JP5650915B2 - Method for producing vinyl chloride hollow particles, vinyl chloride hollow particles, vinyl chloride resin composition, and vinyl chloride molded article - Google Patents
Method for producing vinyl chloride hollow particles, vinyl chloride hollow particles, vinyl chloride resin composition, and vinyl chloride molded article Download PDFInfo
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- JP5650915B2 JP5650915B2 JP2010047313A JP2010047313A JP5650915B2 JP 5650915 B2 JP5650915 B2 JP 5650915B2 JP 2010047313 A JP2010047313 A JP 2010047313A JP 2010047313 A JP2010047313 A JP 2010047313A JP 5650915 B2 JP5650915 B2 JP 5650915B2
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- Prior art keywords
- vinyl chloride
- hollow particles
- polymerization
- weight
- monomer
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- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims description 159
- 239000002245 particle Substances 0.000 title claims description 76
- 239000011342 resin composition Substances 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 25
- 239000000178 monomer Substances 0.000 claims description 83
- 238000006116 polymerization reaction Methods 0.000 claims description 76
- 229920005989 resin Polymers 0.000 claims description 32
- 239000011347 resin Substances 0.000 claims description 32
- 239000002270 dispersing agent Substances 0.000 claims description 24
- 239000000725 suspension Substances 0.000 claims description 12
- 239000003505 polymerization initiator Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 6
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- -1 ethylene oxide modified trimethylolpropane Chemical class 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 239000008119 colloidal silica Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 239000000498 cooling water Substances 0.000 description 8
- 229920000915 polyvinyl chloride Polymers 0.000 description 8
- 239000004800 polyvinyl chloride Substances 0.000 description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 230000005484 gravity Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- NUIZZJWNNGJSGL-UHFFFAOYSA-N 2-phenylpropan-2-yl 2,2-dimethyloctaneperoxoate Chemical compound CCCCCCC(C)(C)C(=O)OOC(C)(C)c1ccccc1 NUIZZJWNNGJSGL-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000001506 calcium phosphate Substances 0.000 description 4
- 229910000389 calcium phosphate Inorganic materials 0.000 description 4
- 235000011010 calcium phosphates Nutrition 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000010558 suspension polymerization method Methods 0.000 description 4
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004609 Impact Modifier Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 3
- 239000013585 weight reducing agent Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-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
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- ISYWECDDZWTKFF-UHFFFAOYSA-N nonadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCCC(O)=O ISYWECDDZWTKFF-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- UKDKWYQGLUUPBF-UHFFFAOYSA-N 1-ethenoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOC=C UKDKWYQGLUUPBF-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- QAPLQMROVGLYLM-UHFFFAOYSA-N 2-butan-2-ylperoxybutane Chemical group CCC(C)OOC(C)CC QAPLQMROVGLYLM-UHFFFAOYSA-N 0.000 description 1
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- ZPOLOEWJWXZUSP-AATRIKPKSA-N bis(prop-2-enyl) (e)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C\C(=O)OCC=C ZPOLOEWJWXZUSP-AATRIKPKSA-N 0.000 description 1
- YLTDNYQTDYMOBH-UHFFFAOYSA-N bis(prop-2-enyl) 2-hydroxybutanedioate Chemical compound C=CCOC(=O)C(O)CC(=O)OCC=C YLTDNYQTDYMOBH-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- HABAXTXIECRCKH-UHFFFAOYSA-N bis(prop-2-enyl) butanedioate Chemical compound C=CCOC(=O)CCC(=O)OCC=C HABAXTXIECRCKH-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- NSGQRLUGQNBHLD-UHFFFAOYSA-N butan-2-yl butan-2-yloxycarbonyloxy carbonate Chemical compound CCC(C)OC(=O)OOC(=O)OC(C)CC NSGQRLUGQNBHLD-UHFFFAOYSA-N 0.000 description 1
- ZGPBOPXFOJBLIV-UHFFFAOYSA-N butoxycarbonyloxy butyl carbonate Chemical compound CCCCOC(=O)OOC(=O)OCCCC ZGPBOPXFOJBLIV-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229960000878 docusate sodium Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
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- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 238000004898 kneading Methods 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 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
- 150000001451 organic peroxides Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000002948 undecyl 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])[H] 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、塩化ビニル系中空粒子の製造方法、塩化ビニル系中空粒子、塩化ビニル系樹脂組成物及び塩化ビニル系成形体に関する。 The present invention relates to a method for producing vinyl chloride hollow particles, a vinyl chloride hollow particle, a vinyl chloride resin composition, and a vinyl chloride molded article.
塩化ビニル樹脂(以下、「PVC」と記載することがある)は、優れた物理化学的性質を有し、かつ、他の樹脂に比べて安価なことから成形品の広い分野で利用されている。しかし、PVCは、比重が1.4と大きいため、他の樹脂、例えば、発泡ポリウレタン(d=0.5〜0.7)と比較すると重いという欠点がある。
そのため、塩化ビニル樹脂成形品の軽量化に対する種々の試みがなされている。
例えば、塩化ビニルプレートのような成形体では、軽量化の目的で化学的に発泡させるなどの試みがなされている(例えば、引用文献1参照)。また、塩化ビニルを高空隙にするために、塩化ビニルモノマーを重合途中で除去する方法が提案されている(例えば、特許文献2参照)。さらに、中空樹脂微粒子の空隙率と強度とを確保するために、非重合性の有機溶媒を用いる方法が提案されている(例えば、引用文献3参照)。
Vinyl chloride resin (hereinafter sometimes referred to as “PVC”) has excellent physicochemical properties and is less expensive than other resins, and is used in a wide range of molded products. . However, since PVC has a large specific gravity of 1.4, there is a disadvantage that it is heavier than other resins such as foamed polyurethane (d = 0.5 to 0.7).
Therefore, various attempts have been made to reduce the weight of vinyl chloride resin molded products.
For example, a molded body such as a vinyl chloride plate has been tried to be chemically foamed for the purpose of weight reduction (see, for example, cited document 1). Moreover, in order to make vinyl chloride into a high space | gap, the method of removing a vinyl chloride monomer in the middle of superposition | polymerization is proposed (for example, refer patent document 2). Furthermore, in order to ensure the porosity and strength of the hollow resin fine particles, a method using a non-polymerizable organic solvent has been proposed (see, for example, cited document 3).
しかし、発泡剤をPVCに配合した成形体では、発泡倍率に制限があり、わずかの条件の違いにより、所望の発泡倍率が得られないことがある。また、独立気泡の他に、相当の割合で連続気泡が含まれる。さらに、成形品の部位により、気泡が不均一に分布することもあった。
従って、加熱後の真空成形のような二次加工成形体では、ゲル化したり、そのセルが潰れたり、気泡が変形するなどにより、比重の低減効果がなくなることがあった。
また、非重合性の有機溶媒を用いる場合には、製造コストが増大するという課題もある。
このような状況下、さらに難燃性を向上させるために、塩化ビニルと同一、塩化ビニルに起因する構成単位をその一部に含むなど、塩化ビニルに類似する素材の中空粒子が求められている。
However, in a molded body in which a foaming agent is blended with PVC, the expansion ratio is limited, and a desired expansion ratio may not be obtained due to a slight difference in conditions. In addition to closed cells, open cells are included in a considerable proportion. Furthermore, air bubbles may be unevenly distributed depending on the part of the molded product.
Therefore, in a secondary processed molded body such as vacuum forming after heating, the effect of reducing specific gravity may be lost due to gelation, collapse of the cell, deformation of bubbles, and the like.
In addition, when a non-polymerizable organic solvent is used, there is a problem that the manufacturing cost increases.
Under such circumstances, in order to further improve the flame retardancy, hollow particles made of a material similar to vinyl chloride, such as the same as vinyl chloride, including a structural unit derived from vinyl chloride as a part thereof, are required. .
本発明は上記問題点に鑑みなされたものであり、塩化ビニル自体の優れた特性を確保しながら、塩化ビニル系の成形体として軽量化を図る、つまり空隙率を確保することができるとともに、二次加工性をも確保して強度の向上を図ることができる塩化ビニル系中空粒子の製造方法、塩化ビニル系中空粒子、該中空粒子を含有する塩化ビニル系樹脂組成物及び該塩化ビニル系樹脂組成物を用いて得られた塩化ビニル系成形体を提供することを目的とする。 The present invention has been made in view of the above problems, and while ensuring the excellent characteristics of vinyl chloride itself, it is possible to reduce the weight as a vinyl chloride-based molded product, that is, to ensure a void ratio. Method for producing vinyl chloride-based hollow particles capable of ensuring the next processability and improving strength, vinyl chloride-based hollow particles, vinyl chloride-based resin composition containing the hollow particles, and vinyl chloride-based resin composition It aims at providing the vinyl chloride type molded object obtained by using a thing.
本発明の塩化ビニル系中空粒子の製造方法は、
(1)主成分としての塩化ビニルと多官能性モノマーとを含むモノマー成分、重合開始剤及び分散剤を極性媒体に混合して懸濁液を調製し、
(2)該懸濁液を加熱してモノマー成分を重合し、該モノマー成分の重合率が75%以下の時点で未反応塩化ビニルを除去して、樹脂粒子を形成し、
(3)該樹脂粒子を脱水及び乾燥する工程を含むことを特徴とする。
The method for producing the vinyl chloride hollow particles of the present invention comprises:
(1) A monomer component containing vinyl chloride as a main component and a polyfunctional monomer, a polymerization initiator and a dispersant are mixed in a polar medium to prepare a suspension,
(2) The suspension is heated to polymerize the monomer component, and when the polymerization rate of the monomer component is 75% or less, unreacted vinyl chloride is removed to form resin particles,
(3) It includes a step of dehydrating and drying the resin particles.
このような塩化ビニル系中空粒子の製造方法では、
塩化ビニルが全モノマー成分の70重量%以上であることが好ましい。
In the method for producing such vinyl chloride hollow particles,
It is preferable that vinyl chloride is 70% by weight or more of the total monomer components.
また、本発明の塩化ビニル系中空粒子は、主成分としての塩化ビニルと多官能性モノマーとを含むモノマー成分と、重合開始剤と、分散剤とを含む系での懸濁重合によって得られ、空隙率が25%以上、75%未満であることを特徴とする。
このような塩化ビニル系中空粒子では、塩化ビニルが、全モノマー成分の70重量%以上であることが好ましい。
The vinyl chloride hollow particles of the present invention are obtained by suspension polymerization in a system containing a monomer component containing vinyl chloride as a main component and a polyfunctional monomer, a polymerization initiator, and a dispersant. The porosity is 25% or more and less than 75%.
In such vinyl chloride-based hollow particles, vinyl chloride is preferably 70% by weight or more of the total monomer components.
さらに、本発明の塩化ビニル系樹脂組成物は、
少なくとも上述した塩化ビニル系中空粒子と、塩化ビニル系樹脂とを含む塩化ビニル系樹脂組成物であって、
前記塩化ビニル系樹脂100重量部に対して、前記中空粒子が3〜50重量部含有されてなることを特徴とする。
Furthermore, the vinyl chloride resin composition of the present invention is
A vinyl chloride resin composition comprising at least the vinyl chloride hollow particles described above and a vinyl chloride resin,
The hollow particles are contained in an amount of 3 to 50 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
また、本発明の塩化ビニル系成形体は、上記塩化ビニル系樹脂組成物によって成形されてなることを特徴とする。 The vinyl chloride-based molded article of the present invention is characterized by being molded from the vinyl chloride-based resin composition.
本発明によれば、塩化ビニル自体の優れた特性を確保しながら、空隙率を確保して、塩化ビニル系の成形体として軽量化を図ることができるとともに、強度を向上させて、二次加工性を良好とすることができる塩化ビニル系中空粒子の製造方法、塩化ビニル系中空粒子、該中空粒子を含有する塩化ビニル系樹脂組成物を得ることができる。 According to the present invention, while ensuring the excellent characteristics of vinyl chloride itself, it is possible to secure a porosity and to reduce the weight as a vinyl chloride-based molded body, to improve the strength, and to perform secondary processing. A method for producing vinyl chloride hollow particles capable of improving the properties, vinyl chloride hollow particles, and a vinyl chloride resin composition containing the hollow particles can be obtained.
また、この塩化ビニル樹脂組成物を用いて得られた塩化ビニル系成形体は、塩化ビニル系樹脂が本来有する耐衝撃性、耐熱性等の物理的性質及び耐溶剤性、耐酸性等の化学的性質に優れた物理化学的性質を備えるとともに、従来の塩化ビニル系成形体に比較して軽量化を図ることができ、種々の用途に用いることができる。 In addition, a vinyl chloride-based molded article obtained using this vinyl chloride resin composition has a physical property such as impact resistance and heat resistance inherent in the vinyl chloride resin and chemical properties such as solvent resistance and acid resistance. In addition to having excellent physicochemical properties, the weight can be reduced as compared with conventional vinyl chloride-based molded articles, and it can be used in various applications.
<塩化ビニル系中空粒子の製造方法>
本発明の塩化ビニル系中空粒子の製造方法では、まず、(1)主成分としての塩化ビニル(以下、「塩ビ」と記載する場合がある)と多官能性モノマーとを含むモノマー成分、重合開始剤及び分散剤を極性溶媒に混合して懸濁液を調製する。
<Method for producing vinyl chloride hollow particles>
In the method for producing vinyl chloride hollow particles of the present invention, first, (1) a monomer component containing vinyl chloride as a main component (hereinafter sometimes referred to as “vinyl chloride”) and a polyfunctional monomer, polymerization initiation A suspension is prepared by mixing the agent and dispersant in a polar solvent.
<モノマー成分>
モノマー成分としては、塩化ビニルと、多官能性モノマーと、任意にその他のモノマー等とからなる混合モノマーを用いることが好ましい。
<Monomer component>
As the monomer component, it is preferable to use a mixed monomer composed of vinyl chloride, a polyfunctional monomer, and optionally other monomers.
塩化ビニルは、モノマー成分において、主成分として含有されていることが適している。主成分とは、全モノマー成分中に占める重量割合が最も多いことを意味する。その量は、50重量%以上であることが適しており、60重量%以上であることが好ましく、70重量%以上、さらには75重量%以上であることがより好ましい。 It is suitable that vinyl chloride is contained as a main component in the monomer component. A main component means that the weight ratio which occupies in all the monomer components is the largest. The amount is suitably 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more, and even more preferably 75% by weight or more.
多官能性モノマーは、塩化ビニル系中空粒子の耐圧縮強度を改善する等の目的で添加するものであり、その種類は、特に限定されない。
例えば、エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、1,6−ヘキサンジオールジ(メタ)アクリレート、トリメチロールプロパンジ(メタ)アクリレート等のジ(メタ)アクリレート;
トリメチロールプロパントリ(メタ)アクリレート、エチレンオキサイド変性トリメチロールプロパントリ(メタ)アクリレート、ペンタエリストールトリ(メタ)アクリレート等のトリ(メタ)アクリレート;
ペンタエリストールテトラ(メタ)アクリレート、ジペンタエリストールヘキサ(メタ)アクリレート、ジアリルフタレート、ジアリルマレート、ジアリルフマレート、ジアリルサクシネート、トリアリルイソシアヌレート等のジ又はトリアリル化合物;
ジビニルベンゼン、ブタジエン等のジビニル化合物等が挙げられる。
これらは単独で用いてもよく、2種以上を併用してもよい。
The polyfunctional monomer is added for the purpose of improving the compression strength of the vinyl chloride hollow particles, and the kind thereof is not particularly limited.
For example, di (meth) acrylate such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane di (meth) acrylate, etc. (Meth) acrylate;
Tri (meth) acrylates such as trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate;
Di- or triallyl compounds such as pentaerythrole tetra (meth) acrylate, dipentaerystol hexa (meth) acrylate, diallyl phthalate, diallyl malate, diallyl fumarate, diallyl succinate, triallyl isocyanurate;
And divinyl compounds such as divinylbenzene and butadiene.
These may be used alone or in combination of two or more.
混合モノマーにおける多官能性モノマーの配合量は、特に限定されないが、0.1重量%以上であることが好ましく、0.3重量%以上であることがより好ましい。上限は特に限定されないが、50重量%以下であることが適しており、30重量%以下であることが好ましい。この範囲とすることにより、塩化ビニルの特性を確保しながら、得られる塩化ビニル系中空粒子の耐圧縮強度を十分に確保することができる。 Although the compounding quantity of the polyfunctional monomer in a mixed monomer is not specifically limited, It is preferable that it is 0.1 weight% or more, and it is more preferable that it is 0.3 weight% or more. The upper limit is not particularly limited, but is suitably 50% by weight or less, and preferably 30% by weight or less. By setting it as this range, the compressive strength of the obtained vinyl chloride hollow particles can be sufficiently ensured while ensuring the characteristics of vinyl chloride.
その他のモノマーとしては、塩化ビニルモノマーと共重合可能な不飽和結合を有するモノマーが挙げられる。例えば、エチレン、プロピレン、ブチレン等のα−オレフィン類;酢酸ビニル、プロピオン酸ビニル等のビニルエステル類;ブチルビニルエーテル、セチルビニルエーテル等のビニルエーテル類;メチル(メタ)アクリレート、エチル(メタ)アクリレート、ブチルアクリレート、フェニルメタクリレート等の(メタ)アクリル酸エステル類;スチレン、α−メチルスチレン等の芳香族ビニル類;塩化ビニリデン、フッ化ビニリデン等のハロゲン化ビニルビニル類;N−フェニルマレイミド、N−シクロヘキシルマレイミド等のN−置換マレイミド類、(メタ)アクリル酸、無水マレイン酸、アクリロニトリル等が挙げられる。これらは単独で用いてもよいし、2種以上併用してもよい。 Examples of other monomers include monomers having an unsaturated bond copolymerizable with a vinyl chloride monomer. For example, α-olefins such as ethylene, propylene and butylene; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as butyl vinyl ether and cetyl vinyl ether; methyl (meth) acrylate, ethyl (meth) acrylate and butyl acrylate (Meth) acrylic acid esters such as phenyl methacrylate; aromatic vinyls such as styrene and α-methylstyrene; vinyl vinyl halides such as vinylidene chloride and vinylidene fluoride; N-phenylmaleimide, N-cyclohexylmaleimide, etc. N-substituted maleimides, (meth) acrylic acid, maleic anhydride, acrylonitrile and the like can be mentioned. These may be used alone or in combination of two or more.
<重合開始剤>
重合開始剤は、上記モノマー成分に可溶である油溶性のフリーラジカルを発生する化合物であれば、特に限定されない。例えば、ベンゾイルパーオキサイド、ラウロイルパーオキサイド、ジブチルパーオキシジカーボネート、α−クミルパーオキシネオデカノエート等の有機系過酸化物等が挙げられる。なかでも、2種以上を組み合わせて用いることが適している。
重合開始剤の添加量は特に限定されないが、モノマー成分100重量部に対して0.01〜3重量部が好ましい。より好まくは、0.1〜0.5重量部である。
<Polymerization initiator>
The polymerization initiator is not particularly limited as long as it is a compound that generates an oil-soluble free radical that is soluble in the monomer component. Examples thereof include organic peroxides such as benzoyl peroxide, lauroyl peroxide, dibutyl peroxydicarbonate, α-cumylperoxyneodecanoate, and the like. Among these, it is suitable to use a combination of two or more.
Although the addition amount of a polymerization initiator is not specifically limited, 0.01-3 weight part is preferable with respect to 100 weight part of monomer components. More preferably, it is 0.1 to 0.5 part by weight.
<分散剤>
分散剤は、塩化ビニル系中空粒子の製造において、媒体中に、モノマー成分からなる液滴を懸濁/分散させ、その分散を安定化する役割を有するものである。
<Dispersant>
The dispersant has a role of suspending / dispersing droplets composed of monomer components in the medium and stabilizing the dispersion in the production of the vinyl chloride hollow particles.
分散剤としては、特に限定されず、例えば、シリカ、リン酸カルシウム、水酸化マグネシウム、水酸化アルミニウム、水酸化第二鉄、硫酸バリウム、硫酸カルシウム、硫酸ナトリウム、蓚酸カルシウム、炭酸カルシウム、炭酸バリウム、炭酸マグネシウムなどが挙げられる。特に、コロイド状の無機系分散剤(例えば、コライダルシリカ、リン酸カルシウム等)が好ましい。
また、例えば、ジエタノールアミンと脂肪族ジカルボン酸との縮合生成物、尿素とホルムアルデヒドとの縮合生成物、ポリビニルアルコール、ポリビニルピロリドン、ポリエチレンオキサイド、ポリエチレンイミン、テトラメチルアンモニウムヒドロキシド、ゼラチン、メチルセルロース、ジオクチルスルホサクシネート、ソルビタンエステル等を使用してもよい。
さらに、例えば、中空粒子の製造において用いられる、後述する極性媒体中に溶解することができるもの、以下の1以上の親水基等(水酸基、カルボキシル基、アミノ基、スルホン酸基、アミド基等)の置換基を備えるもの等が挙げられる。
水酸基を有するものとして、カルボキシメチルセルロース等、カルボキシル基を有するものとして、ポリ(メタ)アクリル酸等、アミノ基を有するものとして、ゼラチン等、スルホン酸基を有するものとして、ポリスチレンスルホン酸等が挙げられる。
アミド基を有するものとして、ポリアクリルアミド類、ポリビニルピロリドン等が挙げられる。
The dispersant is not particularly limited. For example, silica, calcium phosphate, magnesium hydroxide, aluminum hydroxide, ferric hydroxide, barium sulfate, calcium sulfate, sodium sulfate, calcium oxalate, calcium carbonate, barium carbonate, magnesium carbonate. Etc. In particular, colloidal inorganic dispersants (for example, colloidal silica, calcium phosphate, etc.) are preferable.
Also, for example, condensation products of diethanolamine and aliphatic dicarboxylic acids, condensation products of urea and formaldehyde, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, polyethyleneimine, tetramethylammonium hydroxide, gelatin, methylcellulose, dioctylsulfosuccinate Nate, sorbitan ester and the like may be used.
Further, for example, those that can be dissolved in a polar medium described later, used in the production of hollow particles, one or more hydrophilic groups described below (hydroxyl group, carboxyl group, amino group, sulfonic acid group, amide group, etc.) And those having a substituent of the above.
As those having a hydroxyl group, those having a carboxyl group, such as carboxymethyl cellulose, poly (meth) acrylic acid, etc., those having an amino group, gelatin, etc., those having a sulfonic acid group, polystyrene sulfonic acid, etc. .
Examples of those having an amide group include polyacrylamides and polyvinylpyrrolidone.
好ましい分散剤としては、コロイダルシリカと水溶性窒素含有化合物との組み合わせが挙げられる。 A preferable dispersant includes a combination of colloidal silica and a water-soluble nitrogen-containing compound.
水溶性窒素含有化合物としては、例えば、ポリビニルピロリドン、ポリエチレンイミン;ポリオキシエチレンアルキルアミン;ポリジメチルアミノエチルメタクリレート、ポリジメチルアミノエチルアクリレートに代表されるポリジアルキルアミノアルキルアクリレート又はポリジアルキルアミノアルキルメタクリレート;ポリジメチルアミノプロピルアクリルアミド、ポリジメチルアミノプロピルメタクリルアミドに代表されるポリジアルキルアミノアルキルアクリルアミド又はポリジアルキルアミノアルキルメタクリルアミド;ポリアクリルアミド;ポリカチオン性アクリルアミド;ポリアミンサルフォン;ポリアリルアミンが挙げられる。これらは単独で又は2種以上を組み合わせて用いてもよい。
なかでも、コロイダルシリカとポリビニルピロリドンとの組み合わせが適している。コロイダルシリカとポリビニルピロリドンとの添加量によって、得られる中空粒子の粒子径を調整することができる。
特に、コロイダルシリカを使用する場合は、pHを適宜調整することが望ましい。コロイダルシリカは酸性環境である方が好ましい。
Examples of the water-soluble nitrogen-containing compound include polyvinyl pyrrolidone, polyethyleneimine; polyoxyethylene alkylamine; polydialkylaminoalkyl acrylate or polydialkylaminoalkyl methacrylate represented by polydimethylaminoethyl methacrylate and polydimethylaminoethyl acrylate; Examples include dimethylaminopropyl acrylamide, polydialkylaminoalkyl acrylamide or polydialkylaminoalkyl methacrylamide represented by polydimethylaminopropyl methacrylamide; polyacrylamide; polycationic acrylamide; polyamine sulfone; polyallylamine. You may use these individually or in combination of 2 or more types.
Of these, a combination of colloidal silica and polyvinylpyrrolidone is suitable. The particle diameter of the hollow particles obtained can be adjusted by the addition amount of colloidal silica and polyvinylpyrrolidone.
In particular, when colloidal silica is used, it is desirable to adjust pH appropriately. The colloidal silica is preferably in an acidic environment.
さらに他の好ましい分散剤としては、水酸化マグネシウムおよび/またはリン酸カルシウムと乳化剤との組み合わせが挙げられる。
ここでの乳化剤としては、例えば、不飽和ポリオキシエチレンアルキルフェニルエーテル等が挙げられる。
Yet another preferred dispersant is a combination of magnesium hydroxide and / or calcium phosphate and an emulsifier.
As an emulsifier here, unsaturated polyoxyethylene alkylphenyl ether etc. are mentioned, for example.
分散剤の添加量は特に限定されないが、モノマー成分100重量部に対して0.1〜20重量部が好ましい。より好まくは、1〜20重量部、さらに好ましくは、3〜10重量部が挙げられる。
特に、コロイダルシリカを用いる場合には、その粒子径によって調整されるが、モノマー成分100重量部に対して、1〜20重量部、好ましくは2〜10重量部が挙げられる。無機塩を用いる場合には、モノマー成分100重量部に対して、0重量部〜100重量部が挙げられる。ポリビニリピロリドンを用いる場合には、0.05〜2重量部、好ましくは0.1〜2重量部、より好ましくは0.1〜1重量部が挙げられる。
Although the addition amount of a dispersing agent is not specifically limited, 0.1-20 weight part is preferable with respect to 100 weight part of monomer components. More preferably, it is 1-20 weight part, More preferably, 3-10 weight part is mentioned.
In particular, when colloidal silica is used, it is adjusted depending on the particle diameter, but may be 1 to 20 parts by weight, preferably 2 to 10 parts by weight, per 100 parts by weight of the monomer component. In the case of using an inorganic salt, 0 to 100 parts by weight is exemplified with respect to 100 parts by weight of the monomer component. When using polyvinyl pyrrolidone, 0.05-2 weight part, Preferably it is 0.1-2 weight part, More preferably, 0.1-1 weight part is mentioned.
<極性媒体>
モノマー成分を懸濁重合するために、極性媒体を用いることが好ましい。
極性媒体としては、上述したモノマー成分等を含有する溶液と非相溶であれば特に限定されない。例えば、水(脱イオン水等)、メタノール、エタノール、ジメチルスルフォキシド、ジメチルホルムアミド等が挙げられる。これらは単独で用いてもよく、2種以上を併用してもよい。なかでも、取り扱いが容易なことから水が好適である。
<Polar medium>
In order to suspension polymerize the monomer component, it is preferable to use a polar medium.
The polar medium is not particularly limited as long as it is incompatible with the solution containing the monomer component described above. For example, water (deionized water etc.), methanol, ethanol, dimethyl sulfoxide, dimethylformamide and the like can be mentioned. These may be used alone or in combination of two or more. Of these, water is preferable because it is easy to handle.
極性媒体には、分散剤、補助安定剤、pH調整剤、水溶性重合禁止剤、老化防止剤、酸化防止剤、防腐剤等、通常懸濁重合法において用いられる種々の添加剤(例えば、架橋剤等)を含有することができる。これらの添加剤は、当該分野で通常用いられるものを利用することができる。なお、これらの添加剤では、高級脂肪酸(例えば、イソステアリン酸、ステアリン酸、n−ヘプタデカン酸、パルミチン酸、n−ペンタデカン酸、ミリスチン酸、アラギン酸、ノナデカン酸、n−トリデカン酸、ラウリン酸、ウンデシル酸等)、増粘剤等を用いないことが適している。 For the polar medium, various additives usually used in suspension polymerization methods (for example, crosslinking) such as dispersants, auxiliary stabilizers, pH adjusters, water-soluble polymerization inhibitors, antioxidants, antioxidants, preservatives, etc. Agent) and the like. These additives can use what is normally used in the said field | area. In these additives, higher fatty acids (for example, isostearic acid, stearic acid, n-heptadecanoic acid, palmitic acid, n-pentadecanoic acid, myristic acid, alginate, nonadecanoic acid, n-tridecanoic acid, lauric acid, undecyl It is suitable not to use an acid or the like) or a thickener.
具体的には、極性媒体は分散剤を含有し、pHが調節されることが好ましい。
分散安定剤としてコロイダルシリカなどのシリカを使用する場合には、酸性環境で重合が行われることになるため、塩酸等の酸を必要に応じて加えて、系のpHを3〜4に調整することが適している。
また、水酸化マグネシウム又はリン酸カルシウム等を使用する場合には、アルカリ性環境で重合が行われることになるため、系のpHをアルカリ側に調整することが適している。
Specifically, the polar medium preferably contains a dispersant and the pH is adjusted.
When silica such as colloidal silica is used as a dispersion stabilizer, polymerization is performed in an acidic environment, so an acid such as hydrochloric acid is added as necessary to adjust the pH of the system to 3-4. Is suitable.
When magnesium hydroxide or calcium phosphate is used, since polymerization is performed in an alkaline environment, it is suitable to adjust the pH of the system to the alkali side.
懸濁液を調製する場合、具体的には、圧力容器(釜)に、極性溶媒(例えば、水)、分散剤、多官能性モノマーを入れた後に、減圧し、減圧の中で、VCMモノマー(液化ガスモノマー)を添加し、撹拌/混合する。モノマー成分等と極性溶媒との混合/攪拌には、ホモミキサー、バイオミキサー、ホモジナイザー等の機械的攪拌機を用いてもよいし、超音波ホモジナイザー等を用いてもよい。得られる中空粒子の粒子径は懸濁液中の油滴径に依存するため、分散安定剤の種類、量又は撹拌の方法、強度等により適宜制御することができる。 When preparing a suspension, specifically, after putting a polar solvent (for example, water), a dispersing agent and a polyfunctional monomer into a pressure vessel (kettle), the pressure is reduced and the VCM monomer is reduced. (Liquefied gas monomer) is added and stirred / mixed. For mixing / stirring the monomer component and the polar solvent, a mechanical stirrer such as a homomixer, a biomixer, or a homogenizer may be used, or an ultrasonic homogenizer may be used. Since the particle diameter of the obtained hollow particles depends on the oil droplet diameter in the suspension, it can be appropriately controlled depending on the type and amount of the dispersion stabilizer, the stirring method, the strength, and the like.
次いで、(2)懸濁液を加熱してモノマー成分を重合し、重合の途中の時点で未反応塩化ビニルを除去して、樹脂粒子を形成する。
重合するために、まず、得られた懸濁液を加熱する。
加熱温度は、用いるモノマー成分の組成、分子量、重合開始剤の種類及び量等によって適宜調整することができ、例えば、30〜100℃程度が挙げられ、30〜70℃程度が好ましい。
Next, (2) the suspension is heated to polymerize the monomer component, and unreacted vinyl chloride is removed during the polymerization to form resin particles.
In order to polymerize, the suspension obtained is first heated.
The heating temperature can be appropriately adjusted depending on the composition of the monomer component to be used, the molecular weight, the type and amount of the polymerization initiator, and the temperature is, for example, about 30 to 100 ° C, and preferably about 30 to 70 ° C.
重合の途中の時点としては、例えば、モノマー成分の重合率が75%以下のいずれかの時点、つまり、モノマー成分の重合率が10〜70%±5%程度となった時点とすることが適しており、40〜70%±5%程度となった時点とすることが好ましく、50〜65%±5%程度となった時点とすることがより好ましい。具体的には、モノマー成分の重合率が40%付近(例えば、40±5%)となった時点、50%付近(50±5%)となった時点、60%付近となった時点、70%付近となった時点などが挙げられる。本発明においては、重合率を上げると空隙率が下がるというように、重合率が空隙に比例するため、この範囲とすることにより、中空粒子の空隙率を適切に制御することができ、軽量化等の中空粒子の特性を最大限に発揮させることができる。また、収率が良好となり、生産性を向上させることができる。 The point in the middle of the polymerization is preferably, for example, any point where the polymerization rate of the monomer component is 75% or less, that is, the point where the polymerization rate of the monomer component becomes about 10 to 70% ± 5%. Therefore, it is preferable that the time is about 40 to 70% ± 5%, and more preferably about 50 to 65% ± 5%. Specifically, when the polymerization rate of the monomer component is around 40% (for example, 40 ± 5%), around 50% (50 ± 5%), around 60%, 70 The time when it became around%. In the present invention, when the polymerization rate is increased, the porosity decreases, and the polymerization rate is proportional to the voids. By setting this range, the void ratio of the hollow particles can be appropriately controlled, and the weight can be reduced. The characteristics of the hollow particles such as can be exhibited to the maximum. In addition, the yield can be improved and productivity can be improved.
なお、重合中、触媒量、圧力降下(塩ビモノマーガスがポリマーになると圧力が下がってくる)より逆算して、重合をストップする時期を判断することができる。 During the polymerization, the time to stop the polymerization can be determined by calculating back from the catalyst amount and the pressure drop (the pressure decreases when the vinyl chloride monomer gas becomes a polymer).
このような重合の途中の時点で未反応塩化ビニルを除去する方法としては、塩化ビニルモノマーはガス状で存在するために、排ガスする方法又は不活性ガス等の非反応性ガスで塩化ビニルモノマーを置換する方法等が例示される。なかでも、前者が好ましい。 As a method for removing unreacted vinyl chloride in the middle of such polymerization, since the vinyl chloride monomer exists in a gaseous state, the vinyl chloride monomer is removed with a non-reactive gas such as an exhaust gas method or an inert gas. Examples of such a method are as follows. Of these, the former is preferred.
この重合途中での未反応塩化ビニルの除去のタイミングを調整することにより、形成された塩化ビニルの重合体からガスが適切に抜け出て、その内部に中空を効率的に形成することができる。 By adjusting the timing of removal of unreacted vinyl chloride during the polymerization, the gas can be appropriately escaped from the formed vinyl chloride polymer, and a hollow can be efficiently formed therein.
さらに、(3)樹脂粒子を脱水及び乾燥する。
そのために、例えば、加熱等する方法が挙げられる。具体的には、得られた樹脂粒子からなるスラリーを、例えば、セントル脱水する、樹脂粒子を蒸気、熱風等により加熱する及び/又は減圧条件下に載置する等の方法が挙げられる。これにより、中空樹脂粒子を得ることができる。
脱水又は乾燥は、例えば、60℃〜160℃程度の温度範囲で行うことが適しており、好ましくは、80℃〜100℃程度である。脱水又は乾燥の時間は、特に限定されず、その方法によって適宜調整することができる。
なお、一般に、塩化ビニル系樹脂の重合方法として、塊状重合方法、溶液重合方法、乳化重合方法、懸濁重合方法等が知られていることから、上述した懸濁重合法を利用するのみならず、その他の方法に準じて塩化ビニル系中空粒子を製造することもできる。
Further, (3) the resin particles are dehydrated and dried.
For this purpose, for example, a method of heating or the like can be mentioned. Specifically, for example, the obtained slurry made of resin particles may be subjected to, for example, centre dehydration, the resin particles are heated with steam, hot air, and / or placed under reduced pressure. Thereby, hollow resin particles can be obtained.
The dehydration or drying is suitably performed, for example, in a temperature range of about 60 ° C to 160 ° C, and preferably about 80 ° C to 100 ° C. The time for dehydration or drying is not particularly limited, and can be appropriately adjusted depending on the method.
In general, bulk polymerization methods, solution polymerization methods, emulsion polymerization methods, suspension polymerization methods, and the like are known as polymerization methods for vinyl chloride resins. According to other methods, vinyl chloride hollow particles can also be produced.
<塩化ビニル系中空粒子>
本発明の塩化ビニル系中空粒子(以下、単に「中空粒子」と記載することがある)は、実質的に、主成分としての塩化ビニルと、多官能性モノマーと任意に他のモノマーとの反応によって得られたポリマーによって構成される。この塩化ビニル系中空粒子は、その製造過程において重合開始剤、分散剤、極性溶媒、その他の添加剤等が用いられることから、残留物等として、これらの成分が残留していてもよい。
<Vinyl chloride hollow particles>
The vinyl chloride hollow particles of the present invention (hereinafter sometimes simply referred to as “hollow particles”) are substantially a reaction between vinyl chloride as a main component, a polyfunctional monomer, and optionally other monomers. It is comprised by the polymer obtained by. Since these vinyl chloride hollow particles use a polymerization initiator, a dispersant, a polar solvent, other additives, and the like in the production process, these components may remain as residues.
この中空粒子は、例えば、平均粒子径が3〜100μm程度のものが適しており、好ましくは10〜80μm程度である。この範囲とすることにより、ハンドリング性が良好となる。また、この塩化ビニル系中空粒子を用いて成形品を製造した場合に、得られる成形体の物性を良好にすることができる。
中空粒子は、空隙率が20%程度以上、25%程度以上であることが適している。上限は、75%程度以下、70%程度以下が適しており、さらに40%程度以下(又は未満)、38%程度以下、37%程度以下であることが好ましい。この空隙率とすることにより、十分な軽量化とともに強度をも確保することができる。
空隙率は、塩化ビニル系中空粒子の全体積中に占める中空部の体積を百分率(%)で表示したものであり、例えば、アムコ社製ポロシメーター2000を用いて封入水銀圧力2000kg/cm2の条件等にて測定することができる。
For example, those hollow particles having an average particle diameter of about 3 to 100 μm are suitable, and preferably about 10 to 80 μm. By setting it within this range, the handling property is improved. In addition, when a molded product is produced using the vinyl chloride hollow particles, the physical properties of the obtained molded product can be improved.
It is suitable that the hollow particles have a porosity of about 20% or more and about 25% or more. The upper limit is suitably about 75% or less and about 70% or less, more preferably about 40% or less (or less), about 38% or less, or about 37% or less. By setting this porosity, it is possible to ensure sufficient weight and strength.
The porosity is a percentage (%) of the volume of the hollow portion in the total volume of the vinyl chloride-based hollow particles. For example, the porosity of the sealed mercury is 2000 kg / cm 2 using an AMCO Porosimeter 2000. It can measure by.
<塩化ビニル系樹脂組成物>
本発明の塩化ビニル系樹脂組成物は、少なくとも塩化ビニル系樹脂と上述した塩化ビニル系中空粒子とを含有する。ここでの塩化ビニル系中空粒子は、懸濁重合法のみならず、他の重合法によって形成されたものでもよい。
<Vinyl chloride resin composition>
The vinyl chloride resin composition of the present invention contains at least a vinyl chloride resin and the vinyl chloride hollow particles described above. The vinyl chloride hollow particles here may be formed not only by the suspension polymerization method but also by other polymerization methods.
塩化ビニル系樹脂としては、塩化ビニルの単独重合体(塩化ビニルホモポリマー)、塩化ビニルモノマーと共重合可能な不飽和結合を有するモノマーと塩化ビニルモノマー(好ましくは、50重量%以上含む)との共重合体、重合体に塩化ビニルモノマーをグラフト共重合したグラフト共重合体等の塩化ビニル系樹脂等が挙げられる。これら重合体は単独で用いてもよいし、2種以上併用してもよい。 As the vinyl chloride resin, a homopolymer of vinyl chloride (vinyl chloride homopolymer), a monomer having an unsaturated bond copolymerizable with a vinyl chloride monomer, and a vinyl chloride monomer (preferably containing 50% by weight or more) Examples thereof include vinyl chloride resins such as copolymers and graft copolymers obtained by graft copolymerization of vinyl chloride monomers with polymers. These polymers may be used alone or in combination of two or more.
塩化ビニルモノマーと共重合可能な不飽和結合を有するモノマーとしては、上述した多官能性モノマー及びその他のモノマーと同様のものが挙げられる。 Examples of the monomer having an unsaturated bond copolymerizable with the vinyl chloride monomer include the same polyfunctional monomers and other monomers as described above.
塩化ビニルをグラフト共重合する重合体としては、塩化ビニルをグラフト重合させるものであれば特に限定されず、例えば、エチレン−酢酸ビニル共重合体、エチレン−酢酸ビニル−一酸化炭素共重合体、エチレン−エチルアクリレート共重合体、エチレン−ブチルアクリレート−一酸化炭素共重合体、エチレン−メチルメタクリレート共重合体、エチレン−プロピレン共重合体、アクリロニトリル−ブタジエン共重合体、ポリウレタン、塩素化ポリエチレン、塩素化ポリプロピレン等が挙げられる。これらは単独で用いてもよいし、2種以上併用してもよい。 The polymer for graft copolymerization of vinyl chloride is not particularly limited as long as vinyl chloride is graft-polymerized. For example, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-carbon monoxide copolymer, ethylene -Ethyl acrylate copolymer, ethylene-butyl acrylate-carbon monoxide copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, acrylonitrile-butadiene copolymer, polyurethane, chlorinated polyethylene, chlorinated polypropylene Etc. These may be used alone or in combination of two or more.
塩化ビニル系樹脂の重合方法は、特に限定されず、従来公知の任意の重合方法を利用することができる。例えば、塊状重合方法、溶液重合方法、乳化重合方法、懸濁重合方法等が挙げられる。 The polymerization method of the vinyl chloride resin is not particularly limited, and any conventionally known polymerization method can be used. Examples thereof include a bulk polymerization method, a solution polymerization method, an emulsion polymerization method, and a suspension polymerization method.
塩化ビニル系樹脂の重合度は、小さくなると機械的物性が低下する傾向があり、大きくなると成形性が悪化する傾向があるため、400〜2500程度が好ましく、より好ましくは600〜2000程度、600〜1600程度である。
重合度を調整する方法としては、主に重合温度等が例示される。一般に重合温度が高いほど重合度は低くなる。重合度は、JIS K 6720−2に準拠して測定することができる。
When the degree of polymerization of the vinyl chloride resin decreases, the mechanical properties tend to decrease, and when it increases, the moldability tends to deteriorate. Therefore, it is preferably about 400 to 2500, more preferably about 600 to 2000, 600 to It is about 1600.
Examples of the method for adjusting the degree of polymerization mainly include the polymerization temperature. In general, the higher the polymerization temperature, the lower the degree of polymerization. The degree of polymerization can be measured according to JIS K 6720-2.
本発明の塩化ビニル系樹脂組成物では、上述した塩化ビニル系樹脂(以下、「PVC」と記載することがある)100重量部に対して、上述した塩化ビニル系中空粒子を3〜50重量部配合することが適している。この範囲とすることにより、樹脂組成物の軽量化を十分に図ることができるとともに、これを用いて作成した成形品の外観の損傷等を防止することができる。但し、成形品の外観が重要視されないものであれば、50重量部を超えて使用されていてもよい。 In the vinyl chloride resin composition of the present invention, 3 to 50 parts by weight of the vinyl chloride hollow particles described above are added to 100 parts by weight of the vinyl chloride resin (hereinafter sometimes referred to as “PVC”). It is suitable to mix. By setting it as this range, the resin composition can be sufficiently reduced in weight, and damage to the appearance of a molded product produced using the resin composition can be prevented. However, as long as the appearance of the molded product is not important, it may be used in excess of 50 parts by weight.
また、本発明の塩化ビニル系樹脂組成物は、さらに衝撃改質剤と、重量平均分子量が100万〜600万のアクリル系加工助剤とが添加されていることが好ましい。
これらの使用量は、例えば、上述した塩化ビニル系樹脂100重量部に対し、衝撃改質剤1〜30重量部及び重量平均分子量が100万〜600万のアクリル系加工助剤1〜30重量部であることが適している。
The vinyl chloride resin composition of the present invention preferably further contains an impact modifier and an acrylic processing aid having a weight average molecular weight of 1,000,000 to 6,000,000.
The amount of these used is, for example, 1 to 30 parts by weight of an acrylic processing aid having an impact modifier of 1 to 30 parts by weight and a weight average molecular weight of 1 to 6 millions per 100 parts by weight of the vinyl chloride resin. Is suitable.
この塩化ビニル系樹脂組成物は、特に、成形品を作成する際に、さらに、PVCに通常配合される安定剤、充填剤、滑剤、紫外線吸収剤、顔料等を、本発明の目的を阻害しない範囲で配合してもよい。 This vinyl chloride resin composition does not impair the purpose of the present invention, particularly when a molded product is produced, and further, stabilizers, fillers, lubricants, ultraviolet absorbers, pigments and the like that are usually blended in PVC. You may mix | blend in the range.
塩化ビニル系樹脂組成物は、上述した塩化ビニル系樹脂、衝撃改質剤、重量平均分子量が100万〜600万のアクリル系加工助剤、任意に安定剤、充填剤、滑剤、紫外線吸収剤、顔料等を、例えば、リボンブレンダー、V型ブレンダー、ヘンシェルミキサー(商標)等の公知の混合装置に投入し、混合する。
混合装置を用いて、塩化ビニル系樹脂組成物を混合する際には、加熱することがあるが、塩化ビニル系中空粒子は、上述した成分を添加して加熱/混合した場合の昇温終了後に又は冷却時、80℃程度以下となった時点で添加して攪拌することが好ましい。加熱による空隙の変形又は損傷を防止するためである。
また、さらに公知の造粒装置を用いて混練造粒してもよい。造粒装置としては、単軸又は二軸押出機等が挙げられる。ロール加工シートからペレット化してもよい。
造粒装置を用いて、塩化ビニル系樹脂組成物を造粒する際には、加熱することがあるが、塩化ビニル系中空粒子は、170℃以下の樹脂温度にて添加、造粒することが好ましい。
The vinyl chloride resin composition includes the above-described vinyl chloride resin, impact modifier, acrylic processing aid having a weight average molecular weight of 1,000,000 to 6 million, optionally stabilizer, filler, lubricant, ultraviolet absorber, The pigment or the like is charged into a known mixing apparatus such as a ribbon blender, a V-type blender, or a Henschel mixer (trademark) and mixed.
When mixing the vinyl chloride resin composition using a mixing device, it may be heated, but the vinyl chloride hollow particles are added after the heating and mixing in the case where the above components are added and heated / mixed. Or it is preferable to add and stir when it becomes about 80 degrees C or less at the time of cooling. This is to prevent deformation or damage of the air gap due to heating.
Further, kneading granulation may be performed using a known granulating apparatus. Examples of the granulator include a single screw or twin screw extruder. You may pelletize from a roll processing sheet.
When a vinyl chloride resin composition is granulated using a granulator, it may be heated, but vinyl chloride hollow particles may be added and granulated at a resin temperature of 170 ° C. or lower. preferable.
<成形品の製造>
本発明の成形体は、特に限定されるものではなく、例えば、板状又は波形等のプレート、パイプ、パイプ継手、シート、フィルム等種々の用途及び形状を有することができる。
このような成形体は、通常のPVCの成形によって製造することができる。例えば、単軸型、2軸型等の押出成形機、スクリュー等を用いて、任意の形状に成形することができる。
このように、本発明の塩化ビニル系中空粒子を含む塩化ビニル系樹脂組成物によって成形体を形成することにより、比重値が極めて低く、これまでには無い軽量化された塩化ビニル成形体を得ることができる。また、塩化ビニル本来の特性及び軽量化を維持したまま、最大限の難燃性を期待することができる。
<Manufacture of molded products>
The molded body of the present invention is not particularly limited, and can have various uses and shapes such as plates or corrugated plates, pipes, pipe joints, sheets, films, and the like.
Such a molded body can be manufactured by normal PVC molding. For example, it can be formed into an arbitrary shape using a single-shaft type or biaxial type extruder, screw or the like.
Thus, by forming a molded body from the vinyl chloride resin composition containing the vinyl chloride hollow particles of the present invention, a vinyl chloride molded body having a very low specific gravity and a weight that has never been obtained is obtained. be able to. Further, the maximum flame retardancy can be expected while maintaining the original characteristics and weight reduction of vinyl chloride.
以下、本発明の塩化ビニル系中空粒子、その製造方法、塩化ビニル系樹脂組成物及び成形品について、実施例によって、詳細に説明する。 Hereinafter, the vinyl chloride hollow particles, the production method thereof, the vinyl chloride resin composition and the molded product of the present invention will be described in detail with reference to examples.
実施例A:塩化ビニル系中空粒子(A1)の製造
攪拌機の備えられたジャケット付25リットルの耐圧重合器に、表1に示すように、イオン交換水7.89kg、トリメチロールプロパンジ(メタ)アクリレート1.1kg、油溶性ラジカル開始剤としてジsecブチルパーオキシジカーボネート3.7g及びα−クミルパーオキシネオデカノエート5.5g、分散剤として濃度20%のコロイダルシリカ1712g、濃度30%ポリビニルピロリドン30.1g、食塩2790g、塩酸10.9gとを混合した溶液を調製した。得られたモノマー溶液を、溶解した水中に加え、攪拌分散装置を用いて10分間攪拌して、懸濁液を得た。
Example A: Production of vinyl chloride-based hollow particles (A1) As shown in Table 1, 7.25 kg of ion-exchanged water, trimethylolpropane di (meth) were added to a jacketed 25 liter pressure-resistant polymerizer equipped with a stirrer. 1.1 kg of acrylate, 3.7 g of disecbutyl peroxydicarbonate and 5.5 g of α-cumylperoxyneodecanoate as an oil-soluble radical initiator, 1712 g of colloidal silica at a concentration of 20% as a dispersant, and a concentration of 30% polyvinyl A solution in which 30.1 g of pyrrolidone, 2790 g of sodium chloride and 10.9 g of hydrochloric acid were mixed was prepared. The obtained monomer solution was added to dissolved water and stirred for 10 minutes using a stirring and dispersing device to obtain a suspension.
重合器を密閉して空気を排除した後、塩化ビニルモノマー2.6kgを圧入し、次いで、10分間攪拌後、撹拌しながら、54℃(重合度1300)まで昇温し、重合器内の温度が54℃(重合度1300)に保持しながら水懸濁重合を行った。重合開始1.5時間後(重合率60%となるように設定)経過してからジャケットに冷却水を通して重合器を冷却した。その後、重合スラリーを取り出し脱水装置により脱水した。しかる後、真空乾燥し塩ビモノマーを除くと同時に、多孔性の中空樹脂粒子を得た。得られた収量は、2.8kgとなり、収率は73%となった。 After sealing the polymerization vessel and excluding air, 2.6 kg of vinyl chloride monomer was injected, and after stirring for 10 minutes, the temperature was raised to 54 ° C. (degree of polymerization 1300) while stirring. Was suspended in water while maintaining at 54 ° C. (degree of polymerization 1300). After 1.5 hours from the start of polymerization (setting so that the polymerization rate was 60%), the polymerization vessel was cooled by passing cooling water through the jacket. Thereafter, the polymerization slurry was taken out and dehydrated with a dehydrator. Thereafter, it was vacuum dried to remove the vinyl chloride monomer, and at the same time, porous hollow resin particles were obtained. The yield obtained was 2.8 kg, and the yield was 73%.
実施例B:塩化ビニル系中空粒子(A2)の製造
油溶性ラジカル開始剤のα−クミルパーオキシネオデカノエート4.4g、塩化ビニルモノマー4.1kg、重合開始2時間後(重合率70%となるように設定)経過してからジャケットに冷却水を通して重合器を冷却した事以外は(A1)と同様に行った。得られた収量は、3.8kgとなり、収率は73%となった。
Example B: Production of vinyl chloride-based hollow particles (A2) 4.4 g of oil-soluble radical initiator α-cumylperoxyneodecanoate, 4.1 kg of vinyl chloride monomer, 2 hours after the start of polymerization (polymerization rate 70%) This was carried out in the same manner as (A1) except that after the elapse of time, the polymerization vessel was cooled by passing cooling water through the jacket. The yield obtained was 3.8 kg, and the yield was 73%.
実施例C:塩化ビニル系中空粒子(A3)の製造
イオン交換水8.78kg、分散剤としては、濃度10%のポリビニルアルコール558gのみを用い混合、溶液を調製、重合開始1.0時間後(重合率35%となるように設定)経過してからジャケットに冷却水を通して重合器を冷却した事以外は(A1)と同様に行った。得られた収量は、1.3kgとなり、収率は35.5%となった。
Example C: Production of vinyl chloride hollow particles (A3) 8.78 kg of ion-exchanged water and, as a dispersant, only 558 g of polyvinyl alcohol having a concentration of 10% was mixed, a solution was prepared, and 1.0 hour after the start of polymerization ( (Setting was made so that the polymerization rate was 35%) After the elapse of time, it was carried out in the same manner as (A1) except that the polymerization vessel was cooled by passing cooling water through the jacket. The yield obtained was 1.3 kg, and the yield was 35.5%.
実施例D:塩化ビニル系中空粒子(A4)の製造
イオン交換水8.78kg、トリメチロールプロパンジ(メタ)アクリレート0.56kg、分散剤として濃度10%のポリビニルアルコール558gのみを用い、塩化ビニルモノマー3.16kg、重合開始1.0時間後(重合率20%となるように設定)経過してからジャケットに冷却水を通して重合器を冷却した事以外は(A1)と同様に行った。得られた収量は、0.9kgとなり、収率は23.9%となった。
Example D: Production of vinyl chloride hollow particles (A4) Ion-exchanged water 8.78 kg, trimethylolpropane di (meth) acrylate 0.56 kg, using only 558 g of 10% concentration polyvinyl alcohol as a dispersant, vinyl chloride monomer The procedure was the same as (A1) except that the polymerization vessel was cooled by passing cooling water through the jacket after 3.16 kg and 1.0 hour after the start of polymerization (set so that the polymerization rate was 20%). The yield obtained was 0.9 kg, and the yield was 23.9%.
実施例E:塩化ビニル系中空粒子(A5)の製造
イオン交換水8.78kg、トリメチロールプロパンジ(メタ)アクリレート0.56kg、分散剤として濃度10%のポリビニルアルコール558gのみを用い、塩化ビニルモノマー3.16kg、重合開始3.0時間後(重合率65%となるように設定)経過してからジャケットに冷却水を通して重合器を冷却した事以外は(A1)と同様に行った。得られた収量は、2.4kgとなり、収率は65.0%となった。
Example E: Production of vinyl chloride hollow particles (A5) Ion exchange water 8.78 kg, trimethylolpropane di (meth) acrylate 0.56 kg, using only 558 g of 10% polyvinyl alcohol as a dispersant, vinyl chloride monomer The procedure was the same as (A1), except that 3.16 kg and 3.0 hours after the start of polymerization (set to a polymerization rate of 65%) had elapsed, the polymerization vessel was cooled by passing cooling water through the jacket. The yield obtained was 2.4 kg, and the yield was 65.0%.
参考例F:塩化ビニル系中空粒子(A6)の製造
イオン交換水8.78kg、トリメチロールプロパンジ(メタ)アクリレート0.19kg、分散剤として濃度10%のポリビニルアルコール558gのみを用い、塩化ビニルモノマー3.16kg、重合開始1.0時間後(重合率10%となるように設定)経過してからジャケットに冷却水を通して重合器を冷却した事以外は(A1)と同様に行った。得られた収量は、0.4kgとなり、収率は10.0%となった。
Reference Example F: Production of Vinyl Chloride-Based Hollow Particles (A6) 8.78 kg of ion exchange water, 0.19 kg of trimethylolpropane di (meth) acrylate, and using only 558 g of 10% polyvinyl alcohol as a dispersant, vinyl chloride monomer The procedure was the same as (A1) except that the polymerization vessel was cooled by passing cooling water through the jacket after 3.16 kg and 1.0 hour after the start of polymerization (set so that the polymerization rate was 10%). The yield obtained was 0.4 kg, and the yield was 10.0%.
参考例G:塩化ビニル系中空粒子(A7)の製造
イオン交換水8.78kg、トリメチロールプロパンジ(メタ)アクリレート0.19kg、分散剤として濃度10%のポリビニルアルコール558gのみを用い、塩化ビニルモノマー3.16kg、重合開始3.0時間後(重合率65%となるように設定)経過してからジャケットに冷却水を通して重合器を冷却した事以外は(A1)と同様に行った。得られた収量は、1.9kgとなり、収率は51.1%となった。
Reference example G: Production of vinyl chloride hollow particles (A7) 8.78 kg of ion exchange water, 0.19 kg of trimethylolpropane di (meth) acrylate, and 558 g of polyvinyl alcohol having a concentration of 10% as a dispersant, vinyl chloride monomer The procedure was the same as (A1), except that 3.16 kg and 3.0 hours after the start of polymerization (set to a polymerization rate of 65%) had elapsed, the polymerization vessel was cooled by passing cooling water through the jacket. The yield obtained was 1.9 kg, and the yield was 51.1%.
比較例:塩化ビニル(B1)の製造
攪拌機の備えられたジャケット付25リットルの耐圧重合器に、表1に示すように、イオン交換水8.56kg、油溶性ラジカル開始剤としてジsecブチルパーオキシジカーボネート1.9g及びα−クミルパーオキシネオデカノエート2.9g、分散剤として濃度3%のポリビニルアルコール126gとを混合した溶液を調製した。得られたモノマー溶液を、溶解した水中に加え、攪拌分散装置を用いて10分間攪拌して、懸濁液を得た。重合器を密閉して空気を排除した後、塩化ビニルモノマー4.21kgを圧入し、次いで、10分間攪拌後、撹拌しながら、57.5℃(重合度1000)まで昇温し、重合器内の温度が57.5℃(重合度1000)に保持しながら水懸濁重合を行った。重合開始5時間後(重合率85%以上)経過してからジャケットに冷却水を通して重合器を冷却した。その後、重合スラリーを取り出し脱水装置により脱水し、塩ビ樹脂粒子を得た。得られた収量は、3.45kgとなり、収率は82%となった。
Comparative Example: Production of Vinyl Chloride (B1) As shown in Table 1, 8.56 kg of ion-exchanged water and disecbutylperoxy as an oil-soluble radical initiator were added to a 25-liter jacketed pressure-resistant polymerizer equipped with a stirrer. A solution was prepared by mixing 1.9 g of dicarbonate, 2.9 g of α-cumylperoxyneodecanoate, and 126 g of polyvinyl alcohol having a concentration of 3% as a dispersant. The obtained monomer solution was added to dissolved water and stirred for 10 minutes using a stirring and dispersing device to obtain a suspension. After sealing the polymerization vessel and excluding air, 4.21 kg of vinyl chloride monomer was injected, and after stirring for 10 minutes, the temperature was raised to 57.5 ° C. (degree of polymerization 1000) while stirring. Water suspension polymerization was carried out while maintaining the temperature at 57.5 ° C. (degree of polymerization 1000). After 5 hours from the start of polymerization (polymerization rate of 85% or more), the polymerization vessel was cooled by passing cooling water through the jacket. Thereafter, the polymerization slurry was taken out and dehydrated with a dehydrator to obtain polyvinyl chloride resin particles. The yield obtained was 3.45 kg, and the yield was 82%.
(重合率の測定)
上記実施例A〜E、参考例F、G及び比較例での重合率は、予め重合を行い、重合時間と重合率との関係を求めた結果を基準として表した。
つまり、内容積2m3のステンレス製重合器内に、所定量の脱イオン水、所定の種類及び量の分散剤、所定の種類及び量の油溶性ラジカル開始剤、所定量の多官能モノマーを仕込んだ後、重合器の内圧が8kPa・abs(60mmHg)となるまで脱気し、所定量の塩化ビニル単量体を仕込んだ。その後、攪拌しながら所定の種類及び量の重合開始剤を仕込み、同時に昇温を開始し、重合器内温度が57.0℃に達した段階で、その温度を保ち重合を続けた。昇温開始1時間後に冷却を開始し、重合を完全に停止させ、未反応単量体を回収した。重合体スラリーを脱水、乾燥して得られた塩化ビニル重合体の全量を秤量し、下記式により昇温開始1時間後における重合率を求めた。
昇温開始1時間後における重合率(%)=(乾燥後塩化ビニル系重合体量/仕込み多官能モノマー及び塩化ビニル単量体量)×100
同様にして、昇温開始の後、1.5、2、2.5、3、3.5、4、4.5及び5時間後の30分毎の各々の重合率を算出して、重合時間と重合率の関係を求めた。この重合時間と重合率の関係は、所要の重合開始剤の種類及び添加量並びに所定の重合温度について毎々作成した。
(Measurement of polymerization rate)
The polymerization rates in Examples A to E, Reference Examples F and G, and Comparative Examples were expressed based on the results of performing polymerization in advance and determining the relationship between the polymerization time and the polymerization rate.
That is, a predetermined amount of deionized water, a predetermined type and amount of dispersant, a predetermined type and amount of an oil-soluble radical initiator, and a predetermined amount of polyfunctional monomer are charged into a stainless polymerizer having an internal volume of 2 m 3. Thereafter, deaeration was performed until the internal pressure of the polymerization vessel reached 8 kPa · abs (60 mmHg), and a predetermined amount of vinyl chloride monomer was charged. Thereafter, a predetermined type and amount of a polymerization initiator were charged while stirring, and the temperature was raised at the same time. When the temperature in the polymerization vessel reached 57.0 ° C., the temperature was maintained and polymerization was continued. Cooling was started 1 hour after the start of temperature increase, polymerization was completely stopped, and unreacted monomers were recovered. The total amount of the vinyl chloride polymer obtained by dehydrating and drying the polymer slurry was weighed, and the polymerization rate after 1 hour from the start of temperature increase was determined by the following formula.
Polymerization rate (%) 1 hour after the start of temperature increase = (Amount of vinyl chloride polymer after drying / Amount of charged polyfunctional monomer and vinyl chloride monomer) × 100
Similarly, after the start of temperature increase, the polymerization rate was calculated for each of 30 minutes after 1.5, 2, 2.5, 3, 3.5, 4, 4.5 and 5 hours, The relationship between time and polymerization rate was determined. The relationship between the polymerization time and the polymerization rate was prepared for each required type and amount of polymerization initiator and a predetermined polymerization temperature.
(空隙率の測定)
得られた塩化ビニル系中空粒子について、中空粒子の全体積中に占める中空部体積を測定した。測定は、アムコ社製ポロシメーター2000を用いて封入水銀圧力2000kg/cm2の条件で行った。その結果を百分率(%)で表2に示す。
(Measurement of porosity)
About the obtained vinyl chloride type | system | group hollow particle, the hollow part volume which occupies in the whole volume of a hollow particle was measured. The measurement was performed using an AMCO Porosimeter 2000 under the condition of enclosed mercury pressure of 2000 kg / cm 2 . The results are shown in Table 2 in percentage (%).
実施例及び比較例:塩化ビニル系樹脂組成物の調製
塩化ビニル樹脂(商品名「TS800E」、徳山積水工業社製)100重量部に対して、熱安定剤として有機錫系安定剤(オクチル錫メルカプト、商品名「TVS #1380」、日東化成工業社製)2.0重量部、滑剤として商品名「Wax−OP」(ヘキスト社製)2.0重量部をスーパーミキサー(100L、カワタ社製)に、表2に示す実施例A及びBで得られた所定の塩化ビニル系中空粒子を攪拌混合して塩化ビニル系樹脂組成物を得た。
得られた塩化ビニル系樹脂組成物を、8インチロール成形機にて、190℃×3分間混練し、厚さ1.5mmのシートとし、塩化ビニル系樹脂組成物からなる成形体を得た。
Examples and Comparative Examples: Preparation of Vinyl Chloride Resin Compositions With respect to 100 parts by weight of vinyl chloride resin (trade name “TS800E”, manufactured by Tokuyama Sekisui Industry Co., Ltd.), an organic tin stabilizer (octyl tin mercapto) as a heat stabilizer , 2.0 parts by weight of a trade name “TVS # 1380” manufactured by Nitto Kasei Kogyo Co., Ltd. and 2.0 parts by weight of a trade name “Wax-OP” (manufactured by Hoechst) as a lubricant The predetermined vinyl chloride-based hollow particles obtained in Examples A and B shown in Table 2 were stirred and mixed to obtain a vinyl chloride-based resin composition.
The obtained vinyl chloride resin composition was kneaded with an 8-inch roll molding machine at 190 ° C. for 3 minutes to obtain a sheet having a thickness of 1.5 mm, and a molded article made of the vinyl chloride resin composition was obtained.
(比重の測定)
成形した試料片から40×50mmの試験片を切り取り、JISK 7112に従って
、比重を測定した。この結果を表3に示す。
(Measurement of specific gravity)
A 40 × 50 mm test piece was cut out from the molded sample piece, and the specific gravity was measured according to JISK7112. The results are shown in Table 3.
本発明の塩化ビニル系中空粒子、その製造方法、塩化ビニル系樹脂組成物及び塩化ビニル系成形体は、従来用いられていた塩化ビニル樹脂組成物及び成形体の全てにおいて代替として、さらには、より軽量化、機能化が要求される新たな分野への用途、例えば、建材、乗り物の内装等への応用が期待される。 The vinyl chloride hollow particles, the production method thereof, the vinyl chloride resin composition and the vinyl chloride molded article of the present invention can be used as an alternative in all of the conventionally used vinyl chloride resin compositions and molded articles. Applications in new fields where weight reduction and functionalization are required, such as building materials and interiors of vehicles, are expected.
Claims (6)
(2)該懸濁液を加熱してモノマー成分を重合し、該モノマー成分の重合率が75%以下の時点で未反応塩化ビニルを除去して、樹脂粒子を形成し、
(3)該樹脂粒子を脱水及び乾燥する工程を含み、
前記多官能性モノマーが、全モノマー成分の15.0重量%以上である塩化ビニル系中空粒子の製造方法。 (1) A monomer component containing vinyl chloride as a main component and a polyfunctional monomer, a polymerization initiator and a dispersant are mixed in a polar medium to prepare a suspension,
(2) The suspension is heated to polymerize the monomer component, and when the polymerization rate of the monomer component is 75% or less, unreacted vinyl chloride is removed to form resin particles,
(3) including a step of dehydrating and drying the resin particles;
A method for producing vinyl chloride hollow particles, wherein the polyfunctional monomer is 15.0% by weight or more of the total monomer components.
前記多官能性モノマーが、全モノマー成分の15.0重量%以上であり、
空隙率が25%以上、75%未満であることを特徴とする塩化ビニル系中空粒子。 It is obtained by suspension polymerization in a system containing a monomer component containing vinyl chloride as a main component and a polyfunctional monomer, a polymerization initiator, and a dispersant,
The polyfunctional monomer is 15.0% by weight or more of the total monomer components;
A vinyl chloride hollow particle having a porosity of 25% or more and less than 75%.
前記塩化ビニル系樹脂100重量部に対して、前記中空粒子が3〜50重量部含有されてなることを特徴とする塩化ビニル系樹脂組成物。 A vinyl chloride resin composition comprising at least the vinyl chloride hollow particles according to claim 3 or 4, and a vinyl chloride resin,
A vinyl chloride resin composition comprising 3 to 50 parts by weight of the hollow particles with respect to 100 parts by weight of the vinyl chloride resin.
A vinyl chloride-based molded article formed by the vinyl chloride-based resin composition according to claim 5.
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