinyl chloride resin composition characterized by adding a vinyl copolymer resin to a vinyl chloride resin, and is a vinyl chloride resin composition particularly suitable for injection molding. In the present invention, the injection molding method using a vinyl chloride resin is a method in which a resin composition or the like is fed into a heating cylinder using a screw, and the composition or the like is heated and melted by the heat of the cylinder and shearing by the screw to flow. The molten resin composition is injected into a mold, and cooled and solidified to obtain a molded product. The vinyl chloride resin used was measured according to JIS K 7367-2. It is preferred that the K value has an average degree of polymerization in the range of 55-61. The average particle size is not particularly limited, but is usually in the range of 50 to 300 μm.
ここで、「塩化ビニル系共重合樹脂を塩化ビニル系樹脂に添加する」とは、両樹脂を各々重合したのち混ぜ合わせることを指し、その方法としては、本発明の効果を奏する範囲であれば特に制約はなく、重合後のラテックス状および／またはスラリー状のものを混ぜ合わせる方法、ラテックスおよび／またはスラリーを乾燥して得られた粉粒体を混ぜ合わせる方法、ラテックス状またはスラリー状のものと粉粒体とを混ぜ合わせる方法、等が挙げられる。 Here, "adding a vinyl chloride copolymer resin to a vinyl chloride resin" refers to mixing both resins after polymerization, and the method thereof is within the range where the effects of the present invention are exhibited. There is no particular limitation, a method of mixing a latex and / or slurry after polymerization, a method of mixing latex and / or powder obtained by drying the slurry, a latex or slurry The method of mixing a granular material, etc. are mentioned.
本発明で使用される塩化ビニル系共重合樹脂を構成する塩化ビニル系モノマーとしては特に限定はなく、例えば塩化ビニルモノマー、塩化ビニリデンモノマー、酢酸ビニルモノマーまたはこれらの混合物、または、この他にこれらと共重合可能で、好ましくは重合後の重合体主鎖に反応性官能基を有しないモノマー、例えばエチレン、プロピレンなどのα−オレフィン類から選ばれる１種または２種以上の混合物を使用しても良い。２種以上の混合物を使用する場合は、塩化ビニル系モノマー全体に占める塩化ビニルモノマーの含有率を５０重量％以上、特に７０重量％以上とすることが好ましい。中でも得られる共重合樹脂の物性等から、塩化ビニルモノマーあるいは塩化ビニリデンモノマーのいずれか１種のみを使用することが好ましく、塩化ビニルモノマーを使用することがさらに好ましい。 The vinyl chloride monomer constituting the vinyl chloride copolymer resin used in the present invention is not particularly limited. For example, vinyl chloride monomer, vinylidene chloride monomer, vinyl acetate monomer or a mixture thereof, or in addition to these, A monomer that is copolymerizable and preferably has no reactive functional group in the polymer main chain after polymerization, for example, one or a mixture of two or more selected from α-olefins such as ethylene and propylene may be used. good. When using 2 or more types of mixtures, it is preferable that the content rate of the vinyl chloride monomer which occupies for the whole vinyl chloride monomer is 50 weight% or more, especially 70 weight% or more. Among these, from the physical properties of the copolymer resin obtained, it is preferable to use only one of vinyl chloride monomer or vinylidene chloride monomer, and it is more preferable to use vinyl chloride monomer.
一般にマクロモノマーとは、重合体の末端に反応性の官能基を有するオリゴマー分子である。本発明で使用される二重結合を含有するエチレン性不飽和モノマーからなる重合体を主鎖に有するマクロモノマーは、反応性官能基として、アリル基、ビニルシリル基、ビニルエーテル基、ジシクロペンタジエニル基、下記一般式（１）から選ばれる重合性の炭素−炭素二重結合を有する基を、少なくとも１分子あたり１個、分子末端に有する、ラジカル重合によって製造されたものである。
特に、塩化ビニル系モノマーとの反応性が良好なことから、重合性の炭素−炭素二重結合を有する基が、下記一般式（１）：
−ＯＣ（Ｏ）Ｃ（Ｒ）＝ＣＨ2 （１）
で表される基が好ましい。
In general, a macromonomer is an oligomer molecule having a reactive functional group at the end of a polymer. The macromonomer having, in the main chain, a polymer composed of an ethylenically unsaturated monomer containing a double bond used in the present invention is an allyl group, a vinylsilyl group, a vinyl ether group, dicyclopentadienyl as a reactive functional group. It is produced by radical polymerization having at least one group having a polymerizable carbon-carbon double bond selected from the following general formula (1) at the molecular end.
In particular, since the reactivity with the vinyl chloride monomer is good, the group having a polymerizable carbon-carbon double bond is represented by the following general formula (1):
—OC (O) C (R) ═CH 2 (1)
The group represented by these is preferable.
式中、Ｒの具体例としては特に限定されず、例えば、−Ｈ、−ＣＨ3、−ＣＨ2ＣＨ3、−（ＣＨ2）nＣＨ3（ｎは２〜１９の整数を表す）、−Ｃ6Ｈ5、−ＣＨ2ＯＨ、−ＣＮの中から選ばれる基が好ましく、さらに好ましくは−Ｈ、−ＣＨ3である。 In the formula, specific examples of R are not particularly limited. For example, —H, —CH 3 , —CH 2 CH 3 , — (CH 2 ) n CH 3 (n represents an integer of 2 to 19), — A group selected from C 6 H 5 , —CH 2 OH and —CN is preferred, and —H and —CH 3 are more preferred.
本発明で使用されるマクロモノマーの主鎖である、二重結合を含有するエチレン性不飽和モノマーからなる重合体は、ラジカル重合によって製造される。ラジカル重合法は、重合開始剤としてアゾ系化合物、過酸化物などを使用して、特定の官能基を有するモノマーとビニル系モノマーとを単に共重合させる「一般的なラジカル重合法」と、末端などの制御された位置に特定の官能基を導入することが可能な「制御ラジカル重合法」に分類できる。 A polymer composed of an ethylenically unsaturated monomer containing a double bond, which is the main chain of the macromonomer used in the present invention, is produced by radical polymerization. The radical polymerization method uses “a general radical polymerization method” in which a monomer having a specific functional group and a vinyl monomer are simply copolymerized using an azo compound or a peroxide as a polymerization initiator, It is possible to classify into a “controlled radical polymerization method” in which a specific functional group can be introduced at a controlled position.
「一般的なラジカル重合法」は、特定の官能基を有するモノマーは確率的にしか重合体中に導入されないので、官能化率の高い重合体を得ようとした場合には、このモノマーをかなり大量に使用する必要がある。またフリーラジカル重合であるため、分子量分布が広く、粘度の低い重合体は得にくい。 In the “general radical polymerization method”, a monomer having a specific functional group is introduced into the polymer only in a probabilistic manner. Must be used in large quantities. Moreover, since it is free radical polymerization, it is difficult to obtain a polymer having a wide molecular weight distribution and a low viscosity.
「制御ラジカル重合法」は、さらに、特定の官能基を有する連鎖移動剤を使用して重合を行うことにより末端に官能基を有するビニル系重合体が得られる「連鎖移動剤法」と、重合生長末端が停止反応などを起こさずに生長することによりほぼ設計どおりの分子量の重合体が得られる「リビングラジカル重合法」とに分類することができる。 “Controlled radical polymerization method” further includes a “chain transfer agent method” in which a vinyl polymer having a functional group at a terminal is obtained by polymerization using a chain transfer agent having a specific functional group, It can be classified as a “living radical polymerization method” in which a polymer having a molecular weight almost as designed can be obtained by growing a growth terminal without causing a termination reaction or the like.
「連鎖移動剤法」は、官能化率の高い重合体を得ることが可能であるが、開始剤に対して特定の官能基を有する連鎖移動剤を必要とする。また上記の「一般的なラジカル重合法」と同様、フリーラジカル重合であるため分子量分布が広く、粘度の低い重合体は得にくい。 The “chain transfer agent method” can obtain a polymer having a high functionalization rate, but requires a chain transfer agent having a specific functional group with respect to the initiator. Further, like the above-mentioned “general radical polymerization method”, since it is free radical polymerization, it is difficult to obtain a polymer having a wide molecular weight distribution and a low viscosity.
これらの重合法とは異なり、「リビングラジカル重合法」は、本件出願人自身の発明に係る国際公開ＷＯ９９／６５９６３号公報に記載されるように、重合速度が大きく、ラジカル同士のカップリングなどによる停止反応が起こりやすいため制御の難しいとされるラジカル重合でありながら、停止反応が起こりにくく、分子量分布の狭い、例えば、重量平均分子量Ｍｗと数平均分子量Ｍｎの比（Ｍｗ／Ｍｎ）が１．１〜１．５程度の重合体が得られるとともに、モノマーと開始剤の仕込み比によって分子量は自由にコントロールすることができる。 Unlike these polymerization methods, the “living radical polymerization method” has a high polymerization rate due to coupling between radicals and the like as described in International Publication WO99 / 65963 relating to the applicant's own invention. Although radical polymerization is considered to be difficult to control because it tends to cause a termination reaction, the termination reaction is difficult to occur and the molecular weight distribution is narrow. For example, the ratio of the weight average molecular weight Mw to the number average molecular weight Mn (Mw / Mn) While a polymer of about 1 to 1.5 is obtained, the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.
従って「リビングラジカル重合法」は、分子量分布が狭く、粘度が低い重合体を得ることができる上に、特定の官能基を有するモノマーを重合体のほぼ任意の位置に導入することができるため、本発明において、上記の如き特定の官能基を有するビニル系重合体の製造方法としてはより好ましい重合法である。 Accordingly, the “living radical polymerization method” can obtain a polymer having a narrow molecular weight distribution and a low viscosity, and a monomer having a specific functional group can be introduced at almost any position of the polymer. In the present invention, the method for producing a vinyl polymer having a specific functional group as described above is a more preferable polymerization method.
「リビングラジカル重合法」の中でも、有機ハロゲン化物あるいはハロゲン化スルホニル化合物等を開始剤、遷移金属錯体を触媒としてビニル系モノマーを重合する「原子移動ラジカル重合法」（Ａｔｏｍ Ｔｒａｎｓｆｅｒ Ｒａｄｉｃａｌ Ｐｏｌｙｍｅｒｉｚａｔｉｏｎ：ＡＴＲＰ）は、上記の「リビングラジカル重合法」の特徴に加えて、官能基変換反応に比較的有利なハロゲン等を末端に有し、開始剤や触媒の設計の自由度が大きいことから、特定の官能基を有するビニル系重合体の製造方法としてはさらに好ましい。この原子移動ラジカル重合法としては例えばＭａｔｙｊａｓｚｅｗｓｋｉら、ジャーナル・オブ・アメリカン・ケミカルソサエティー（Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．）１９９５年、１１７巻、５６１４頁等が挙げられる。 Among “Living Radical Polymerization Methods”, “Atom Transfer Radical Polymerization (ATRP)” is a method in which vinyl halide monomers are polymerized using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst. In addition to the above-mentioned characteristics of the “living radical polymerization method”, it has a halogen or the like that is relatively advantageous for functional group conversion reaction at the end, and has a large degree of freedom in designing initiators and catalysts. It is further preferable as a method for producing a vinyl-based polymer having Examples of this atom transfer radical polymerization method include Matyjaszewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614.
本発明で使用される塩化ビニル系共重合樹脂を構成するマクロモノマーの製法として、これらのうちどの方法を使用するかは特に制約はないが、通常、制御ラジカル重合法が利用され、さらに制御の容易さなどからリビングラジカル重合法が好ましく用いられ、特に原子移動ラジカル重合法が最も好ましい。 There is no particular restriction as to which of these methods is used as a method for producing the macromonomer constituting the vinyl chloride copolymer resin used in the present invention, but usually a controlled radical polymerization method is used, and further control is performed. The living radical polymerization method is preferably used because of easiness and the like, and the atom transfer radical polymerization method is most preferable.
また本発明で使用される塩化ビニル系共重合樹脂を構成するマクロモノマーの主鎖が有する、二重結合を含有するエチレン性不飽和モノマーからなる重合体としては特に制約はなく、該重合体を構成する二重結合を含有するエチレン性不飽和モノマーとしては、各種のものを使用することができる。例えば（メタ）アクリル酸、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸−ｎ−プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸−ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸−ｔｅｒｔ−ブチル、（メタ）アクリル酸−ｎ−ペンチル、（メタ）アクリル酸−ｎ−ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸−ｎ−ヘプチル、（メタ）アクリル酸−ｎ−オクチル、（メタ）アクリル酸−２−エチルヘキシル、（メタ）アクリル酸ノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸フェニル、（メタ）アクリル酸トルイル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸−２−メトキシエチル、（メタ）アクリル酸−３−メトキシブチル、（メタ）アクリル酸−２−ヒドロキシエチル、（メタ）アクリル酸−２−ヒドロキシプロピル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸グリシジル、（メタ）アクリル酸２−アミノエチル、γ−（メタクリロイルオキシプロピル）トリメトキシシラン、（メタ）アクリル酸のエチレンオキサイド付加物、（メタ）アクリル酸トリフルオロメチルメチル、（メタ）アクリル酸２−トリフルオロメチルエチル、（メタ）アクリル酸２−パーフルオロエチルエチル、（メタ）アクリル酸２−パーフルオロエチル−２−パーフルオロブチルエチル、（メタ）アクリル酸２−パーフルオロエチル、（メタ）アクリル酸パーフルオロメチル、（メタ）アクリル酸ジパーフルオロメチルメチル、（メタ）アクリル酸２−パーフルオロメチル−２−パーフルオロエチルメチル、（メタ）アクリル酸２−パーフルオロヘキシルエチル、（メタ）アクリル酸２−パーフルオロデシルエチル、（メタ）アクリル酸２−パーフルオロヘキサデシルエチル等の（メタ）アクリル酸系モノマー；スチレン、ビニルトルエン、α−メチルスチレン、クロルスチレン、スチレンスルホン酸およびその塩等のスチレン系モノマー；パーフルオロエチレン、パーフルオロプロピレン、フッ化ビニリデン等のフッ素含有ビニルモノマー；ビニルトリメトキシシラン、ビニルトリエトキシシラン等のケイ素含有ビニルモノマー；無水マレイン酸、マレイン酸、マレイン酸のモノアルキルエステルおよびジアルキルエステル；フマル酸、フマル酸のモノアルキルエステルおよびジアルキルエステル；マレイミド、メチルマレイミド、エチルマレイミド、プロピルマレイミド、ブチルマレイミド、ヘキシルマレイミド、オクチルマレイミド、ドデシルマレイミド、ステアリルマレイミド、フェニルマレイミド、シクロヘキシルマレイミド等のマレイミド系モノマー；アクリロニトリル、メタクリロニトリル等のニトリル基含有ビニル系モノマー；アクリルアミド、メタクリルアミド等のアミド基含有ビニル系モノマー；酢酸ビニル、プロピオン酸ビニル、ピバリン酸ビニル、安息香酸ビニル、桂皮酸ビニル等のビニルエステル類；エチレン、プロピレン等のアルケン類；ブタジエン、イソプレン等の共役ジエン類；塩化アリル、アリルアルコール等が挙げられる。これらは単独で使用しても良いし、２種以上を共重合させても構わない。中でも生成物の物性等から、スチレン系モノマーあるいは（メタ）アクリル酸系モノマーが好ましい。より好ましくはアクリル酸エステルモノマーあるいはメタクリル酸エステルモノマーであり、さらに好ましくはアクリル酸エステルモノマーであり、最も好ましくはアクリル酸ブチルである。本発明においてはこれらの好ましいモノマーを他のモノマーと共重合させたものを用いても良く、その際はこれらの好ましいモノマーが重量比で４０％以上含まれていることが好ましい。ここで、例えば「（メタ）アクリル酸」とは、アクリル酸あるいはメタクリル酸を意味するものである。 In addition, there is no particular limitation on the polymer composed of an ethylenically unsaturated monomer containing a double bond, which is included in the main chain of the macromonomer constituting the vinyl chloride copolymer resin used in the present invention. Various kinds of ethylenically unsaturated monomers containing a double bond can be used. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n-butyl, (meth ) Isobutyl acrylate, (meth) acrylic acid-tert-butyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid-n- Heptyl, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, Toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (meth) 3-methoxybutyl crylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic acid 2 -Aminoethyl, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, (meth ) 2-perfluoroethylethyl acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, (meta ) Diperfluoromethyl methyl acrylate, (meth) acrylic 2-perfluoromethyl-2-perfluoroethyl methyl phosphate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecyl (meth) acrylate (Meth) acrylic acid monomers such as ethyl; styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; fluorine such as perfluoroethylene, perfluoropropylene, vinylidene fluoride -Containing vinyl monomers; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters of fumaric acid and dia Kill esters; maleimide monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; containing nitrile groups such as acrylonitrile and methacrylonitrile Vinyl monomers; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; butadiene And conjugated dienes such as isoprene; allyl chloride, allyl alcohol and the like. These may be used alone or two or more of them may be copolymerized. Of these, a styrene monomer or a (meth) acrylic acid monomer is preferred from the viewpoint of physical properties of the product. An acrylate monomer or a methacrylic acid ester monomer is more preferable, an acrylate monomer is more preferable, and butyl acrylate is most preferable. In the present invention, those obtained by copolymerizing these preferable monomers with other monomers may be used, and in this case, it is preferable that these preferable monomers are contained in a weight ratio of 40% or more. Here, for example, “(meth) acrylic acid” means acrylic acid or methacrylic acid.
本発明で使用される塩化ビニル系共重合樹脂を構成するマクロモノマーは、これら二重結合を含有するエチレン性不飽和モノマーからなる重合体を主鎖に有し、さらに反応性官能基を、少なくとも１分子あたり１個、分子末端に有することを特徴としている。 The macromonomer constituting the vinyl chloride copolymer resin used in the present invention has a polymer composed of an ethylenically unsaturated monomer containing these double bonds in the main chain, and further has at least a reactive functional group. It is characterized by having one per molecule at the molecular end.
さらに、本発明で使用される塩化ビニル系共重合樹脂を構成する、塩化ビニル系モノマーと共重合可能なマクロモノマーは１種のみを用いてもよく、構成するエチレン性不飽和モノマーが異なるマクロモノマーを２種以上併用してもよい。 Furthermore, only one type of macromonomer copolymerizable with the vinyl chloride monomer constituting the vinyl chloride copolymer resin used in the present invention may be used, and the macromonomer having a different ethylenically unsaturated monomer may be used. Two or more of these may be used in combination.
本発明で使用される塩化ビニル系共重合樹脂全体に占める、二重結合を含有するエチレン性不飽和モノマーからなる重合体を主鎖に有するマクロモノマー成分の分率は、本発明の効果を奏する範囲であれば特に制約はないが、５重量％以上５０重量％以下であることが好ましい。二重結合を含有するエチレン性不飽和モノマーからなる重合体を主鎖に有するマクロモノマー成分の分率が５重量％以上５０重量％以下の範囲であれば、共重合反応が安定である上に、得られる塩化ビニル系共重合樹脂が粉粒体になり、加工方法の自由度を増すという効果が期待できる。 The fraction of the macromonomer component having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the entire vinyl chloride copolymer resin used in the present invention has the effect of the present invention. There is no particular limitation as long as it is within the range, but it is preferably 5% by weight or more and 50% by weight or less. If the fraction of the macromonomer component having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain is in the range of 5% by weight to 50% by weight, the copolymerization reaction is stable. The resulting vinyl chloride copolymer resin becomes a powder and can be expected to increase the degree of freedom in the processing method.
本発明で使用される塩化ビニル系共重合樹脂の平均重合度または平均分子量は特に限定されず、通常製造および使用される塩化ビニル系樹脂と同様に、ＪＩＳ Ｋ ７３６７−２に従って測定したＫ値が５０〜９５の範囲である。また、平均粒径としては、通常０．０１〜５００μｍの範囲であり、好ましくは０．１〜３００μｍの範囲であり、さらに好ましくは、５０〜３００μｍの範囲である。平均粒径が５０〜３００μｍの範囲であれば、成形加工時の流動性および成形品の強度物性にバランスがとれた素材を提供することができる。 The average degree of polymerization or the average molecular weight of the vinyl chloride copolymer resin used in the present invention is not particularly limited, and the K value measured according to JIS K 7367-2 is the same as that of the vinyl chloride resin usually manufactured and used. It is in the range of 50-95. Moreover, as an average particle diameter, it is the range of 0.01-500 micrometers normally, Preferably it is the range of 0.1-300 micrometers, More preferably, it is the range of 50-300 micrometers. When the average particle size is in the range of 50 to 300 μm, it is possible to provide a material in which the fluidity during the molding process and the strength properties of the molded product are balanced.
本発明で使用される塩化ビニル系共重合樹脂の製造方法については、特に制約はないが、重合制御の簡便性から水性媒体中での共重合が好ましく、そのような重合方法としては、例えば、懸濁重合法、微細懸濁重合法、乳化重合法等の製造方法が挙げられる。中でも、平均粒径が５０〜３００μｍの範囲の塩化ビニル系共重合樹脂を得るために懸濁重合法が好ましい。このような製造方法によれば、該共重合樹脂はラテックス状あるいはスラリー状で得られるが、これを乾燥して粉粒体の共重合樹脂を得る方法としては特に制約はなく、例えば、ラテックスをスプレー乾燥法により乾燥する方法、スラリーを脱水したのち流動乾燥法により乾燥する方法、等が挙げられる。 The production method of the vinyl chloride copolymer resin used in the present invention is not particularly limited, but copolymerization in an aqueous medium is preferable from the viewpoint of simplicity of polymerization control. Examples of such polymerization methods include: Examples of the production method include suspension polymerization, fine suspension polymerization, and emulsion polymerization. Among these, the suspension polymerization method is preferable in order to obtain a vinyl chloride copolymer resin having an average particle size in the range of 50 to 300 μm. According to such a production method, the copolymer resin can be obtained in the form of a latex or a slurry. However, there is no particular limitation on the method of drying the copolymer resin to obtain a granular copolymer resin. Examples include a method of drying by a spray drying method, a method of dehydrating a slurry and then drying by a fluidized drying method, and the like.
本発明においては、塩化ビニル系モノマーと二重結合を含有するエチレン性不飽和モノマーからなる重合体を主鎖に有するマクロモノマーとを共重合してなる塩化ビニル系共重合樹脂を塩化ビニル系樹脂に添加するが、該塩化ビニル系樹脂を構成するモノマーは塩化ビニルモノマーを主成分とするモノマーであり、具体的には、塩化ビニルモノマー単独、または塩化ビニルモノマーを５０重量％以上、特に７０重量％以上含有する、塩化ビニルモノマーと共重合可能で、好ましくは重合後の重合体主鎖に反応性官能基を有しないモノマーと塩化ビニルモノマーとの混合物である。塩化ビニルモノマーと共重合可能なモノマーとしては、例えば酢酸ビニル、プロピオン酸ビニル等のビニルエステル類；エチレン、プロピレン、イソブチルビニルエーテル等のα−オレフィン類；１−クロロプロピレン、２−クロロブチレン等のクロル化オレフィン類；（メタ）アクリル酸メチル等の（メタ）アクリル酸エステル類；無水マレイン酸、アクリロニトリル、スチレン、塩化ビニリデン等が挙げられ、これらは単独で用いることも、２種以上組み合わせて用いることも可能である。 In the present invention, a vinyl chloride copolymer resin obtained by copolymerizing a vinyl chloride monomer and a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain is used as the vinyl chloride resin. The monomer constituting the vinyl chloride resin is a monomer mainly composed of vinyl chloride monomer. Specifically, the vinyl chloride monomer alone or the vinyl chloride monomer is 50% by weight or more, particularly 70% by weight. It is a mixture of a monomer and a vinyl chloride monomer, which can be copolymerized with the vinyl chloride monomer, and preferably has no reactive functional group in the polymer main chain after polymerization. Examples of monomers copolymerizable with vinyl chloride monomer include vinyl esters such as vinyl acetate and vinyl propionate; α-olefins such as ethylene, propylene and isobutyl vinyl ether; chloro such as 1-chloropropylene and 2-chlorobutylene. Olefins; (meth) acrylic acid esters such as methyl (meth) acrylate; maleic anhydride, acrylonitrile, styrene, vinylidene chloride, and the like. These may be used alone or in combination of two or more. Is also possible.
本発明で使用される塩化ビニル系樹脂の製造方法については、特に制約はないが、重合制御の簡便性から水性媒体中での重合が好ましく、そのような重合方法としては、例えば、懸濁重合法、微細懸濁重合法、乳化重合法等の製造方法が挙げられる。中でも、射出成形法に通常用いられる塩化ビニル系樹脂と同様に、懸濁重合法により製造されることが好ましい。このような製造方法によれば、該塩化ビニル系樹脂はラテックス状あるいはスラリー状で得られるが、これを乾燥して粉粒体の塩化ビニル系樹脂を得る方法としては特に制約はなく、例えば、ラテックスをスプレー乾燥法により乾燥する方法、スラリーを脱水したのち流動乾燥法により乾燥する方法、等が挙げられる。 The method for producing the vinyl chloride resin used in the present invention is not particularly limited, but polymerization in an aqueous medium is preferable from the viewpoint of ease of polymerization control. Examples of such polymerization methods include suspension weight. Examples of the production method include a combination method, a fine suspension polymerization method, and an emulsion polymerization method. Especially, it is preferable to manufacture by the suspension polymerization method similarly to the vinyl chloride resin normally used for the injection molding method. According to such a production method, the vinyl chloride resin can be obtained in the form of a latex or a slurry, but there is no particular limitation on the method of drying this to obtain a granular vinyl chloride resin, for example, Examples thereof include a method of drying latex by a spray drying method, a method of drying a slurry after dehydrating the slurry, and the like.
本発明においては、塩化ビニル系モノマーと二重結合を含有するエチレン性不飽和モノマーからなる重合体を主鎖に有するマクロモノマーとを共重合してなる塩化ビニル系共重合樹脂を塩化ビニル系樹脂に添加して用いるが、塩化ビニル系樹脂１００重量部を基準とした、塩化ビニル系共重合樹脂中の二重結合を含有するエチレン性不飽和モノマーからなる重合体を主鎖に有するマクロモノマー成分の含量は、本発明の効果を奏する範囲であれば特に制約はないが、０．１重量部以上１量部以下の範囲となるように、該共重合樹脂を添加することが好ましい。塩化ビニル系樹脂１００重量部を基準とした、塩化ビニル系共重合樹脂中の二重結合を含有するエチレン性不飽和モノマーからなる重合体を主鎖に有するマクロモノマー成分の含量が、０．１重量部以上１重量部以下の範囲であれば、成形加工時の流動性および成形品の強度物性にバランスがとれた素材を提供することができる。 In the present invention, a vinyl chloride copolymer resin obtained by copolymerizing a vinyl chloride monomer and a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain is used as the vinyl chloride resin. A macromonomer component having a polymer composed of an ethylenically unsaturated monomer containing a double bond in a vinyl chloride copolymer resin based on 100 parts by weight of a vinyl chloride resin as a main chain. Although there is no restriction | limiting in particular if it is the range which has the effect of this invention, it is preferable to add this copolymer resin so that it may become the range of 0.1 to 1 part by weight. Based on 100 parts by weight of the vinyl chloride resin, the content of the macromonomer component having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the vinyl chloride copolymer resin in the main chain is 0.1. If it is in the range of from 1 part by weight to 1 part by weight, it is possible to provide a material in which the fluidity during molding and the strength properties of the molded product are balanced.
ここで、塩化ビニル系樹脂１００重量部を基準とした、塩化ビニル系共重合樹脂中の二重結合を含有するエチレン性不飽和モノマーからなる重合体を主鎖に有するマクロモノマー成分の含量は、下記計算式（２）により算出される。 Here, based on 100 parts by weight of the vinyl chloride resin, the content of the macromonomer component having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the vinyl chloride copolymer resin in the main chain is as follows: It is calculated by the following calculation formula (2).
Ｚ＝Ｘ×Ｙ÷１００ （２）
Ｚ：塩化ビニル系樹脂１００重量部を基準とした、塩化ビニル系共重合樹脂中の
二重結合を含有するエチレン性不飽和モノマーからなる重合体を主鎖に有
するマクロモノマー成分の含量（重量部）
Ｘ：塩化ビニル系共重合樹脂全体に占める、二重結合を含有するエチレン性不飽
和モノマーからなる重合体を主鎖に有するマクロモノマー成分の分率
（重量％）
Ｙ：塩化ビニル系樹脂１００重量部に対する、塩化ビニル系共重合樹脂の添加部
数（重量部）
本発明の射出成形品用塩化ビニル系樹脂組成物中には、塩化ビニル系樹脂および塩化ビニル系モノマーと二重結合を含有するエチレン性不飽和モノマーからなる重合体を主鎖に有するマクロモノマーとを共重合してなる塩化ビニル系共重合樹脂を必須成分とし、必要に応じ熱安定剤、滑剤、安定化助剤、加工助剤、充填剤、酸化防止剤、光安定剤、顔料等を、本発明の目的を損なわない範囲で適宜配合することができ、また可塑剤も、本発明の目的を損なわない範囲で、必要に応じ適宜使用することができる。
Z = X × Y ÷ 100 (2)
Z: in vinyl chloride copolymer resin based on 100 parts by weight of vinyl chloride resin
The main chain has a polymer composed of ethylenically unsaturated monomers containing double bonds.
Macromonomer component content (parts by weight)
X: Ethylenic unsaturation containing double bonds in the entire vinyl chloride copolymer resin
Fraction of macromonomer component having polymer composed of sum monomer in main chain
(weight%)
Y: Addition part of vinyl chloride copolymer resin to 100 parts by weight of vinyl chloride resin
Number (parts by weight)
In the vinyl chloride resin composition for injection-molded articles of the present invention, a macromonomer having a polymer consisting of a vinyl chloride resin and a vinyl chloride monomer and an ethylenically unsaturated monomer containing a double bond in the main chain; As an essential component, a vinyl chloride copolymer resin obtained by copolymerization of a heat stabilizer, a lubricant, a stabilizing aid, a processing aid, a filler, an antioxidant, a light stabilizer, a pigment, etc. It can mix | blend suitably in the range which does not impair the objective of this invention, and a plasticizer can also be suitably used as needed in the range which does not impair the objective of this invention.
熱安定剤としては、特に限定されず、本発明の目的を損なわない範囲のものを用いることができる。そのような熱安定剤としては、例えばジメチル錫メルカプト、ジブチル錫メルカプト、ジオクチル錫メルカプト、ジブチル錫マレート、ジブチル錫マレートポリマー、ジオクチル錫マレート、ジオクチル錫マレートポリマー、ジブチル錫ラウレート、ジブチル錫ラウレートポリマー等の有機錫安定剤；ステアリン酸鉛、二塩基性亜燐酸鉛、三塩基性硫酸鉛等の鉛系安定剤；カルシウム−亜鉛系安定剤；バリウム−亜鉛系安定剤；カドミウム−バリウム系安定剤等が挙げられ、これらは単独で用いても２種以上を併用しても良い。またその使用量も特に限定されず、本発明の目的を損なわない範囲であれば良い。 It does not specifically limit as a heat stabilizer, The thing of the range which does not impair the objective of this invention can be used. Examples of such heat stabilizers include dimethyl tin mercapto, dibutyl tin mercapto, dioctyl tin mercapto, dibutyl tin malate, dibutyl tin malate polymer, dioctyl tin malate, dioctyl tin malate polymer, dibutyl tin laurate, dibutyl tin laurate. Organic tin stabilizers such as polymers; lead stabilizers such as lead stearate, dibasic lead phosphite and tribasic lead sulfate; calcium-zinc stabilizers; barium-zinc stabilizers; cadmium-barium stabilizers An agent etc. are mentioned, These may be used independently or may use 2 or more types together. Further, the amount used is not particularly limited as long as the object of the present invention is not impaired.
また滑剤としては、特に限定されず、本発明の目的を損なわない範囲のものを用いることができる。そのような滑剤としては、例えばパラフィンワックス系滑剤、ポリオレフィンワックス系滑剤、ステアリン酸系滑剤、アルコール系滑剤、エステル系滑剤等が挙げられ、これらは単独で用いても２種以上を併用しても良い。またその使用量も特に限定されず、本発明の目的を損なわない範囲であれば良い。 Moreover, it does not specifically limit as a lubricant, The thing of the range which does not impair the objective of this invention can be used. Examples of such lubricants include paraffin wax-based lubricants, polyolefin wax-based lubricants, stearic acid-based lubricants, alcohol-based lubricants, and ester-based lubricants. These may be used alone or in combination of two or more. good. Further, the amount used is not particularly limited as long as the object of the present invention is not impaired.
さらに安定化助剤としては、特に限定されず、本発明の目的を損なわない範囲のものを用いることができる。そのような安定化助剤としては、例えばエポキシ化大豆油、エポキシ化アマニ油、エポキシ化テトラヒドロフタレート、エポキシ化ポリブタジエン、燐酸エステル等が挙げられ、これらは単独で用いても２種以上を併用しても良い。またその使用量も特に限定されず、本発明の目的を損なわない範囲であれば良い。 Furthermore, it does not specifically limit as a stabilizing aid, The thing of the range which does not impair the objective of this invention can be used. Examples of such stabilizing aids include epoxidized soybean oil, epoxidized linseed oil, epoxidized tetrahydrophthalate, epoxidized polybutadiene, and phosphoric acid ester. These may be used alone or in combination of two or more. May be. Further, the amount used is not particularly limited as long as the object of the present invention is not impaired.
また加工助剤としては、特に限定されず、本発明の目的を損なわない範囲のものを用いることができる。そのような加工助剤としては、例えばアクリル酸−ｎ−ブチル／メタクリル酸メチル共重合体、アクリル酸−２−エチルヘキシル／メタクリル酸メチル共重合体、アクリル酸−２−エチルヘキシル／メタクリル酸メチル／メタクリル酸−ｎ−ブチル共重合体等のアクリル系加工助剤等が挙げられ、これらは単独で用いても２種以上を併用しても良い。またその使用量も特に限定されず、本発明の目的を損なわない範囲であれば良い。 Moreover, it does not specifically limit as a processing aid, The thing of the range which does not impair the objective of this invention can be used. Examples of such processing aids include acrylic acid-n-butyl / methyl methacrylate copolymer, acrylic acid-2-ethylhexyl / methyl methacrylate copolymer, acrylic acid-2-ethylhexyl / methyl methacrylate / methacrylic acid. Examples thereof include acrylic processing aids such as acid-n-butyl copolymer, and these may be used alone or in combination of two or more. Further, the amount used is not particularly limited as long as the object of the present invention is not impaired.
さらに充填剤としては、特に限定されず、本発明の目的を損なわない範囲のものを用いることができる。そのような充填剤としては、例えば炭酸カルシウム、炭酸マグネシウム、炭酸リチウム、カオリングレー、石膏、マイカ、タルク、水酸化マグネシウム、珪酸カルシウム、硼砂等が挙げられ、これらは単独で用いても２種以上を併用しても良い。またその使用量も特に限定されず、本発明の目的を損なわない範囲であれば良い。 Furthermore, it does not specifically limit as a filler, The thing of the range which does not impair the objective of this invention can be used. Examples of such fillers include calcium carbonate, magnesium carbonate, lithium carbonate, kaolin clay, gypsum, mica, talc, magnesium hydroxide, calcium silicate, borax and the like. May be used in combination. Further, the amount used is not particularly limited as long as the object of the present invention is not impaired.
また酸化防止剤としては、特に限定されず、本発明の目的を損なわない範囲のものを用いることができる。そのような酸化防止剤としては、例えばフェノール系抗酸化剤等が挙げられ、これらは単独で用いても２種以上を併用しても良い。またその使用量も特に限定されず、本発明の目的を損なわない範囲であれば良い。 Moreover, it does not specifically limit as an antioxidant, The thing of the range which does not impair the objective of this invention can be used. Examples of such antioxidants include phenolic antioxidants, and these may be used alone or in combination of two or more. Further, the amount used is not particularly limited as long as the object of the present invention is not impaired.
さらに光安定剤としては、特に限定されず、本発明の目的を損なわない範囲のものを用いることができる。そのような光安定剤としては、例えばサリチル酸エステル系、ベンゾフェノン系、ベンゾトリアゾール系、シアノアクリレート系等の紫外線吸収剤；ヒンダードアミン系の光安定剤等が挙げられ、これらは単独で用いても２種以上を併用しても良い。またその使用量も特に限定されず、本発明の目的を損なわない範囲であれば良い。 Furthermore, it does not specifically limit as a light stabilizer, The thing of the range which does not impair the objective of this invention can be used. Examples of such light stabilizers include salicylic acid ester-based, benzophenone-based, benzotriazole-based, and cyanoacrylate-based UV absorbers; hindered amine-based light stabilizers, and the like. You may use the above together. Further, the amount used is not particularly limited as long as the object of the present invention is not impaired.
また顔料としては、特に限定されず、本発明の目的を損なわない範囲のものを用いることができる。そのような顔料としては、例えばアゾ系、フタロシアニン系、スレン系、染料レーキ系等の有機顔料；酸化物系、クロム酸モリブデン系、硫化物・セレン化物系、フェロシアン化物系等の無機顔料等が挙げられ、これらは単独で用いても２種以上を併用しても良い。またその使用量も特に限定されず、本発明の目的を損なわない範囲であれば良い。 Moreover, it does not specifically limit as a pigment, The thing of the range which does not impair the objective of this invention can be used. Examples of such pigments include organic pigments such as azo, phthalocyanine, selenium and dye lakes; inorganic pigments such as oxides, molybdenum chromates, sulfides / selenides, ferrocyanides, etc. These may be used alone or in combination of two or more. Further, the amount used is not particularly limited as long as the object of the present invention is not impaired.
さらに可塑剤としては、特に限定されず、本発明の目的を損なわない範囲のものを用いることができる。そのような可塑剤としては、例えばジ−２−エチルヘキシルフタレート、ジ−ｎ−オクチルフタレート、ジイソノニルフタレート、ジブチルフタレート等のフタル酸エステル系可塑剤；トリクレジルフォスフェート、トリキシリルホスフェート、トリフェニルフォスフェート等のリン酸エステル系可塑剤；ジ−２−エチルヘキシルアジペート、ジ−２−エチルヘキシルセバケート等の脂肪酸エステル系可塑剤等が挙げられ、これらは単独で用いても２種以上を併用しても良い。またその使用量も特に限定されず、本発明の目的を損なわない範囲であれば良い。 Furthermore, it does not specifically limit as a plasticizer, The thing of the range which does not impair the objective of this invention can be used. Examples of such plasticizers include phthalate plasticizers such as di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisononyl phthalate, and dibutyl phthalate; tricresyl phosphate, trixyl phosphate, triphenyl phosphate Phosphate plasticizers such as fetes; fatty acid ester plasticizers such as di-2-ethylhexyl adipate and di-2-ethylhexyl sebacate, etc., and these may be used alone or in combination of two or more. Also good. Further, the amount used is not particularly limited as long as the object of the present invention is not impaired.
その他、本発明の目的を損なわない範囲の難燃剤、帯電防止剤、強化剤、改質剤等も必要に応じて適宜配合することができ、その使用量も特に限定されず、本発明の目的を損なわない範囲であれば良い。 In addition, flame retardants, antistatic agents, reinforcing agents, modifiers and the like within a range that does not impair the object of the present invention can be appropriately blended as necessary, and the amount used is not particularly limited, and the object of the present invention As long as it is within a range that does not impair.
本発明の射出成形品用塩化ビニル系樹脂組成物の製造方法には特に限定はなく、塩化ビニル系樹脂および塩化ビニル系共重合樹脂を所定量配合し、要すれば使用される各種添加剤（熱安定剤、滑剤、安定化助剤、加工助剤、充填剤、酸化防止剤、光安定剤、顔料、可塑剤等）を配合したものを、例えばリボンブレンダー、スーパーミキサー、タンブラーミキサー、バンバリーミキサー、ヘンシェルミキサー、ミキシングロール等の混合機および／または混合混練機等を用いて、ホットブレンドまたはコールドブレンド等の常法によって均一に混合または混合混練するなどの方法で製造すれば良い。その際の配合順序等に特に限定はなく、本発明の目的を損なわない範囲の技術を任意に用いることができる。例えば塩化ビニル系樹脂、塩化ビニル系共重合樹脂、各種添加剤を一括して配合する方法、液状の添加剤を均一に配合する目的で先に塩化ビニル系樹脂、塩化ビニル系共重合樹脂、粉粒体の各種添加剤を配合したのち液状添加剤を配合する方法または先に塩化ビニル系樹脂および塩化ビニル系共重合樹脂を配合したのち液状添加剤を配合し、最後に粉粒体の各種添加剤を配合する方法、さらに、まず塩化ビニル系樹脂および各種添加剤を配合し、次いで塩化ビニル系共重合樹脂を配合する方法、等を用いることができる。 The method for producing the vinyl chloride resin composition for injection molded articles of the present invention is not particularly limited, and a predetermined amount of vinyl chloride resin and vinyl chloride copolymer resin is blended, and if necessary, various additives ( Heat blenders, lubricants, stabilization aids, processing aids, fillers, antioxidants, light stabilizers, pigments, plasticizers, etc.), for example, ribbon blenders, super mixers, tumbler mixers, Banbury mixers They may be produced by a method such as uniform mixing or mixing and kneading by a conventional method such as hot blending or cold blending using a mixer such as a Henschel mixer or a mixing roll and / or a mixing kneader. There is no particular limitation on the blending order and the like at that time, and any technique within the range not impairing the object of the present invention can be used. For example, a vinyl chloride resin, a vinyl chloride copolymer resin, a method of blending various additives all together, a vinyl chloride resin, a vinyl chloride copolymer resin, a powder for the purpose of uniformly blending liquid additives Method of blending liquid additives after blending various additives of granules, or blending liquid additives after blending vinyl chloride resin and vinyl chloride copolymer resin first, and finally adding various additives of granules A method of blending an agent, a method of blending a vinyl chloride resin and various additives, and then blending a vinyl chloride copolymer resin can be used.
このようにして製造された本発明の射出成形品用塩化ビニル系樹脂組成物は、そのまま射出成形加工に供しても良いし、さらにコニーダー、押出機、ペレタイザー等の混練機および／または混練造粒機等を用いて混練または混練造粒したのち、射出成形加工に供しても良い。 The vinyl chloride resin composition for injection molded articles of the present invention thus produced may be used for injection molding as it is, and further kneaders such as a kneader, an extruder and a pelletizer and / or kneading granulation. After kneading or kneading granulation using a machine or the like, it may be used for injection molding.
本発明の射出成形品用塩化ビニル系樹脂組成物は、継手、バルブ、等の製品に成形加工されて用いられる。 The vinyl chloride resin composition for injection molded products of the present invention is used after being molded into products such as joints and valves.
次に本発明を実施例に基づいて詳細に説明するが、本発明は以下の実施例に限定されるものではない。ここで、特に断りのない限り、実施例中の「部」は「重量部」を、「％」は「重量％」を意味する。
＜二重結合を含有するエチレン性不飽和モノマーからなる重合体を主鎖に有するマクロモノマーの製造＞
二重結合を含有するエチレン性不飽和モノマーからなる重合体を主鎖に有するマクロモノマーの製造は、下記の製造例に示す手順に従って行った。
EXAMPLES Next, although this invention is demonstrated in detail based on an Example, this invention is not limited to a following example. Here, unless otherwise specified, “parts” in the examples means “parts by weight” and “%” means “% by weight”.
<Manufacture of a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain>
Production of a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain was carried out according to the procedure shown in the following production example.
（製造例１）
還流管および攪拌機付きの２Ｌのセパラブルフラスコに、ＣｕＢｒ（５．５４ｇ）を仕込み、反応容器内を窒素置換した。アセトニトリル（７３．８ｍｌ）を加え、オイルバス中７０℃で３０分間攪拌した。これにアクリル酸−ｎ−ブチル（１３２ｇ）、２−ブロモプロピオン酸メチル（７．２ｍｌ）、ペンタメチルジエチレントリアミン（４．６９ｍｌ）を加え、反応を開始した。７０℃で加熱攪拌しながら、アクリル酸−ｎ−ブチル（５２８ｇ）を９０分かけて連続的に滴下し、さらに８０分間加熱攪拌した。
(Production Example 1)
CuBr (5.54 g) was charged into a 2 L separable flask equipped with a reflux tube and a stirrer, and the inside of the reaction vessel was purged with nitrogen. Acetonitrile (73.8 ml) was added, and the mixture was stirred in an oil bath at 70 ° C. for 30 minutes. To this, n-butyl acrylate (132 g), methyl 2-bromopropionate (7.2 ml) and pentamethyldiethylenetriamine (4.69 ml) were added to initiate the reaction. While heating and stirring at 70 ° C., acrylate-n-butyl (528 g) was continuously added dropwise over 90 minutes, and the mixture was further heated and stirred for 80 minutes.
反応混合物をトルエンで希釈し、活性アルミナカラムを通したのち、揮発分を減圧留去することにより、片末端Ｂｒ基ポリ（アクリル酸−ｎ−ブチル）を得た。 The reaction mixture was diluted with toluene, passed through an activated alumina column, and then the volatile component was distilled off under reduced pressure to obtain one-terminal Br group poly (acrylic acid-n-butyl).
フラスコに、メタノール（８００ｍｌ）を仕込み、０℃に冷却した。そこへ、ｔ−ブトキシカリウム（１３０ｇ）を数回に分けて加えた。この反応溶液を０℃に保持して、アクリル酸（１００ｇ）のメタノール溶液を滴下した。滴下終了後、反応液の温度を０℃から室温に戻したのち、反応液の揮発分を減圧留去することにより、アクリル酸カリウム（ＣＨ2＝ＣＨＣＯ2Ｋ）を得た。 The flask was charged with methanol (800 ml) and cooled to 0 ° C. Thereto, t-butoxypotassium (130 g) was added in several portions. The reaction solution was kept at 0 ° C., and a methanol solution of acrylic acid (100 g) was added dropwise. After completion of the dropwise addition, the temperature of the reaction solution was returned from 0 ° C. to room temperature, and then the volatile content of the reaction solution was distilled off under reduced pressure to obtain potassium acrylate (CH 2 = CHCO 2 K).
還流管付き５００ｍＬフラスコに、得られた片末端Ｂｒ基ポリ（アクリル酸−ｎ−ブチル）（１５０ｇ）、アクリル酸カリウム（７．４５ｇ）、ジメチルアセトアミド（１５０ｍｌ）を仕込み、７０℃で３時間加熱攪拌した。反応混合物よりジメチルアセトアミドを留去し、トルエンに溶解させ、活性アルミナカラムを通したのち、トルエンを留去することにより片末端アクリロイル基ポリ（アクリル酸−ｎ−ブチル）マクロモノマーを得た。
＜塩化ビニル系モノマーと二重結合を含有するエチレン性不飽和モノマーからなる重合体を主鎖に有するマクロモノマーとを共重合してなる塩化ビニル系共重合樹脂の製造＞
塩化ビニル系モノマーと二重結合を含有するエチレン性不飽和モノマーからなる重合体を主鎖に有するマクロモノマーとを共重合してなる塩化ビニル系共重合樹脂の製造は、下記の製造例に示す手順に従って行った。
A 500 mL flask equipped with a reflux tube was charged with the obtained one-terminal Br group poly (acrylic acid-n-butyl) (150 g), potassium acrylate (7.45 g), dimethylacetamide (150 ml), and heated at 70 ° C. for 3 hours. Stir. Dimethylacetamide was distilled off from the reaction mixture, dissolved in toluene, passed through an activated alumina column, and then toluene was distilled off to obtain a one-terminal acryloyl group poly (acrylic acid-n-butyl) macromonomer.
<Production of vinyl chloride copolymer resin obtained by copolymerizing a vinyl monomer and a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain>
Production of a vinyl chloride copolymer resin obtained by copolymerizing a vinyl monomer and a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain is shown in the following production examples. Followed the procedure.
（製造例Ａ）マクロモノマー成分の分率が５％である塩化ビニル系共重合樹脂の製造
ジャケットおよび攪拌機を備えた内容量２５リットルのステンレス鋼製重合反応機を脱気したのち塩化ビニルモノマー９５部を仕込み、次いで製造例１の片末端アクリロイル基ポリ（アクリル酸−ｎ−ブチル）マクロモノマー５部を仕込んだのち、ジャケットに温水を通じて重合反応機内温を３０℃まで昇温し、１分間当たり９００回転の回転速度で５分間攪拌した。ジャケットに水を通じて重合反応機内温を２０℃以下まで冷却したのち、鹸化度約８０モル％、平均重合度約２０００の部分鹸化ポリ酢酸ビニル０．１部、ｔ−ブチルパーオキシネオデカノエイト０．０３部、１，１，３，３−テトラメチルブチルパーオキシネオデカノエート０．０１部を仕込んだのち６０℃の温水１５０部を仕込み、重合温度５７℃で約６時間重合した。重合機内の未反応モノマーを回収したのち重合機を冷却し、スラリーを払い出した。得られたスラリーを脱水して熱風乾燥機にて５５℃で２４時間乾燥し、塩化ビニル／ポリ（アクリル酸−ｎ−ブチル）グラフト共重合樹脂Ａを白色粉末として得た。
(Production Example A) Production of a vinyl chloride copolymer resin having a macromonomer component fraction of 5% After degassing a stainless steel polymerization reactor having a volume of 25 liters equipped with a jacket and a stirrer, vinyl chloride monomer 95 Then, 5 parts of acryloyl group poly (n-butyl acrylate) macromonomer of Production Example 1 was charged, and then the temperature inside the polymerization reactor was raised to 30 ° C. through warm water in the jacket, per minute The mixture was stirred for 5 minutes at a rotation speed of 900 rpm. After cooling the temperature inside the polymerization reactor to 20 ° C. or less through water through the jacket, 0.1 part of partially saponified polyvinyl acetate having a saponification degree of about 80 mol% and an average degree of polymerization of about 2000, t-butyl peroxyneodecanoate 0 0.03 part and 0.01 part of 1,1,3,3-tetramethylbutylperoxyneodecanoate were added, and then 150 parts of hot water at 60 ° C. was added, and polymerization was carried out at a polymerization temperature of 57 ° C. for about 6 hours. After recovering unreacted monomers in the polymerization machine, the polymerization machine was cooled and the slurry was discharged. The obtained slurry was dehydrated and dried with a hot air dryer at 55 ° C. for 24 hours to obtain a vinyl chloride / poly (n-butyl acrylate) graft copolymer resin A as a white powder.
（製造例Ｂ）マクロモノマー成分の分率が２０％である塩化ビニル系共重合樹脂の製造
ジャケットおよび攪拌機を備えた内容量２５リットルのステンレス鋼製重合反応機を脱気したのち塩化ビニルモノマー８０部を仕込み、次いで製造例１の片末端アクリロイル基ポリ（アクリル酸−ｎ−ブチル）マクロモノマー２０部を仕込んだのち、ジャケットに温水を通じて重合反応機内温を３０℃まで昇温し、１分間当たり９００回転の回転速度で３０分間攪拌した。ジャケットに水を通じて重合反応機内温を２０℃以下まで冷却したのち、鹸化度約８０モル％、平均重合度約２０００の部分鹸化ポリ酢酸ビニル０．１部、ｔ−ブチルパーオキシネオデカノエイト０．０３部、１，１，３，３−テトラメチルブチルパーオキシネオデカノエート０．０１部を仕込んだのち６０℃の温水１５０部を仕込み、重合温度５７℃で約６時間重合した。重合機内の未反応モノマーを回収したのち重合機を冷却し、スラリーを払い出した。得られたスラリーを脱水して熱風乾燥機にて５５℃で２４時間乾燥し、塩化ビニル／ポリ（アクリル酸−ｎ−ブチル）グラフト共重合樹脂Ｂを白色粉末として得た。
(Production Example B) Production of vinyl chloride copolymer resin having a macromonomer component fraction of 20% After degassing a 25 liter stainless steel polymerization reactor equipped with a jacket and a stirrer, vinyl chloride monomer 80 Then, 20 parts of acryloyl group poly (n-butyl acrylate) macromonomer of Production Example 1 was charged, and then the temperature inside the polymerization reactor was raised to 30 ° C. through warm water in the jacket, and then per minute It stirred for 30 minutes at the rotation speed of 900 rotations. After cooling the temperature inside the polymerization reactor to 20 ° C. or less through water through the jacket, 0.1 part of partially saponified polyvinyl acetate having a saponification degree of about 80 mol% and an average degree of polymerization of about 2000, t-butyl peroxyneodecanoate 0 0.03 part and 0.01 part of 1,1,3,3-tetramethylbutylperoxyneodecanoate were added, and then 150 parts of hot water at 60 ° C. was added, and polymerization was carried out at a polymerization temperature of 57 ° C. for about 6 hours. After recovering unreacted monomers in the polymerization machine, the polymerization machine was cooled and the slurry was discharged. The obtained slurry was dehydrated and dried in a hot air dryer at 55 ° C. for 24 hours to obtain a vinyl chloride / poly (n-butyl acrylate) graft copolymer resin B as a white powder.
（製造例Ｃ）マクロモノマー成分の分率が５０％である塩化ビニル系共重合樹脂の製造
ジャケットおよび攪拌機を備えた内容量２５リットルのステンレス鋼製重合反応機を脱気したのち塩化ビニルモノマー５０部を仕込み、次いで製造例１の片末端アクリロイル基ポリ（アクリル酸−ｎ−ブチル）マクロモノマー５０部を仕込んだのち、ジャケットに温水を通じて重合反応機内温を３０℃まで昇温し、１分間当たり９００回転の回転速度で３０分間攪拌した。ジャケットに水を通じて重合反応機内温を２０℃以下まで冷却したのち、鹸化度約８０モル％、平均重合度約２０００の部分鹸化ポリ酢酸ビニル０．１部、ｔ−ブチルパーオキシネオデカノエイト０．０３部、１，１，３，３−テトラメチルブチルパーオキシネオデカノエート０．０１部を仕込んだのち６０℃の温水１５０部を仕込み、重合温度５７℃で約６時間重合した。重合機内の未反応モノマーを回収したのち重合機を冷却し、スラリーを払い出した。得られたスラリーを脱水して熱風乾燥機にて５５℃で２４時間乾燥し、塩化ビニル／ポリ（アクリル酸−ｎ−ブチル）グラフト共重合樹脂Ｃを白色粉末として得た。
(Production Example C) Production of vinyl chloride copolymer resin having a fraction of macromonomer component of 50% Vinyl chloride monomer 50 after degassing a 25 liter stainless steel polymerization reactor equipped with a jacket and a stirrer Then, 50 parts of acryloyl group poly (n-butyl acrylate) macromonomer of Production Example 1 was charged, and then the temperature inside the polymerization reactor was raised to 30 ° C. through warm water in the jacket, per minute It stirred for 30 minutes at the rotation speed of 900 rotations. After cooling the temperature inside the polymerization reactor to 20 ° C. or less through water through the jacket, 0.1 part of partially saponified polyvinyl acetate having a saponification degree of about 80 mol% and an average degree of polymerization of about 2000, t-butyl peroxyneodecanoate 0 0.03 part and 0.01 part of 1,1,3,3-tetramethylbutylperoxyneodecanoate were added, and then 150 parts of hot water at 60 ° C. was added, and polymerization was carried out at a polymerization temperature of 57 ° C. for about 6 hours. After recovering unreacted monomers in the polymerization machine, the polymerization machine was cooled and the slurry was discharged. The obtained slurry was dehydrated and dried in a hot air dryer at 55 ° C. for 24 hours to obtain a vinyl chloride / poly (n-butyl acrylate) graft copolymer resin C as a white powder.
（実施例１）
一般用ポリ塩化ビニル樹脂（カネビニールＳ１００７：鐘淵化学工業（株）製、塩化ビニル単独重合樹脂、Ｋ値５７）１００部に対し、有機錫系安定剤（ＴＶＳ＃８８３１：日東化成（株）製、ジオクチル錫メルカプト）２．０部、酸化ポリエチレン系滑剤（ＡＣＰＥ６２９Ａ：アライドケミカル（株）製）０．２部、二塩基酸エステル系滑剤（Ｌｏｘｉｏｌ Ｇ−６０：コグニスジャパン（株）製）０．５部を、ヘンシェルミキサーを用いて樹脂温度が１１０℃になるまで混合し、その後５０℃以下まで冷却したものに、製造例Ａで得た塩化ビニル／ポリ（アクリル酸−ｎ−ブチル）グラフト共重合樹脂Ａを、ポリ塩化ビニル樹脂１００部当たり２部配合して塩化ビニル系樹脂組成物を得た。該組成物を単軸押出機（田辺プラスチックス機会（株）製ＶＳ５０ｍ／ｍ押出機ＦＨ５０−２３９）に供給し、吐出ストランドをペレタイザー（いすず化工機（株）製プラスチックス用加工機械ＳＣＦ−１００）にてペレット化した。該ペレットを射出成形機（ＦＡＮＵＣ社製 ＡＵＴＯＳＨＯＴ Ｔ Ｓｅｒｉｅｓ ７５Ｄ）に供給してスパイラルフローを評価した。スパイラルフロー長さが長いほど成形加工時の流動性が良好である。
(Example 1)
For 100 parts of general-purpose polyvinyl chloride resin (Kane Vinyl S1007: Kaneka Chemical Industry Co., Ltd., vinyl chloride homopolymer resin, K value 57), organotin stabilizer (TVS # 8831: Nitto Kasei Co., Ltd.) Made by dioctyltin mercapto 2.0 parts, polyethylene oxide lubricant (ACPE629A: Allied Chemical Co., Ltd.) 0.2 parts, dibasic acid ester lubricant (Loxiol G-60: Cognis Japan Co., Ltd.) 0 .5 parts was mixed with a Henschel mixer until the resin temperature reached 110 ° C., and then cooled to 50 ° C. or lower, and the vinyl chloride / poly (n-butyl acrylate) graft obtained in Production Example A was used. 2 parts of copolymer resin A was blended per 100 parts of polyvinyl chloride resin to obtain a vinyl chloride resin composition. The composition is supplied to a single screw extruder (VS50m / m extruder FH50-239 manufactured by Tanabe Plastics Opportunity Co., Ltd.), and the discharged strand is processed into a pelletizer (Isuzu Chemical Industries Co., Ltd. plastics processing machine SCF-100). ). The pellets were supplied to an injection molding machine (AUTOSHOT T Series 75D manufactured by FANUC) to evaluate spiral flow. The longer the spiral flow length, the better the fluidity during molding.
次いで同射出成形機にて耐衝撃性評価用短冊および引張試験用ダンベルを成形し、評価に供した。耐衝撃性の評価に当たっては、ＪＩＳ Ｋ７１１０に規定のアイゾット衝撃強さ試験方法に準じ、タイプ１の試験片に切削加工でタイプＡのノッチを付けた試験片を、室温２３℃および相対湿度５０％の恒温恒湿室中に４８時間静置したものを用いて、２３℃におけるアイゾット衝撃強さ（以下Ｉｚｏｄ衝撃強さと記す。単位はｋＪ／ｍ2。）を求めて評価した。引張強度の評価に当たっては、ＪＩＳ Ｋ７１６２に規定の引張試験方法に準じ、１Ａ型試験片を室温２３℃および相対湿度５０％の恒温恒湿室中に４８時間静置したものを用いて、試験速度１０ｍｍ／ｍｉｎで２３℃における抗張力（以下σｙと記す。単位はＭＰａ。）を求めて評価した。結果を表１に示す。 Next, a strip for impact resistance evaluation and a dumbbell for tensile test were molded by the same injection molding machine and subjected to evaluation. For the evaluation of impact resistance, in accordance with the Izod impact strength test method stipulated in JIS K7110, a type 1 test piece with a type A notch formed by cutting was used at a room temperature of 23 ° C. and a relative humidity of 50%. The Izod impact strength at 23 ° C. (hereinafter referred to as Izod impact strength. The unit is kJ / m 2 ) was used for evaluation. In the evaluation of tensile strength, in accordance with the tensile test method stipulated in JIS K7162, a 1A type test piece was allowed to stand for 48 hours in a constant temperature and humidity chamber at room temperature 23 ° C. and relative humidity 50%. Tensile strength at 23 ° C. at 10 mm / min (hereinafter referred to as σy; unit is MPa) was determined and evaluated. The results are shown in Table 1.
なお、ペレット化、スパイラルフロー評価、短冊およびダンベル成形、の各条件は以下の通りに設定した。
＜ペレット化条件＞
スクリュー回転数 ： ３０ｒｐｍ
シリンダー温度
シリンダー１ ： １５０℃
シリンダー２ ： １７０℃
シリンダー３ ： １８０℃
注：シリンダー番号は、原料供給側（ホッパー側）から押出方向に向かって、即ち
スクリュー先端に向かって、１、２、３の順で番号を付した。
The conditions for pelletization, spiral flow evaluation, strip and dumbbell molding were set as follows.
<Pelletization conditions>
Screw rotation speed: 30rpm
Cylinder temperature Cylinder 1: 150 ° C
Cylinder 2: 170 ° C
Cylinder 3: 180 ° C
Note: The cylinder numbers are assigned in the order of 1, 2, and 3 from the raw material supply side (hopper side) toward the extrusion direction, that is, toward the screw tip.
ヘッド温度
ダイ１ ： １９０℃
ダイ２ ： １９０℃
注：ダイ番号は、スクリュー先端から押出方向に向かって１、２の順で番号を付した。
＜スパイラルフロー評価＞
射出ユニット温度
ユニット１ ： １７０℃
ユニット２ ： １８０℃
ユニット３ ： １９０℃
注：ユニット番号は、原料供給側（ホッパー側）から押出方向に向かって、即ち
スクリュー先端に向かって、１、２、３の順で番号を付した。
Head temperature Die 1: 190 ° C
Die 2: 190 ° C
Note: Die numbers are assigned in the order of 1, 2 from the screw tip toward the extrusion direction.
<Spiral flow evaluation>
Injection unit temperature Unit 1: 170 ° C
Unit 2: 180 ° C
Unit 3: 190 ° C
Note: Unit numbers are assigned in the order of 1, 2, and 3 from the raw material supply side (hopper side) toward the extrusion direction, that is, toward the screw tip.
ノズル温度 ： １９０℃
金型温度 ： ４０℃
射出速度 ： ５０ｍｍ／ｓ
保圧 ： １３００ｋｇ／ｃｍ2
保圧保持時間 ： ３ｓｅｃ
射出・保圧切替位置： ２ｍｍ
最大射出圧力 ： １３００ｋｇ／ｃｍ2
最大射出時間 ： ３ｓｅｃ
最大保圧速度 ： ５ｍｍ／ｓ
背圧 ： １００ｋｇ／ｃｍ2
スクリュー回転数 ： ５０ｒｐｍ
冷却時間 ： ２０ｓｅｃ
＜短冊およびダンベル成形＞
射出ユニット温度
ユニット１ ： １７０℃
ユニット２ ： １８０℃
ユニット３ ： １９０℃
注：ユニット番号は、原料供給側（ホッパー側）から押出方向に向かって、即ち
スクリュー先端に向かって、１、２、３の順で番号を付した。
Nozzle temperature: 190 ° C
Mold temperature: 40 ℃
Injection speed: 50mm / s
Holding pressure: 1300 kg / cm 2
Holding pressure holding time: 3 sec
Injection / holding pressure switching position: 2mm
Maximum injection pressure: 1300kg / cm 2
Maximum injection time: 3 sec
Maximum holding pressure speed: 5mm / s
Back pressure: 100kg / cm 2
Screw rotation speed: 50rpm
Cooling time: 20 sec
<Strip and dumbbell molding>
Injection unit temperature Unit 1: 170 ° C
Unit 2: 180 ° C
Unit 3: 190 ° C
Note: Unit numbers are assigned in the order of 1, 2, and 3 from the raw material supply side (hopper side) toward the extrusion direction, that is, toward the screw tip.
ノズル温度 ： １９０℃
金型温度 ： ４０℃
射出速度 ： ２０ｍｍ／ｓ
保圧 ： ８００ｋｇ／ｃｍ2
保圧保持時間 ： ５ｓｅｃ
射出・保圧切替位置： ５ｍｍ
最大射出圧力 ： １５００ｋｇ／ｃｍ2
最大射出時間 ： ５ｓｅｃ
最大保圧速度 ： ５ｍｍ／ｓ
背圧 ： １００ｋｇ／ｃｍ2
スクリュー回転数 ： ５０ｒｐｍ
冷却時間 ： ２０ｓｅｃ
なお、該組成物は、ポリ塩化ビニル樹脂１００部を基準としたポリ（アクリル酸−ｎ−ブチル）マクロモノマー成分の含量が０．１部のものである。
Nozzle temperature: 190 ° C
Mold temperature: 40 ℃
Injection speed: 20mm / s
Holding pressure: 800 kg / cm 2
Holding pressure holding time: 5 sec
Injection / holding pressure switching position: 5mm
Maximum injection pressure: 1500 kg / cm 2
Maximum injection time: 5 sec
Maximum holding pressure speed: 5mm / s
Back pressure: 100kg / cm 2
Screw rotation speed: 50rpm
Cooling time: 20 sec
The composition has a poly (n-butyl acrylate) macromonomer component content of 0.1 part based on 100 parts of polyvinyl chloride resin.
（実施例２）
実施例１において、製造例Ａで得た塩化ビニル／ポリ（アクリル酸−ｎ−ブチル）グラフト共重合樹脂Ａの代わりに、製造例Ｂで得た塩化ビニル／ポリ（アクリル酸−ｎ−ブチル）グラフト共重合樹脂Ｂを、ポリ塩化ビニル樹脂１００部当たり０．５部配合すること以外は、実施例１と同様にして塩化ビニル系樹脂組成物を得、該組成物を実施例１と同様の方法を用いて、スパイラルフロー長さ、Ｉｚｏｄ衝撃強さおよびσｙを評価した。結果を表１に示す。
(Example 2)
In Example 1, instead of the vinyl chloride / poly (n-butyl acrylate) graft copolymer resin A obtained in Production Example A, the vinyl chloride / poly (n-butyl acrylate) obtained in Production Example B was used. Except for blending 0.5 parts of graft copolymer resin B per 100 parts of polyvinyl chloride resin, a vinyl chloride resin composition was obtained in the same manner as in Example 1, and the composition was the same as in Example 1. Methods were used to evaluate spiral flow length, Izod impact strength and σy. The results are shown in Table 1.
なお該組成物は、ポリ塩化ビニル樹脂１００部を基準としたポリ（アクリル酸−ｎ−ブチル）マクロモノマー成分の含量が０．１部のものである。 The composition has a poly (n-butyl acrylate) macromonomer component content of 0.1 part based on 100 parts of polyvinyl chloride resin.
（実施例３）
実施例２において、塩化ビニル／ポリ（アクリル酸−ｎ−ブチル）グラフト共重合樹脂Ｂを、ポリ塩化ビニル樹脂１００部当たり５部配合すること以外は、実施例２と同様にして塩化ビニル系樹脂組成物を得、該組成物を実施例２と同様の方法を用いて、スパイラルフロー長さ、Ｉｚｏｄ衝撃強さおよびσｙを評価した。結果を表１に示す。
(Example 3)
In Example 2, a vinyl chloride resin in the same manner as in Example 2 except that 5 parts of vinyl chloride / poly (n-butyl acrylate) graft copolymer resin B is blended per 100 parts of polyvinyl chloride resin. A composition was obtained, and the spiral flow length, Izod impact strength and σy of the composition were evaluated using the same method as in Example 2. The results are shown in Table 1.
なお該組成物は、ポリ塩化ビニル樹脂１００部を基準としたポリ（アクリル酸−ｎ−ブチル）マクロモノマー成分の含量が１部のものである。 The composition has a poly (n-butyl acrylate) macromonomer component content of 1 part based on 100 parts of polyvinyl chloride resin.
（実施例４）
実施例１において、製造例Ａで得た塩化ビニル／ポリ（アクリル酸−ｎ−ブチル）グラフト共重合樹脂Ａの代わりに、製造例Ｃで得た塩化ビニル／ポリ（アクリル酸−ｎ−ブチル）グラフト共重合樹脂Ｃを、ポリ塩化ビニル樹脂１００部当たり０．２部配合すること以外は、実施例１と同様にして塩化ビニル系樹脂組成物を得、該組成物を実施例１と同様の方法を用いて、スパイラルフロー長さ、Ｉｚｏｄ衝撃強さおよびσｙを評価した。結果を表１に示す。
Example 4
In Example 1, instead of the vinyl chloride / poly (n-butyl acrylate) graft copolymer resin A obtained in Production Example A, the vinyl chloride / poly (n-butyl acrylate) obtained in Production Example C was used. Except for blending 0.2 parts of graft copolymer resin C per 100 parts of polyvinyl chloride resin, a vinyl chloride resin composition was obtained in the same manner as in Example 1, and the composition was the same as in Example 1. Methods were used to evaluate spiral flow length, Izod impact strength and σy. The results are shown in Table 1.
なお該組成物は、ポリ塩化ビニル樹脂１００部を基準としたポリ（アクリル酸−ｎ−ブチル）マクロモノマー成分の含量が０．１部のものである。 The composition has a poly (n-butyl acrylate) macromonomer component content of 0.1 part based on 100 parts of polyvinyl chloride resin.
（実施例５）
実施例４において、塩化ビニル／ポリ（アクリル酸−ｎ−ブチル）グラフト共重合樹脂Ｃを、ポリ塩化ビニル樹脂１００部当たり２部配合すること以外は、実施例４と同様にして塩化ビニル系樹脂組成物を得、該組成物を実施例４と同様の方法を用いて、スパイラルフロー長さ、Ｉｚｏｄ衝撃強さおよびσｙを評価した。結果を表１に示す。
(Example 5)
In Example 4, a vinyl chloride resin in the same manner as in Example 4 except that 2 parts of vinyl chloride / poly (n-butyl acrylate) graft copolymer resin C is blended per 100 parts of polyvinyl chloride resin. A composition was obtained, and the spiral flow length, Izod impact strength, and σy of the composition were evaluated using the same method as in Example 4. The results are shown in Table 1.
なお該組成物は、ポリ塩化ビニル樹脂１００部を基準としたポリ（アクリル酸−ｎ−ブチル）マクロモノマー成分の含量が１部のものである。 The composition has a poly (n-butyl acrylate) macromonomer component content of 1 part based on 100 parts of polyvinyl chloride resin.
（比較例１）
実施例１において、製造例Ａで得た塩化ビニル／ポリ（アクリル酸−ｎ−ブチル）グラフト共重合樹脂Ａを配合しないこと以外は、実施例１と同様にして塩化ビニル系樹脂組成物を得、該組成物を実施例１と同様の方法を用いて、スパイラルフロー長さ、Ｉｚｏｄ衝撃強さおよびσｙを評価した。結果を表１に示す。スパイラルフロー長さ、Ｉｚｏｄ衝撃強さおよびσｙの値がいずれも全ての実施例より低く、好ましくない。
(Comparative Example 1)
In Example 1, a vinyl chloride resin composition was obtained in the same manner as in Example 1 except that the vinyl chloride / poly (acrylic acid-n-butyl) graft copolymer resin A obtained in Production Example A was not blended. The composition was evaluated for spiral flow length, Izod impact strength and σy using the same method as in Example 1. The results are shown in Table 1. The values of spiral flow length, Izod impact strength, and σy are all lower than in all the examples and are not preferable.
（比較例２）
比較例１において、さらに衝撃強化剤（メタブレンＣ−３２３Ａ：三菱レイヨン（株）製、ＭＢＳ樹脂）を３部配合すること以外は比較例１と同様にして塩化ビニル系樹脂組成物を得、該組成物を比較例１と同様の方法を用いて、スパイラルフロー長さ、Ｉｚｏｄ衝撃強さおよびσｙを評価した。結果を表１に示す。スパイラルフロー長さおよびσｙの値がいずれも全ての実施例より低く、向上効果は不充分である。
(Comparative Example 2)
In Comparative Example 1, a vinyl chloride resin composition was obtained in the same manner as in Comparative Example 1, except that 3 parts of an impact strengthener (Methbrene C-323A: manufactured by Mitsubishi Rayon Co., Ltd., MBS resin) was further blended. Using the same method as in Comparative Example 1, the composition was evaluated for spiral flow length, Izod impact strength, and σy. The results are shown in Table 1. Both the spiral flow length and the value of σy are lower than in all the examples, and the improvement effect is insufficient.
（比較例３）
比較例２において、衝撃強化剤の代わりにＣＰＥ（（株）ダイソー製、ダイソラックＨ−１３５）を３部配合すること以外は比較例２と同様にして塩化ビニル系樹脂組成物を得、該組成物を比較例２と同様の方法を用いて、スパイラルフロー長さ、Ｉｚｏｄ衝撃強さおよびσｙを評価した。結果を表１に示す。スパイラルフロー長さおよびσｙの値がいずれも全ての実施例より低く、向上効果は不充分である。
(Comparative Example 3)
In Comparative Example 2, a vinyl chloride resin composition was obtained in the same manner as in Comparative Example 2 except that 3 parts of CPE (Daisolac H-135, manufactured by Daiso Co., Ltd.) was used instead of the impact strengthening agent. Using the same method as in Comparative Example 2, the spiral flow length, Izod impact strength, and σy were evaluated. The results are shown in Table 1. Both the spiral flow length and the value of σy are lower than in all the examples, and the improvement effect is insufficient.
（比較例４）
比較例２において、衝撃強化剤の代わりに可塑剤としてジ−２−エチルヘキシルフタレート（製品名ＤＯＰ、（株）ジェイ・プラス製、以下ＤＯＰと略す）を５部配合すること以外は比較例２と同様にして塩化ビニル系樹脂組成物を得、該組成物を比較例２と同様の方法を用いて、スパイラルフロー長さ、Ｉｚｏｄ衝撃強さおよびσｙを評価した。結果を表１に示す。Ｉｚｏｄ衝撃強さおよびσｙの値がいずれも全ての実施例より低く、向上効果は不充分である。
(Comparative Example 4)
Comparative Example 2 is the same as Comparative Example 2 except that 5 parts of di-2-ethylhexyl phthalate (product name: DOP, manufactured by J Plus Co., Ltd., hereinafter abbreviated as DOP) is used as a plasticizer instead of an impact enhancer. Similarly, a vinyl chloride resin composition was obtained, and the spiral flow length, Izod impact strength and σy of the composition were evaluated using the same method as in Comparative Example 2. The results are shown in Table 1. The values of Izod impact strength and σy are both lower than in all examples, and the improvement effect is insufficient.
（比較例５）
比較例２において、衝撃強化剤の代わりにメタクリル酸メチル系加工助剤（メタブレンＰ−５５１Ａ：三菱レイヨン（株）製）を１部配合すること以外は比較例２と同様にして塩化ビニル系樹脂組成物を得、該組成物を比較例２と同様の方法を用いて、スパイラルフロー長さ、Ｉｚｏｄ衝撃強さおよびσｙを評価した。結果を表１に示す。スパイラルフロー長さおよびσｙの値がいずれも全ての実施例より低く、向上効果は不充分である。
(Comparative Example 5)
In Comparative Example 2, a vinyl chloride resin was used in the same manner as in Comparative Example 2 except that 1 part of a methyl methacrylate-based processing aid (methabrene P-551A: manufactured by Mitsubishi Rayon Co., Ltd.) was used instead of the impact enhancer. A composition was obtained, and the spiral flow length, Izod impact strength, and σy of the composition were evaluated using the same method as in Comparative Example 2. The results are shown in Table 1. Both the spiral flow length and the value of σy are lower than in all the examples, and the improvement effect is insufficient.
（比較例６）
実施例１において、製造例Ａで得た塩化ビニル／ポリ（アクリル酸−ｎ−ブチル）グラフト共重合樹脂Ａを、ポリ塩化ビニル樹脂１００部当たり１部配合すること以外は、実施例１と同様にして塩化ビニル系樹脂組成物を得、該組成物を実施例１と同様の方法を用いて、スパイラルフロー長さ、Ｉｚｏｄ衝撃強さおよびσｙを評価した。結果を表１に示す。スパイラルフロー長さ、Ｉｚｏｄ衝撃強さおよびσｙの値がいずれも全ての実施例より低く、比較例１とほぼ同等であり、向上効果は不充分である。
(Comparative Example 6)
In Example 1, the same procedure as in Example 1 except that 1 part of the vinyl chloride / poly (n-butyl acrylate) graft copolymer resin A obtained in Production Example A is blended per 100 parts of polyvinyl chloride resin. Thus, a vinyl chloride resin composition was obtained, and the spiral flow length, Izod impact strength and σy of the composition were evaluated in the same manner as in Example 1. The results are shown in Table 1. The values of spiral flow length, Izod impact strength, and σy are all lower than in all examples and are almost the same as in Comparative Example 1, and the improvement effect is insufficient.
なお該組成物は、ポリ塩化ビニル樹脂１００部を基準としたポリ（アクリル酸−ｎ−ブチル）マクロモノマー成分の含量が０．０５部のものである。 The composition has a poly (n-butyl acrylate) macromonomer component content of 0.05 parts based on 100 parts of polyvinyl chloride resin.
（比較例７）
実施例４において、製造例Ｃで得た塩化ビニル／ポリ（アクリル酸−ｎ−ブチル）グラフト共重合樹脂Ｃを、ポリ塩化ビニル樹脂１００部当たり１．５部配合すること以外は、実施例４と同様にして塩化ビニル系樹脂組成物を得、該組成物を実施例４と同様の方法を用いて、スパイラルフロー長さ、Ｉｚｏｄ衝撃強さおよびσｙを評価した。結果を表１に示す。Ｉｚｏｄ衝撃強さおよびσｙの値がいずれも全ての実施例より低く、向上効果は不充分である。
(Comparative Example 7)
In Example 4, Example 4 except that 1.5 parts of polyvinyl chloride / poly (n-butyl acrylate) graft copolymer resin C obtained in Production Example C is blended per 100 parts of polyvinyl chloride resin. A vinyl chloride resin composition was obtained in the same manner as described above, and the spiral flow length, Izod impact strength, and σy of the composition were evaluated in the same manner as in Example 4. The results are shown in Table 1. The values of Izod impact strength and σy are both lower than in all examples, and the improvement effect is insufficient.
なお該組成物は、ポリ塩化ビニル樹脂１００部を基準としたポリ（アクリル酸−ｎ−ブチル）マクロモノマー成分の含量が１．５部のものである。 The composition has a poly (n-butyl acrylate) macromonomer component content of 1.5 parts based on 100 parts of polyvinyl chloride resin.
Claims (3)
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004099121A JP2005281570A (en) | 2004-03-30 | 2004-03-30 | Vinyl chloride resin composition for injection-molded article |
| US10/594,586 US20080242802A1 (en) | 2004-03-30 | 2005-03-16 | Vinyl Chloride Resin Composition |
| PCT/JP2005/004598 WO2005097889A1 (en) | 2004-03-30 | 2005-03-16 | Vinyl chloride resin composition |
| KR1020067022030A KR20070006858A (en) | 2004-03-30 | 2005-03-16 | Vinyl chloride resin composition |
| TW094108578A TW200604276A (en) | 2004-03-30 | 2005-03-21 | Vinyl chlorided-based resin composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004099121A JP2005281570A (en) | 2004-03-30 | 2004-03-30 | Vinyl chloride resin composition for injection-molded article |
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|---|---|
| JP2005281570A true JP2005281570A (en) | 2005-10-13 |
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| JP2004099121A Pending JP2005281570A (en) | 2004-03-30 | 2004-03-30 | Vinyl chloride resin composition for injection-molded article |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006103809A1 (en) * | 2005-03-25 | 2006-10-05 | Kaneka Corporation | Gamma-ray-resistant, flexible vinyl chloride molded article |
| WO2006103806A1 (en) * | 2005-03-25 | 2006-10-05 | Kaneka Corporation | Vinyl chloride copolymer resin composition and vinyl chloride injection molded article produced from the same |
| WO2006103808A1 (en) * | 2005-03-25 | 2006-10-05 | Kaneka Corporation | Stain-proof vinyl chloride film |
| WO2006103807A1 (en) * | 2005-03-25 | 2006-10-05 | Kaneka Corporation | Vinyl chloride sheet |
| WO2006112076A1 (en) * | 2005-03-31 | 2006-10-26 | Kaneka Corporation | Vinyl chloride resin dope composition |
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| WO2006103809A1 (en) * | 2005-03-25 | 2006-10-05 | Kaneka Corporation | Gamma-ray-resistant, flexible vinyl chloride molded article |
| WO2006103806A1 (en) * | 2005-03-25 | 2006-10-05 | Kaneka Corporation | Vinyl chloride copolymer resin composition and vinyl chloride injection molded article produced from the same |
| WO2006103808A1 (en) * | 2005-03-25 | 2006-10-05 | Kaneka Corporation | Stain-proof vinyl chloride film |
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| WO2006112076A1 (en) * | 2005-03-31 | 2006-10-26 | Kaneka Corporation | Vinyl chloride resin dope composition |
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