JP2009001695A - Vinyl chloride based resin for paste and vinyl chloride based resin composition for paste - Google Patents
Vinyl chloride based resin for paste and vinyl chloride based resin composition for paste Download PDFInfo
- Publication number
- JP2009001695A JP2009001695A JP2007164808A JP2007164808A JP2009001695A JP 2009001695 A JP2009001695 A JP 2009001695A JP 2007164808 A JP2007164808 A JP 2007164808A JP 2007164808 A JP2007164808 A JP 2007164808A JP 2009001695 A JP2009001695 A JP 2009001695A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- polymer
- weight
- paste
- requirement
- 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.)
- Granted
Links
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 229920005989 resin Polymers 0.000 title claims abstract description 91
- 239000011347 resin Substances 0.000 title claims abstract description 91
- 239000011342 resin composition Substances 0.000 title claims description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 158
- 239000002245 particle Substances 0.000 claims abstract description 116
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 claims abstract description 54
- 239000006185 dispersion Substances 0.000 claims description 85
- 239000004014 plasticizer Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000003381 stabilizer Substances 0.000 claims description 13
- 239000004088 foaming agent Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000945 filler Substances 0.000 claims description 8
- 238000013329 compounding Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 abstract description 18
- 238000009826 distribution Methods 0.000 abstract description 7
- -1 canvas Substances 0.000 description 21
- 239000000178 monomer Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- 239000010410 layer Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 239000004744 fabric Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 239000007921 spray Substances 0.000 description 14
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 13
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 229910001220 stainless steel Inorganic materials 0.000 description 12
- 239000010935 stainless steel Substances 0.000 description 12
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000007720 emulsion polymerization reaction Methods 0.000 description 9
- 239000008187 granular material Substances 0.000 description 9
- 239000012528 membrane Substances 0.000 description 9
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 9
- 230000002265 prevention Effects 0.000 description 9
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- 239000003505 polymerization initiator Substances 0.000 description 8
- 238000010557 suspension polymerization reaction Methods 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000009849 vacuum degassing Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- 229920000915 polyvinyl chloride Polymers 0.000 description 5
- 239000004800 polyvinyl chloride Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 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
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 238000010558 suspension polymerization method Methods 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000010556 emulsion polymerization method Methods 0.000 description 3
- 238000009408 flooring Methods 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- OWHSTLLOZWTNTQ-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS OWHSTLLOZWTNTQ-UHFFFAOYSA-N 0.000 description 2
- LVAGMBHLXLZJKZ-UHFFFAOYSA-N 2-o-decyl 1-o-octyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC LVAGMBHLXLZJKZ-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 239000004135 Bone phosphate Substances 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-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
- 239000004593 Epoxy Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229920001944 Plastisol Polymers 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000012933 diacyl peroxide 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
- 238000004049 embossing Methods 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000004999 plastisol Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- MGMPGUIDKNPENO-RXSVEWSESA-N (2r)-2-[(1s)-1,2-dihydroxyethyl]-3,4-dihydroxy-2h-furan-5-one;iron Chemical compound [Fe].OC[C@H](O)[C@H]1OC(=O)C(O)=C1O MGMPGUIDKNPENO-RXSVEWSESA-N 0.000 description 1
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- OXYKVVLTXXXVRT-UHFFFAOYSA-N (4-chlorobenzoyl) 4-chlorobenzenecarboperoxoate Chemical compound C1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1 OXYKVVLTXXXVRT-UHFFFAOYSA-N 0.000 description 1
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- IOSXLUZXMXORMX-UHFFFAOYSA-N 1-ethenoxypentane Chemical compound CCCCCOC=C IOSXLUZXMXORMX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 description 1
- PRIUALOJYOZZOJ-UHFFFAOYSA-L 2-ethylhexyl 2-[dibutyl-[2-(2-ethylhexoxy)-2-oxoethyl]sulfanylstannyl]sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS[Sn](CCCC)(CCCC)SCC(=O)OCC(CC)CCCC PRIUALOJYOZZOJ-UHFFFAOYSA-L 0.000 description 1
- ALKCLFLTXBBMMP-UHFFFAOYSA-N 3,7-dimethylocta-1,6-dien-3-yl hexanoate Chemical compound CCCCCC(=O)OC(C)(C=C)CCC=C(C)C ALKCLFLTXBBMMP-UHFFFAOYSA-N 0.000 description 1
- SIXWIUJQBBANGK-UHFFFAOYSA-N 4-(4-fluorophenyl)-1h-pyrazol-5-amine Chemical compound N1N=CC(C=2C=CC(F)=CC=2)=C1N SIXWIUJQBBANGK-UHFFFAOYSA-N 0.000 description 1
- NKFIBMOQAPEKNZ-UHFFFAOYSA-N 5-amino-1h-indole-2-carboxylic acid Chemical compound NC1=CC=C2NC(C(O)=O)=CC2=C1 NKFIBMOQAPEKNZ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 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
- 229940126062 Compound A Drugs 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical class C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class 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
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 description 1
- SLETZFVTVXVPLS-UHFFFAOYSA-N [Zn].[Cd].[Ba] Chemical compound [Zn].[Cd].[Ba] SLETZFVTVXVPLS-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 229940056585 ammonium laurate Drugs 0.000 description 1
- CAMXVZOXBADHNJ-UHFFFAOYSA-N ammonium nitrite Chemical compound [NH4+].[O-]N=O CAMXVZOXBADHNJ-UHFFFAOYSA-N 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- VJCJAQSLASCYAW-UHFFFAOYSA-N azane;dodecanoic acid Chemical compound [NH4+].CCCCCCCCCCCC([O-])=O VJCJAQSLASCYAW-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 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
- 235000019400 benzoyl peroxide Nutrition 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
- WXZOXVVKILCOPG-UHFFFAOYSA-N bis(2-ethylhexyl) benzene-1,3-dicarboxylate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC(C(=O)OCC(CC)CCCC)=C1 WXZOXVVKILCOPG-UHFFFAOYSA-N 0.000 description 1
- ZDWGXBPVPXVXMQ-UHFFFAOYSA-N bis(2-ethylhexyl) nonanedioate Chemical compound CCCCC(CC)COC(=O)CCCCCCCC(=O)OCC(CC)CCCC ZDWGXBPVPXVXMQ-UHFFFAOYSA-N 0.000 description 1
- VQZMFJVOYYLAHM-UHFFFAOYSA-N buta-1,2,3-trienylbenzene Chemical compound C=C=C=CC1=CC=CC=C1 VQZMFJVOYYLAHM-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- FKGRVAMVXPHISR-PQYRJTSOSA-L copper (2R)-2-[(1S)-1,2-dihydroxyethyl]-3,4-dihydroxy-2H-furan-5-one sulfate Chemical compound O=C1C(O)=C(O)[C@H](O1)[C@@H](O)CO.S(=O)(=O)([O-])[O-].[Cu+2] FKGRVAMVXPHISR-PQYRJTSOSA-L 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- BSVQJWUUZCXSOL-UHFFFAOYSA-N cyclohexylsulfonyl ethaneperoxoate Chemical compound CC(=O)OOS(=O)(=O)C1CCCCC1 BSVQJWUUZCXSOL-UHFFFAOYSA-N 0.000 description 1
- XJOBOFWTZOKMOH-UHFFFAOYSA-N decanoyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(=O)CCCCCCCCC XJOBOFWTZOKMOH-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- HCQHIEGYGGJLJU-UHFFFAOYSA-N didecyl hexanedioate Chemical compound CCCCCCCCCCOC(=O)CCCCC(=O)OCCCCCCCCCC HCQHIEGYGGJLJU-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 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
- RZMWTGFSAMRLQH-UHFFFAOYSA-L disodium;2,2-dihexyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCC RZMWTGFSAMRLQH-UHFFFAOYSA-L 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 229960000878 docusate sodium Drugs 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- NHOGGUYTANYCGQ-UHFFFAOYSA-N ethenoxybenzene Chemical compound C=COC1=CC=CC=C1 NHOGGUYTANYCGQ-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- ZQZUENMXBZVXIZ-UHFFFAOYSA-N ethenyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OC=C ZQZUENMXBZVXIZ-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000007561 laser diffraction method Methods 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
- YJOMWQQKPKLUBO-UHFFFAOYSA-L lead(2+);phthalate Chemical compound [Pb+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O YJOMWQQKPKLUBO-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
- 239000010985 leather Substances 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
- OFUAIAKLWWIPTC-UHFFFAOYSA-L magnesium;naphthalene-2-carboxylate Chemical compound [Mg+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 OFUAIAKLWWIPTC-UHFFFAOYSA-L 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- WCJQKTUPBIICNI-UHFFFAOYSA-N octoxycarbonyloxyperoxy octyl carbonate Chemical compound CCCCCCCCOC(=O)OOOOC(=O)OCCCCCCCC WCJQKTUPBIICNI-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000001818 polyoxyethylene sorbitan monostearate Substances 0.000 description 1
- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229940114930 potassium stearate Drugs 0.000 description 1
- HSJXWMZKBLUOLQ-UHFFFAOYSA-M potassium;2-dodecylbenzenesulfonate Chemical compound [K+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HSJXWMZKBLUOLQ-UHFFFAOYSA-M 0.000 description 1
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 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
- 229950005425 sodium myristyl sulfate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- UPUIQOIQVMNQAP-UHFFFAOYSA-M sodium;tetradecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCOS([O-])(=O)=O UPUIQOIQVMNQAP-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000003981 vehicle Substances 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
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、ペースト用塩化ビニル系樹脂及びペースト用塩化ビニル系樹脂組成物に関するものである。 The present invention relates to a vinyl chloride resin for paste and a vinyl chloride resin composition for paste.
ペースト用塩化ビニル樹脂は、難燃性等に優れた特性を有し、しかも作業性にも優れたいるので、壁材、床材、レザー、帆布、車両内装品、鋼板コート、綿材コート、糸コート、作業手袋、玩具、日用雑貨品等の製品の製造に使用されており、極めて有用なものである。このため、ペースト用塩化ビニル樹脂に関する技術については、各種のものが開発されている。 Since the vinyl chloride resin for paste has excellent properties such as flame retardancy and also excellent workability, it can be used for wall materials, flooring materials, leather, canvas, vehicle interior products, steel plate coating, cotton material coating, It is used for the manufacture of products such as yarn coats, work gloves, toys, and sundries, and is extremely useful. For this reason, various technologies relating to the vinyl chloride resin for paste have been developed.
通常の用途のものとしては、例えば、（１）粒子径が０．０１μｍ以上０．４５μｍ未満であるポリ塩化ビニル系樹脂粒子（Ａ）が３０〜５０重量％、粒子径が０．４５μｍ以上４．５μｍ未満であるポリ塩化ビニル系樹脂粒子（Ｂ）が３５〜５５重量％、粒子径が４．５μｍ以上２０μｍ以下であるポリ塩化ビニル系樹脂粒子（Ｃ）が１０〜３０重量％よりなり、かつ、顆粒における平均粒子径が２０〜１３０μｍであることを特徴とするペースト加工用ポリ塩化ビニル系樹脂顆粒（特許文献１）、（２）塩化ビニル系樹脂の平均重合度が１５００以上で０．０５〜０．２μｍの平均粒径を持つ微小粒子８〜３０重量％と、塩化ビニル系樹脂の平均重合度１０００以下で０．８〜３μｍの平均粒径を持つ粒子７０〜９２重量％からなり、その平均重合度が１３００以下であることを特徴とするペースト加工用塩化ビニル系樹脂（特許文献２）、（３）レーザー回折法の測定による重合体粒子の粒径が、少なくとも０.２〜５μｍの範囲に連続的に分布し、頻度に二つの極大値を有し、小粒子の群の極大値を与える粒径が０.２〜０.６μｍの範囲に、大粒子の群の極大値を与える粒径が１.０〜４.０μｍの範囲にそれぞれあり、全体の平均粒径が０.６〜３.０μｍであって、粒径０.１〜０.７μｍの粒子と粒径０.８〜５μｍの粒子との比率が５〜４０重量％対６０〜９５重量％である粒径分布を有し、該樹脂１００重量部とジ−２−エチルヘキシルフタレート６０重量部とを混合して得られるペーストの未分散粒子率が０.１重量％以下で、セーバーズ流出量が３０ｇ／１００秒以上であることを特徴とするペースト加工用塩化ビニル系樹脂顆粒（特許文献３）等がある。 For example, (1) 30 to 50% by weight of polyvinyl chloride resin particles (A) having a particle diameter of 0.01 μm or more and less than 0.45 μm, and a particle diameter of 0.45 μm or more 4 The polyvinyl chloride resin particles (B) having a particle diameter of less than 5 μm are 35 to 55% by weight, and the polyvinyl chloride resin particles (C) having a particle diameter of 4.5 μm or more and 20 μm or less are 10 to 30% by weight, And the average particle diameter in a granule is 20-130 micrometers, The polyvinyl chloride resin granule for paste processing (patent document 1) characterized by the above-mentioned. (2) The average degree of polymerization of vinyl chloride resin is 1500 or more and 0.00. 8-30% by weight of fine particles having an average particle diameter of 05-0.2 μm and 70-92% by weight of particles having an average polymerization degree of vinyl chloride resin of 1000 or less and an average particle diameter of 0.8-3 μm. The average A vinyl chloride resin for paste processing (patent document 2) characterized in that the degree of integration is 1300 or less (3) The particle size of the polymer particles measured by laser diffraction method is at least in the range of 0.2 to 5 μm. The particle size which gives the maximum value of the group of large particles in the range of 0.2 to 0.6 μm, which is continuously distributed, has two maximum values in frequency, and gives the maximum value of the group of small particles Are in the range of 1.0 to 4.0 μm, the overall average particle size is 0.6 to 3.0 μm, and the particle size is 0.1 to 0.7 μm and the particle size is 0.8 to 5 μm. Of a paste obtained by mixing 100 parts by weight of the resin with 60 parts by weight of di-2-ethylhexyl phthalate, having a particle size distribution of 5 to 40% by weight to 60 to 95% by weight. The undispersed particle ratio is 0.1% by weight or less, and the saver spillage is 30 g / 100 seconds or more. And vinyl chloride resin granules (Patent Document 3) for paste processing.
また、特定の用途のものとしては、例えば、（４） 基布とパイルとによって形成された表層部と、表層部裏面に積層された裏層部とからなり、該裏層部は、ポリ塩化ビニル１００重量部に対して可塑剤７０〜１００重量部、無機充填剤３００〜５００重量部、有機発泡剤１〜３重量部及び発泡安定剤１〜３重量部が配合され、有機発泡剤の活性化による１．１〜１．８倍に発泡させた発泡層と、ポリ塩化ビニル１００重量部に対して無機充填剤３００〜５００重量部が含まれる非発泡層と、発泡層と非発泡層の間に介在するガラス繊維布層とで形成され、発泡層を表層部裏面側に配置させて積層してなるタイルカーペット（特許文献４）、（５）上部織物層と下部裏打ち層からなるタイルカーペットを製造する方法において、上部織物層として、該織物層１ｍ２ あたり、ペースト塩ビ樹脂、可塑剤、安定剤を主成分とする塩化ビニルプラスチゾル組成物を０．５Ｋｇ〜２Ｋｇ含浸した上部織物層を使用することを特徴とするタイルカーペットの製造方法（特許文献５）、（６）２層構造のシート材料において、上部に主としてガラス繊維からなる無機繊維層、下部に化学合成繊維からなる有機繊維層が配置され、該シートの有機繊維層を構成する化学合成繊維として、１４０℃における熱収縮率が、３０から６０％である化学合成繊維が使用され、前記化学合成繊維の配合量が、シート重量に対して２０から５０重量％であることを特徴とするシート材料（特許文献６）、（７）塩化ビニル−酢酸ビニル共重合体と、ペースト塩化ビニル系樹脂と、可塑剤と、充填材と、短繊維とを含有する樹脂組成物を板状に成形してなる床材用シートであって、短繊維が８〜１３重量％含まれていることを特徴とする床材用シート（特許文献７）等がある。
上記の（１）〜（３）は、特定の粒度等からなる塩化ビニル樹脂に関するものであって、粉体流動性、発泡性、ケミカルエンボス特性等の向上を図ったものである。
また、上記の（４）〜（７）は、ペースト塩化ビニル系樹脂を用いたタイルカーペットや床材用シート等に関するものであって、耐久性、反り防止、寸法安定性等を図ったものである。
In addition, specific applications include, for example, (4) a surface layer portion formed of a base fabric and a pile, and a back layer portion laminated on the back surface of the surface layer portion. 70 to 100 parts by weight of plasticizer, 300 to 500 parts by weight of inorganic filler, 1 to 3 parts by weight of organic foaming agent, and 1 to 3 parts by weight of foaming stabilizer are blended with 100 parts by weight of vinyl. A foam layer that has been foamed 1.1 to 1.8 times, a non-foam layer containing 300 to 500 parts by weight of an inorganic filler with respect to 100 parts by weight of polyvinyl chloride, and a foam layer and a non-foam layer. Tile carpet (Patent Document 4) formed with a glass fiber cloth layer interposed therebetween and laminated with a foam layer disposed on the back side of the surface layer part (Patent Document 4), Tile carpet composed of an upper fabric layer and a lower backing layer In the method of manufacturing the upper fabric layer An upper fabric layer impregnated with 0.5 kg to 2 kg of vinyl chloride plastisol composition mainly composed of a paste vinyl chloride resin, a plasticizer and a stabilizer is used per 1 m 2 of the fabric layer. Manufacturing method (Patent Document 5), (6) In a sheet material having a two-layer structure, an inorganic fiber layer mainly made of glass fiber is arranged on the upper part, and an organic fiber layer made of chemically synthesized fiber is arranged on the lower part, and the organic fiber layer of the sheet Is used as a chemically synthesized fiber having a heat shrinkage rate at 140 ° C. of 30 to 60%, and the compounding amount of the chemically synthesized fiber is 20 to 50% by weight with respect to the sheet weight. (7) A vinyl chloride-vinyl acetate copolymer, a paste vinyl chloride resin, a plasticizer, a filler, and a short fiber. There is a sheet for flooring formed by molding a resin composition to be contained into a plate shape, which includes 8 to 13% by weight of short fibers (Patent Document 7). .
The above (1) to (3) relate to a vinyl chloride resin having a specific particle size and the like, and are intended to improve powder flowability, foamability, chemical embossing characteristics, and the like.
The above (4) to (7) relate to tile carpets and flooring sheets using a paste vinyl chloride resin, and are intended for durability, warpage prevention, dimensional stability, etc. is there.
タイルカーペットは、オフィスビルなど主に建築物の床面に敷かれる一辺が約５０cmの正方形状のカーペットである。従来から使用されているフロアーカーペットに比べ、オフィスの椅子、机等により傷んだ場合、その箇所だけ取り替えれば良い機能的な部分と、最近オフィス空間の環境のレベルアップのニーズの高まりに伴って堅調に需要が拡大している分野である。
タイルカーペットは、ナイロンやポリエステル繊維のカーペットに塩化ビニル樹脂層を裏打ちしたものであり、ゾル（塩化ビニル樹脂）をエンドレスベルトに塗布するが、先ず、第１コーターで１〜２ｍｍでゾルを塗布し、この上にガラス不織布を乗せ、更に第２コーターでゾルを塗布した後、更にその上に基布（ポリエステル不織布にナイロン繊維等のパイルが織り込まれている）を乗せ、加熱炉でゲル化溶融されることにより製造されるが、この場合、加熱温度による基布の熱収縮を考慮して、炉の上層（基布側）は１４０〜１５０℃、下層（ベルト下側）約２００℃で成形されるのが通常である。しかし、最近では、加熱温度による基布の熱収縮を考慮して、１２０℃付近での加熱処理においても優れた強度を有するもの、即ち、低温特性に優れたものが求められているのが実状である。
以上のように、タイルカーペットの製造においては、加熱処理により基布の熱収縮が生起するので、この点の配慮が重要になる。このため、強度（耐久性、反り防止、寸法安定性等）が求められるタイルカーペット等の製造においては、加熱処理温度を低くすることができるペースト用塩化ビニル系樹脂が求められている。
A tile carpet is a square carpet with a side of about 50 cm, which is mainly laid on the floor of an office building or the like. Compared to traditional floor carpets, when damaged by office chairs, desks, etc., functional parts that only need to be replaced, and with the recent increase in the level of office space environment This is a field where demand is steadily expanding.
The tile carpet is a nylon or polyester fiber carpet lined with a vinyl chloride resin layer, and sol (vinyl chloride resin) is applied to the endless belt. First, the sol is applied at 1 to 2 mm with the first coater. Put a glass nonwoven fabric on top of this, apply sol with a second coater, then place a base fabric (a polyester nonwoven fabric is woven with a pile of nylon fibers, etc.) on it, and gel and melt it in a heating furnace. In this case, considering the thermal shrinkage of the base fabric due to the heating temperature, the upper layer (base fabric side) of the furnace is molded at 140 to 150 ° C. and the lower layer (belt lower side) at about 200 ° C. It is usually done. However, in recent years, considering the thermal shrinkage of the base fabric due to the heating temperature, a material having an excellent strength even in a heat treatment at around 120 ° C., that is, a material having excellent low-temperature characteristics has been demanded. It is.
As described above, in the production of tile carpet, heat shrinkage of the base fabric occurs due to the heat treatment, and thus this point is important. For this reason, in the manufacture of tile carpets and the like that require strength (durability, warpage prevention, dimensional stability, etc.), a vinyl chloride resin for paste that can lower the heat treatment temperature is required.
本発明の課題は、強度（耐久性、反り防止、寸法安定性等）が求められるタイルカーペット等の製造において、加熱処理温度を低くすることができるペースト用塩化ビニル系樹脂を提供することにある。 An object of the present invention is to provide a vinyl chloride resin for paste that can lower the heat treatment temperature in the production of tile carpets and the like that require strength (durability, warpage prevention, dimensional stability, etc.). .
本発明者らは、上記の課題を解決するため鋭意研究を重ねたところ、粒度と平均重合度が異なる２種類の塩化ビニル系樹脂を特定の割合で配合すると、強度（耐久性、反り防止、寸法安定性等）が求められるタイルカーペット等の製造において、加熱処理温度を低くすることができるペースト用塩化ビニル系樹脂が得られることを知り、更に研究を重ねた結果、本発明を完成するに至った。
即ち、本発明は、以下の発明から構成されるものである。
１．塩化ビニル系樹脂が、以下の要件１を満たす塩化ビニル系重合体Ａと要件２を満たす塩化ビニル系重合体Ｂからなるものであって、しかも該重合体Ａと重合体Ｂの関係が、以下の要件３を満たすことを特徴とするペースト用塩化ビニル系樹脂。
要件１：塩化ビニル系重合体Ａ
平均粒径０．１〜０．２５μｍ、
平均重合度１０００〜１４００
要件２：塩化ビニル系重合体Ｂ
平均粒径１．０〜２．５μｍ、
平均重合度６００〜８００
要件３：塩化ビニル系重合体Ａと塩化ビニル系重合体Ｂの割合
塩化ビニル系重合体Ａ１５〜４０重量％、
塩化ビニル系重合体Ｂ６０〜８５重量％
２．要件１を満たす塩化ビニル系重合体Ａの分散水溶液と要件２を満たす塩化ビニル系重合体Ｂの分散水溶液を、要件３を満たすように配合して得た、要件１〜要件３を満たす塩化ビニル系樹脂の分散水溶液を噴霧乾燥することを特徴とする上記１又は２記載のペースト用塩化ビニル系樹脂の製造方法。
３．上記１記載のペースト用塩化ビニル系樹脂及び可塑剤からなる配合剤から構成されるペースト用塩化ビニル系樹脂組成物。
４．配合剤が、安定剤、充填剤、又は発泡剤からなる群の一種又は二種以上からなる成分を含有するものである上記３記載のペースト用塩化ビニル系樹脂組成物。
The inventors of the present invention have made extensive studies in order to solve the above problems. As a result, when two kinds of vinyl chloride resins having different particle sizes and average polymerization degrees are blended at a specific ratio, strength (durability, warpage prevention, In the manufacture of tile carpets and the like that require dimensional stability, etc., it has been found that a vinyl chloride resin for paste that can reduce the heat treatment temperature can be obtained, and as a result of further research, the present invention is completed. It came.
That is, this invention is comprised from the following invention.
1. The vinyl chloride resin is composed of a vinyl chloride polymer A satisfying the following requirement 1 and a vinyl chloride polymer B satisfying the requirement 2, and the relationship between the polymer A and the polymer B is as follows: A vinyl chloride resin for paste, which satisfies the requirement 3 of the above.
Requirement 1: Vinyl chloride polymer A
Average particle size 0.1-0.25 μm,
Average degree of polymerization 1000-1400
Requirement 2: Vinyl chloride polymer B
Average particle size 1.0-2.5 μm,
Average polymerization degree 600-800
Requirement 3: Ratio of vinyl chloride polymer A and vinyl chloride polymer B
Vinyl chloride polymer A 15 to 40% by weight,
Vinyl chloride polymer B60-85% by weight
2. Vinyl chloride satisfying requirements 1 to 3 obtained by blending a dispersion aqueous solution of vinyl chloride polymer A satisfying requirement 1 and a dispersion aqueous solution of vinyl chloride polymer B satisfying requirement 2 so as to satisfy requirement 3. 3. The method for producing a vinyl chloride resin for paste according to 1 or 2 above, wherein the dispersion aqueous solution of the resin is spray-dried.
3. A vinyl chloride resin composition for paste comprising the compounding agent comprising the vinyl chloride resin for paste and the plasticizer according to 1 above.
4). 4. The vinyl chloride resin composition for paste as described in 3 above, wherein the compounding agent contains one or more components of the group consisting of a stabilizer, a filler, or a foaming agent.
本発明のペースト用塩化ビニル系樹脂は、上記の要件１を満たす塩化ビニル系重合体Ａと要件２を満たす塩化ビニル系重合体Ｂからなり、塩化ビニル系重合体Ａと塩化ビニル系重合体Ｂは、上記の要件３を満たすことを特徴とするものであって、強度（耐久性、反り防止、寸法安定性等）が要求される用途（タイルカーペット等）に最適な特性を有する点で優れている。
本発明は、以下の知見に基づいてなされたものである。
前述したように、通常の用途の場合、ペースト用塩化ビニル系樹脂は、その特性としては、粉体流動性、発泡性、ケミカルエンボス特性等の向上に資するものが要求されるが、タイルカーペット等のような用途の場合、ペースト用塩化ビニル系樹脂は、その特性としては、強度（耐久性、反り防止、寸法安定性等）の向上に資するものが要求される。
このような現状下、強度（耐久性、反り防止、寸法安定性等）の特性向上に資するペースト用塩化ビニル系樹脂について研究を重ねたところ、塩化ビニル系樹脂の粒子径、平均重合度、配合割合等が重要な因子であることが分かった。
そこで、更に研究を重ねた結果、上記の要件１と２を満たす塩化ビニル系重合体Ａと塩化ビニル系重合体Ｂからなるものであって、重合体Ａと重合体Ｂは、上記の要件３を満たすようにしたところ、優れた特性を有するペースト用塩化ビニル系樹脂が得られることをつきとめ、本発明を完成した。
The vinyl chloride resin for paste of the present invention comprises a vinyl chloride polymer A satisfying the above requirement 1 and a vinyl chloride polymer B satisfying the requirement 2, and the vinyl chloride polymer A and the vinyl chloride polymer B. Is characterized by satisfying the above requirement 3, and is excellent in that it has optimum characteristics for applications (such as tile carpet) that require strength (durability, warpage prevention, dimensional stability, etc.). ing.
The present invention has been made based on the following findings.
As described above, in the case of normal use, the vinyl chloride resin for paste is required to contribute to improvement of powder flowability, foamability, chemical embossing characteristics, etc. In the case of such applications, the vinyl chloride resin for paste is required to have a characteristic that contributes to improvement in strength (durability, warpage prevention, dimensional stability, etc.).
Under such circumstances, research on vinyl chloride resin for paste that contributes to improving the properties of strength (durability, warpage prevention, dimensional stability, etc.) revealed that the particle size, average degree of polymerization, and blending of vinyl chloride resin It was found that the ratio was an important factor.
Therefore, as a result of further research, it is composed of a vinyl chloride polymer A and a vinyl chloride polymer B that satisfy the above requirements 1 and 2, and the polymer A and the polymer B are the above requirements 3 As a result, it was found that a vinyl chloride resin for paste having excellent characteristics was obtained, and the present invention was completed.
以上のように、本発明のペースト用塩化ビニル系樹脂は、上記の要件１〜３を満たすものであって、優れた低温特性（強度）を有する点おいて、特段の効果を奏するが、このようなことは、以下述べるように、全く意外な結果である。
通常、塩化ビニル系樹脂の引張強度（抗張力）は、加熱温度１２０℃から測定可能となり、ホモポリマーの場合１８０℃、コポリマーの場合１６０℃で、それぞれ最高強度に達するとされており、塩化ビニル系樹脂の１２０℃の引張強さは、低いのが普通である。
これに対して、本発明の塩化ビニル系樹脂は、１２０℃において優れた強度を有し、最高強度に達する温度は１６０℃付近となる。このため、最高強度に達する温度は、従来より２０℃程度低くなることからみて、本発明の塩化ビニル系樹脂は、従来の塩化ビニル系樹脂とは全く異なる特性を有しているということができる。
前述したように、タイルカーペットの製造では、加熱処理による基布の熱収縮を考慮して、加熱処理は１４０〜１５０℃で実施されているのが通常である。
従って、従来のホモポリマーを用いる場合、タイルカーペットの製造の加熱処理は、該樹脂の最高強度温度である１８０℃付近ではなく、該最高強度温度より３０〜４０℃も低い温度で実施していることになる。このため、従来では、使用した樹脂の強度が低い温度で実施することになるので、強度に優れた特性を有するタイルカーペットを製造することが困難であった。
これに対して、本発明のペースト用塩化ビニル系樹脂は、１２０〜１６０℃の強度が優れているから、タイルカーペットの製造の加熱処理は、１２０〜１６０℃での低温実施が可能となるため、加熱処理による基布の熱収縮が防止し得るので、大変有利である。
このように、本発明の塩化ビニル系樹脂組成物は、低温特性に優れているので、タイルカーペットの製造において、低温での加熱処理が可能となる。
従って、本発明の塩化ビニル系樹脂を採用すると、加熱処理による基布の熱収縮が防止し得るので、特に低温特性が要求される用途、例えば、パイルカーペット等に最適である。
上記のような本発明の優れた効果は、本発明の要件１〜３の何れが欠けても、達成できないことからみて、本発明の優れた効果は、該要件の複合的な相乗効果により達成されたものと推察される。
何れにしても、本発明の特段の効果からみて、本発明の要件１〜３の選択には格別の意義があるとするのが自然であろう。
As described above, the vinyl chloride resin for paste of the present invention satisfies the above-mentioned requirements 1 to 3, and has a special effect in that it has excellent low-temperature characteristics (strength). This is a completely unexpected result as described below.
Normally, the tensile strength (tensile strength) of vinyl chloride resin can be measured from a heating temperature of 120 ° C, and the maximum strength is reached at 180 ° C for homopolymers and 160 ° C for copolymers. The tensile strength at 120 ° C. of the resin is usually low.
In contrast, the vinyl chloride resin of the present invention has excellent strength at 120 ° C., and the temperature reaching the maximum strength is around 160 ° C. For this reason, it can be said that the vinyl chloride resin of the present invention has completely different characteristics from the conventional vinyl chloride resin, since the temperature at which the maximum strength is reached is about 20 ° C. lower than the conventional one. .
As described above, in the manufacture of tile carpet, the heat treatment is usually performed at 140 to 150 ° C. in consideration of the thermal shrinkage of the base fabric due to the heat treatment.
Therefore, when the conventional homopolymer is used, the heat treatment for the production of tile carpet is not performed at around 180 ° C., which is the maximum strength temperature of the resin, but at a temperature 30 to 40 ° C. lower than the maximum strength temperature. It will be. For this reason, conventionally, since the strength of the used resin is carried out at a low temperature, it has been difficult to produce a tile carpet having excellent strength characteristics.
On the other hand, since the vinyl chloride resin for paste of the present invention has an excellent strength of 120 to 160 ° C., the heat treatment for manufacturing the tile carpet can be performed at a low temperature of 120 to 160 ° C. Since the heat shrinkage of the base fabric due to the heat treatment can be prevented, it is very advantageous.
Thus, since the vinyl chloride resin composition of the present invention is excellent in low temperature characteristics, heat treatment at a low temperature is possible in the production of tile carpet.
Accordingly, when the vinyl chloride resin of the present invention is employed, thermal shrinkage of the base fabric due to heat treatment can be prevented, which is particularly suitable for applications requiring low temperature characteristics, such as pile carpets.
In view of the fact that the excellent effects of the present invention as described above cannot be achieved without any of the requirements 1 to 3 of the present invention, the excellent effects of the present invention are achieved by a combined synergistic effect of the requirements. It is inferred that
In any case, in view of the special effects of the present invention, it will be natural that the selection of requirements 1 to 3 of the present invention has special significance.
以下、本発明を更に詳細に説明する。
本発明の特徴は、本発明の要件１を満たす塩化ビニル系重合体Ａと要件２を満たす塩化ビニル系重合体Ｂからなり、該重合体Ａと重合体Ｂの関係が、本発明の要件３を満たすことを特徴とするペースト用塩化ビニル系樹脂、及び該ペースト用塩化ビニル系樹脂及び可塑剤、安定剤、充填剤、又は発泡剤からなる配合剤から構成されるペースト用塩化ビニル系樹脂組成物にある。
本発明のペースト用塩化ビニル系樹脂、及びペースト用塩化ビニル系樹脂組成物について、以下説明する。
Hereinafter, the present invention will be described in more detail.
A feature of the present invention is a vinyl chloride polymer A satisfying the requirement 1 of the present invention and a vinyl chloride polymer B satisfying the requirement 2. The relationship between the polymer A and the polymer B is the requirement 3 of the present invention. And a vinyl chloride resin composition for paste composed of a vinyl chloride resin for paste and a compounding agent comprising a plasticizer, a stabilizer, a filler, or a foaming agent. It is in the thing.
The vinyl chloride resin for paste and the vinyl chloride resin composition for paste of the present invention will be described below.
（１）ペースト用塩化ビニル系樹脂
本発明のペースト用塩化ビニル系樹脂は、本発明の要件１又は２を満たす塩化ビニル系重合体Ａ又はＢを含有する水性分散液を、本発明の要件３を満足するように、ブレンドする方法により得ることができる。
上記の塩化ビニル系重合体の水性分散液のブレンド方法としては、ブレンドすることが可能であればいかなる方法もとることが可能である。
例えば、水性分散液同士をブレンドする方法、水性分散液から塩化ビニル系樹脂をろ過又は遠心分離によりウェットケーキとした後、これを直接又は水で水性分散液に戻してブレンドする方法等、何れでもよい。
塩化ビニル系重合体の水性分散液の濃縮方法としては、例えば、透析膜や限外ろ過膜を用いた濃縮、真空蒸発器による濃縮、薄膜蒸発器による濃縮などを挙げることができる。これらの中で、膜濃縮に使用する膜には特に制限はなく、例えば、酢酸セルロース系膜、ポリスルホン系膜、ポリアミド系膜、ポリアクリロニトリル系膜、フッ素樹脂系膜などを挙げることができる。
本発明方法においては、上記の特定の粒径分布を有する塩化ビニル系重合体の固形分濃度が５５〜７５重量％、好ましくは６０〜７０重量％の塩化ビニル系重合体の水性分散液を噴霧乾燥処理する。
使用する噴霧乾燥機に特に制限はなく、例えば、噴霧形式としては、回転円盤型アトマイザー、二流体ノズル型アトマイザー、加圧ノズル型アトマイザーなどを挙げることができるが、これらの中で回転円盤式アトマイザーは、水性分散液の流量、密度、粘度などの変動に広く対応できるので好適に使用することができる。熱風と液滴群の接触方式にも特に制限はないが、併流方式が樹脂顆粒の熱履歴分布を小さくする上で好ましい。乾燥用空気は、大気から採取することができ、ことさらに湿度の調整を行う必要はないが、調湿を制限するものではない。乾燥用空気の入口温度は高いほど乾燥能率の上昇が望めるが、２００℃を超えると樹脂顆粒のゾル分散性が悪化する。しかし、従来技術のように１００℃以下の低い温度が必須ではなくて、１００℃より高く２００℃以下でよく、特に、１１０〜１７０℃の範囲が好ましい。また、乾燥用空気の出口温度は、４０〜７０℃の範囲が好ましく、４５〜５５℃の範囲がより好ましい。乾燥の程度は、乾燥された顆粒に含まれる水分が０.０５〜１.５重量％であることが好ましく、０.１〜１.０重量％であることがより好ましい。乾燥用空気の出口温度と、乾燥された顆粒の水分率は、塩化ビニル系重合体の水性分散液の供給速度と、乾燥用熱風の温度と風量を制御することにより調整することができる。
噴霧液滴径は、塩化ビニル系重合体の水性分散液の供給速度や固形分濃度と、回転円盤型アトマイザーでは円盤回転数により、二流体ノズル型アトマイザーではアトマイズ空気圧と風量により、加圧ノズル型アトマイザーでは圧力を主たる因子として制御することができる。塩化ビニル系重合体の水性分散液の噴霧乾燥により、目的の平均粒径の顆粒を得ることができる。
(1) Vinyl chloride resin for paste The vinyl chloride resin for paste of the present invention is an aqueous dispersion containing a vinyl chloride polymer A or B satisfying the requirement 1 or 2 of the present invention. Can be obtained by a blending method.
As a method for blending the aqueous dispersion of the above-mentioned vinyl chloride polymer, any method can be used as long as blending is possible.
For example, either a method of blending aqueous dispersions, a method of blending a vinyl chloride resin from aqueous dispersions by filtering or centrifuging them into wet cakes and then returning them to aqueous dispersions directly or with water, etc. Good.
Examples of the concentration method of the aqueous dispersion of the vinyl chloride polymer include concentration using a dialysis membrane or an ultrafiltration membrane, concentration using a vacuum evaporator, and concentration using a thin film evaporator. Among these, the membrane used for membrane concentration is not particularly limited, and examples thereof include a cellulose acetate membrane, a polysulfone membrane, a polyamide membrane, a polyacrylonitrile membrane, and a fluororesin membrane.
In the method of the present invention, an aqueous dispersion of a vinyl chloride polymer having a specific particle size distribution of the vinyl chloride polymer having a solid content concentration of 55 to 75% by weight, preferably 60 to 70% by weight is sprayed. Dry.
There is no particular limitation on the spray dryer to be used. For example, examples of the spray type include a rotary disk atomizer, a two-fluid nozzle atomizer, and a pressure nozzle atomizer. Among these, a rotary disk atomizer is included. Can be suitably used because it can widely cope with fluctuations in the flow rate, density, viscosity and the like of the aqueous dispersion. There is no particular limitation on the contact method between the hot air and the droplet group, but the combined flow method is preferable for reducing the thermal history distribution of the resin granules. The drying air can be collected from the atmosphere, and it is not necessary to adjust the humidity. However, humidity adjustment is not limited. The higher the inlet temperature of the drying air, the higher the drying efficiency can be expected. However, when the temperature exceeds 200 ° C., the sol dispersibility of the resin granules deteriorates. However, a low temperature of 100 ° C. or lower as in the prior art is not essential, and may be higher than 100 ° C. and 200 ° C. or lower, particularly preferably in the range of 110 to 170 ° C. Moreover, the range of 40-70 degreeC is preferable and, as for the exit temperature of drying air, the range of 45-55 degreeC is more preferable. The degree of drying is preferably 0.05 to 1.5% by weight, more preferably 0.1 to 1.0% by weight, of water contained in the dried granule. The outlet temperature of the drying air and the moisture content of the dried granules can be adjusted by controlling the supply rate of the aqueous dispersion of the vinyl chloride polymer and the temperature and air volume of the drying hot air.
The spray droplet diameter depends on the supply rate and solid content of the aqueous dispersion of the vinyl chloride polymer, the rotational speed of the disk for the rotary disk type atomizer, the atomizing air pressure and the air volume for the two-fluid nozzle type atomizer, and the pressurized nozzle type. In the atomizer, pressure can be controlled as a main factor. By spray-drying an aqueous dispersion of a vinyl chloride polymer, granules having a desired average particle diameter can be obtained.
（塩化ビニル系重合体）
本発明におけるペースト用塩化ビニル系樹脂を構成する塩化ビニル系重合体は、塩化ビニル単独重合体若しくは塩化ビニル共重合体又はこれらの混合物の何れよりなるものでもよい。
塩化ビニル系単量体としては、塩化ビニル単量体又は塩化ビニル単量体と塩化ビニル単量体との共重合可能なビニル単量体との混合物である。
上記の塩化ビニル単量体と共重合し得るビニル単量体としては、例えば、酢酸ビニル、プロピオン酸ビニル、ミリスチン酸ビニル、安息香酸ビニル等のビニルエステル類；アクリル酸、メタクリル酸、マレイン酸、フマル酸等の不飽和カルボン酸又はその無水物類；アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル等のアクリル酸エステル類；メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ブチル等のメタクリル酸エステル類；マレイン酸エステル、フマル酸エステル、桂皮酸エステル等の不飽和カルボン酸エステル類；ビニルメチルエーテル、ビニルアミルエーテル、ビニルフェニルエーテル等のビニルエーテル類；エチレン、プロピレン、ブテン、ペンテン等のモノオレフィン類；塩化ビニリデン、スチレン及びその誘導体、アクリロニトリル、メタクリロニトリル等が挙げられ、これらは１種又は２種以上で用いることが可能である。
(Vinyl chloride polymer)
The vinyl chloride polymer constituting the vinyl chloride resin for paste in the present invention may be any of a vinyl chloride homopolymer, a vinyl chloride copolymer, or a mixture thereof.
The vinyl chloride monomer is a vinyl chloride monomer or a mixture of a vinyl chloride monomer and a vinyl monomer copolymerizable with a vinyl chloride monomer.
Examples of the vinyl monomer that can be copolymerized with the above vinyl chloride monomer include vinyl esters such as vinyl acetate, vinyl propionate, vinyl myristate, and vinyl benzoate; acrylic acid, methacrylic acid, maleic acid, Unsaturated carboxylic acids such as fumaric acid or anhydrides; acrylic esters such as methyl acrylate, ethyl acrylate and butyl acrylate; methacrylic esters such as methyl methacrylate, ethyl methacrylate and butyl methacrylate; Unsaturated carboxylic acid esters such as maleic acid ester, fumaric acid ester and cinnamic acid ester; vinyl ethers such as vinyl methyl ether, vinyl amyl ether and vinyl phenyl ether; monoolefins such as ethylene, propylene, butene and pentene; Vinylidene, styrene and its Conductor, acrylonitrile, methacrylonitrile, etc. These can be used singly or in combination.
（塩化ビニル系重合体の水性分散液）
塩化ビニル系重合体の水性分散液の製造方法としては、特に制限はなく、一般にペースト用塩化ビニル系重合体の製造方法として知られている方法でよい。
例えば、塩化ビニル系単量体を脱イオン水、界面活性剤、水溶性重合開始剤と共に緩やかな撹拌下で重合を行う乳化重合法；乳化重合法で得られた粒子をシードとして用い乳化重合を行うシード乳化重合法；塩化ビニル系単量体を脱イオン水、界面活性剤、必要に応じて高級アルコール、水溶性高分子等の分散補助剤、油溶性重合開始剤をホモジナイザー等で混合分散した後、緩やかな撹拌下で重合を行うミクロ懸濁重合法；ミクロ懸濁重合法で得られた油溶性重合開始剤を含有するシードを用い重合を行うシードミクロ懸濁重合法；塩化ビニル系単量体を脱イオン水、水溶性高分子、必要に応じて界面活性剤等の分散補助剤、油溶性重合開始剤を激しい撹拌下で重合を行う懸濁重合法等が挙げられる。この際、何れの方法においても、３０〜８０℃の温度範囲において重合することが好ましい。
(Aqueous dispersion of vinyl chloride polymer)
The method for producing the aqueous dispersion of the vinyl chloride polymer is not particularly limited, and may be a method generally known as a method for producing a vinyl chloride polymer for paste.
For example, an emulsion polymerization method in which a vinyl chloride monomer is polymerized with gentle stirring with deionized water, a surfactant, and a water-soluble polymerization initiator; emulsion polymerization is performed using particles obtained by the emulsion polymerization method as a seed. Seed emulsion polymerization method: vinyl chloride monomer was mixed and dispersed with deionized water, surfactant, if necessary, higher alcohol, dispersion aid such as water-soluble polymer, oil-soluble polymerization initiator with homogenizer etc. Thereafter, a micro suspension polymerization method in which polymerization is performed with gentle stirring; a seed micro suspension polymerization method in which polymerization is performed using a seed containing an oil-soluble polymerization initiator obtained by the micro suspension polymerization method; Examples of the polymerization method include deionized water, a water-soluble polymer, a dispersion aid such as a surfactant as required, and a suspension polymerization method in which an oil-soluble polymerization initiator is polymerized with vigorous stirring. At this time, in any method, it is preferable to polymerize in a temperature range of 30 to 80 ° C.
（界面活性剤）
塩化ビニル系重合体の水性分散液を製造する際に、界面活性剤を使用することも可能である。
その場合の界面活性剤としては、例えば、ラウリル硫酸エステルナトリウム，ミリスチル硫酸エステルナトリウムのようなアルキル硫酸エステル塩類、ドデシルベンゼンスルホン酸ナトリウム，ドデシルベンゼンスルホン酸カリウムのようなアルキルアリールスルホン酸塩類、ジオクチルスルホコハク酸ナトリウム，ジヘキシルスルホコハク酸ナトリウムのようなスルホコハク酸エステル塩類、ラウリン酸アンモニウム，ステアリン酸カリウムの如き脂肪酸塩類、ポリオキシエチレンアルキル硫酸エステル塩類、ポリオキシエチレンアルキルアリール硫酸エステル塩類等のアニオン界面活性剤；ソルビタンモノオレート，ポリオキシエチレンソルビタンモノステアレートのようなソルビタンエステル類、ポリオキシエチレンアルキルフェニルエーテル類、ポリオキシエチレンアルキルエステル類などのノニオン界面活性剤類などの従来より知られているものを１種以上で用いることができ、これらの界面活性剤は、重合時に使用する以外に、改質を目的として重合後の水性分散液に添加することも可能である。
(Surfactant)
In producing an aqueous dispersion of a vinyl chloride polymer, a surfactant may be used.
Examples of the surfactant include alkyl sulfates such as sodium lauryl sulfate and sodium myristyl sulfate, alkylaryl sulfonates such as sodium dodecylbenzenesulfonate and potassium dodecylbenzenesulfonate, and dioctylsulfosuccinate. Anionic surfactants such as sodium sulfate, sulfosuccinic acid ester salts such as sodium dihexyl sulfosuccinate, fatty acid salts such as ammonium laurate and potassium stearate, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl aryl sulfate salts; Sorbitan esters such as sorbitan monooleate, polyoxyethylene sorbitan monostearate, polyoxyethylene alkylphenyl One or more conventionally known nonionic surfactants such as ethers and polyoxyethylene alkyl esters can be used, and these surfactants can be modified in addition to being used during polymerization. It is also possible to add to the aqueous dispersion after polymerization for the purpose of quality.
（分散剤）
塩化ビニル系重合体の水性分散液を製造する際に、必要に応じて、分散剤を使用することも可能である。
その場合の分散剤としては、例えばセチルアルコール，ラウリルアルコール等の高級アルコール、ラウリル酸，パルミチン酸，ステアリン酸等の高級脂肪酸又はそのエステル類、芳香族炭化水素、高級脂肪族炭化水素、塩素化パラフィン等のハロゲン化炭化水素、ポリビニルアルコール，ヒドロキシメチルセルロース，ポリビニルピロリドン等の水溶性高分子等が挙げられ、これらを１種以上で用いることができる。
(Dispersant)
When producing an aqueous dispersion of a vinyl chloride polymer, a dispersant may be used as necessary.
Examples of the dispersant include higher alcohols such as cetyl alcohol and lauryl alcohol, higher fatty acids such as lauric acid, palmitic acid, and stearic acid or esters thereof, aromatic hydrocarbons, higher aliphatic hydrocarbons, and chlorinated paraffins. And water-soluble polymers such as polyvinyl alcohol, hydroxymethyl cellulose, polyvinyl pyrrolidone and the like, and one or more of them can be used.
（重合開始剤）
塩化ビニル系重合体の水性分散液を製造する際には、重合開始剤を使用することができる。
例えば、過硫酸カリウム、過硫酸アンモニウム、過酸化水素等の水溶性重合開始剤；ベンゾイルパーオキサイド，ｐ−クロロベンゾイルパーオキサイド等の芳香族ジアシルパーオキサイド、カプロイルパーオキサイド，ラウロイルパーオキサイド等の脂肪族ジアシルパーオキサイド、アゾビスイソブチロニトリル，アゾビスイソバレロニトリル等のアゾ化合物、ｔ−ブチルパーオキシピバレート等の有機酸のパーオキシジエステル、ジイソプロピルパーオキシジカーボネート，ジオクチルパーオキシジカーボネート等のパーオキシジカーボネート、アセチルシクロヘキシルスルホニルパーオキサイド等の油溶性開始剤が挙げられる。そして、これらは単独又は２種類以上の組合わせで用いることが可能である。
そして、重合温度が、重合開始剤の１０時間半減期温度よりも低い場合は、重合温度をコントロールする目的で、例えばチオ硫酸ナトリウム、アスコルビン酸などの還元剤を単独で重合時に添加するか、硫酸鉄−アスコルビン酸、硫酸銅−アスコルビン酸のようなレドックス系開始剤との併用で重合を行ってもよい。
(Polymerization initiator)
A polymerization initiator can be used when producing an aqueous dispersion of a vinyl chloride polymer.
For example, water-soluble polymerization initiators such as potassium persulfate, ammonium persulfate and hydrogen peroxide; aromatic diacyl peroxides such as benzoyl peroxide and p-chlorobenzoyl peroxide; aliphatics such as caproyl peroxide and lauroyl peroxide Azo compounds such as diacyl peroxide, azobisisobutyronitrile, azobisisovaleronitrile, peroxy diesters of organic acids such as t-butyl peroxypivalate, diisopropyl peroxy dicarbonate, dioctyl peroxy dicarbonate, etc. Examples thereof include oil-soluble initiators such as peroxydicarbonate and acetylcyclohexylsulfonyl peroxide. And these can be used individually or in combination of 2 or more types.
When the polymerization temperature is lower than the 10-hour half-life temperature of the polymerization initiator, for the purpose of controlling the polymerization temperature, for example, a reducing agent such as sodium thiosulfate or ascorbic acid is added alone during the polymerization, or sulfuric acid is used. Polymerization may be performed in combination with a redox initiator such as iron-ascorbic acid or copper sulfate-ascorbic acid.
（２）ペースト用塩化ビニル系樹脂組成物
本ペースト用塩化ビニル系樹脂組成物は、上記のペースト用塩化ビニル系樹脂に、可塑剤、安定剤、充填剤、発泡剤等の配合剤を配合することにより得ることができる。
（可塑剤）
本可塑剤は、成型加工性に優れたゾル粘度と適当な硬度を有する成型品を得るために、使用するものである。
本可塑剤としては、塩化ビニル系樹脂加工に用いられるものであれば、特に制限はなく、使用することができる。
例えば、フタル酸ジ−ｎ−ブチル、フタル酸ジ−２−エチルヘキシル（以下、ＤＯＰという）、フタル酸ジイソオクチル、フタル酸オクチルデシル、フタル酸ジイソデシル、フタル酸ブチルベンジル、イソフタル酸ジ−２−エチルヘキシル等のフタル酸系可塑剤；アジピン酸ジ−２−エチルヘキシル、アジピン酸ジ−ｎ−デシル、アジピン酸ジイソデシル、アゼライン酸ジ−２−エチルヘキシル、セバシン酸ジブチル、セバシン酸ジ−２−エチルヘキシル等の脂肪酸エステル系可塑剤；リン酸トリブチル、リン酸トリ−２−エチルヘキシルジフェニル、リン酸トリクレジル等のリン酸エステル系可塑剤；エポキシ化大豆油、エポキシ化トール油、脂肪酸−２−エチルヘキシル等のエポキシ系可塑剤等があげられ、これらの１種又は２種以上を混合して使用してもよい。
可塑剤の使用量は、ペースト用塩化ビニル系樹脂１００重量部に対し３０〜２００重量部、好ましくは４０〜１００重量部であることが好ましい。
(2) Vinyl chloride resin composition for paste The vinyl chloride resin composition for paste contains compounding agents such as a plasticizer, a stabilizer, a filler, and a foaming agent in the vinyl chloride resin for paste. Can be obtained.
(Plasticizer)
This plasticizer is used in order to obtain a molded product having a sol viscosity excellent in molding processability and an appropriate hardness.
The plasticizer is not particularly limited as long as it is used for vinyl chloride resin processing, and can be used.
For example, di-n-butyl phthalate, di-2-ethylhexyl phthalate (hereinafter referred to as DOP), diisooctyl phthalate, octyl decyl phthalate, diisodecyl phthalate, butyl benzyl phthalate, di-2-ethylhexyl isophthalate, etc. Phthalic acid plasticizers; fatty acid esters such as di-2-ethylhexyl adipate, di-n-decyl adipate, diisodecyl adipate, di-2-ethylhexyl azelate, dibutyl sebacate, di-2-ethylhexyl sebacate Phosphate plasticizers such as tributyl phosphate, tri-2-ethylhexyl diphenyl phosphate, tricresyl phosphate; Epoxy plasticizers such as epoxidized soybean oil, epoxidized tall oil, and fatty acid-2-ethylhexyl Such as one or more of these It may be used in the combined.
The amount of the plasticizer used is 30 to 200 parts by weight, preferably 40 to 100 parts by weight, based on 100 parts by weight of the vinyl chloride resin for paste.
（安定剤）
本安定剤は、成型加工性に優れたものを得るために、使用することができる。
例えば、鉛白、塩基性ケイ酸鉛、三塩基性硫酸鉛、三塩基性亜リン酸鉛、三塩基性フタル酸鉛等の無機鉛塩系安定剤；ステアリン酸、ラウリン酸、リシノール酸、ナフテン酸、２−エチルヘキソイン酸等の脂肪酸；ナフテン酸カドミウム、ナフテン酸バリウム、ナフテン酸カルシウム、ナフテン酸亜鉛、ナフテン酸スズ、ナフテン酸マグネシウム等の金属塩からなる金属石鹸；バリウム−カドミウム系、バリウム−亜鉛系、カドミウム−バリウム−亜鉛系、カルシウム−亜鉛系、マグネシウム−亜鉛系等の液状安定剤；ジブチルスズジラウレート、ジブチルスズマレエート、ジブチルスズメルカプチドのような有機スズ安定剤；その他にエポキシ系安定剤、有機亜リン酸化合物等が挙げられ、これら２種以上を混合して用いてもよい。
安定剤の使用量としては、ペースト用塩化ビニル系樹脂１００重量部に対し１〜１０重量部、好ましくは２〜５重量部であることが好ましい。
(Stabilizer)
This stabilizer can be used in order to obtain an excellent molding processability.
Inorganic lead salt stabilizers such as lead white, basic lead silicate, tribasic lead sulfate, tribasic lead phosphite, tribasic lead phthalate; stearic acid, lauric acid, ricinoleic acid, naphthene Acids, fatty acids such as 2-ethylhexoic acid; metal soaps composed of metal salts such as cadmium naphthenate, barium naphthenate, calcium naphthenate, zinc naphthenate, tin naphthenate, magnesium naphthenate; barium-cadmium, barium-zinc , Cadmium-barium-zinc, calcium-zinc, magnesium-zinc, etc. liquid stabilizers; organotin stabilizers such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin mercaptide; other epoxy stabilizers, organic A phosphorous acid compound etc. are mentioned, and these 2 or more types may be mixed and used.
The amount of the stabilizer used is 1 to 10 parts by weight, preferably 2 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin for paste.
（充填剤）
本充填剤は、製品の柔軟性、風合い、強度等のために使用するものである。
例えば、炭酸カルシウム、ケイソウ土、炭酸マグネシウムを併用することも可能である。
充填剤の使用量は、ペースト用塩化ビニル系樹脂１００重量部に対し３０〜３００重量部、好ましくは５０〜１５０重量部であることが好ましい。
(filler)
This filler is used for the flexibility, texture, strength, etc. of the product.
For example, calcium carbonate, diatomaceous earth, and magnesium carbonate can be used in combination.
The amount of filler used is 30 to 300 parts by weight, preferably 50 to 150 parts by weight, based on 100 parts by weight of the vinyl chloride resin for paste.
(発泡剤)
本発泡剤は、優れた発泡性を有するものを得るために、使用することができる。
例えば、重炭酸ナトリウム、重炭酸アンモニウム、亜硝酸アンモニウム、アミド化合物、ホウ水素化ナトリウム等の無機発泡剤；イソシアネート化合物、アゾ化合物、ヒドラジン誘導体、セミカルバジド化合物、アジ化合物、ニトロソ化合物、トリアゾール化合物等の有機系発泡剤等が挙げられ、これら各種発泡剤を２種以上を混合して使用してもよい。
また、必要に応じて、亜鉛華（酸化亜鉛）等の分解促進剤を併用することも可能である。 発泡剤の使用量としては、ペースト用塩化ビニル系樹脂１００重量部に対し１〜２０重量部、好ましくは２〜７重量部であることが好ましい。
(Foaming agent)
This foaming agent can be used in order to obtain what has the outstanding foamability.
For example, inorganic foaming agent such as sodium bicarbonate, ammonium bicarbonate, ammonium nitrite, amide compound, sodium borohydride; organic system such as isocyanate compound, azo compound, hydrazine derivative, semicarbazide compound, azide compound, nitroso compound, triazole compound A foaming agent etc. are mentioned, You may use these various foaming agents in mixture of 2 or more types.
Further, if necessary, a decomposition accelerator such as zinc white (zinc oxide) can be used in combination. The amount of the foaming agent used is 1 to 20 parts by weight, preferably 2 to 7 parts by weight, based on 100 parts by weight of the vinyl chloride resin for paste.
(その他の添加剤)
その他の添加剤として、必要に応じて、酸化チタン等の顔料、難燃剤、希釈剤等の有機溶媒等を添加しても差し支えない。
(Other additives)
As other additives, pigments such as titanium oxide, organic solvents such as flame retardants and diluents may be added as necessary.
本発明のペースト用塩化ビニル系樹脂は、強度（耐久性、反り防止、寸法安定性等）の点に優れた特性を有するが、特に低温特性（強度）において、特段の効果を奏する。
即ち、本発明のペースト用塩化ビニル系樹脂は、１２０〜１６０℃の強度が優れているから、タイルカーペットの製造の加熱処理は、１２０〜１６０℃での低温実施が可能となるため、加熱処理による基布の熱収縮が防止し得る。
従って、特に低温特性が要求される用途、例えば、パイルカーペット等に最適である。
The vinyl chloride resin for pastes of the present invention has excellent properties in terms of strength (durability, warpage prevention, dimensional stability, etc.), but has a particular effect particularly in low temperature properties (strength).
That is, since the vinyl chloride resin for paste of the present invention has excellent strength at 120 to 160 ° C., the heat treatment for manufacturing the tile carpet can be performed at a low temperature at 120 to 160 ° C. The thermal contraction of the base fabric due to can be prevented.
Therefore, it is most suitable for applications requiring low temperature characteristics, such as pile carpets.
以下、実施例等を挙げて本発明を更に詳細に説明するが、本発明はこれらのものに限定されない。
実施例等における塩化ビニル系重合体の、（１）平均粒径、（２）平均重合度、（３）引張強さは、以下の測定方法に基づいて測定した。
（１）平均粒径
強制遠心一斉沈降法粒度分布測定装置［ＢＲＯＯＫＨＡＶＥＮ ＩＮＳＴＲＵＭＥＮＴ ＣＯＲＰ.製、ＢＩ−ＤＣＰ］を用い、１２００ｐｐｍで回転しているディスクにスピン液として１５ｍｌのイオン交換水を入れ、次いでバッファ液としてメタノール１ｍｌを、続いて試料濃度１重量％水分散液０.２５mlを注入し、測定時間２時間にて塩化ビニル系重合体水性分散液の粒子又は乾燥により得られた顆粒の累積粒径分布を測定し、５０重量％に相当する粒径を平均粒径とした。
（２）平均重合度
ＪＩＳ−Ｋ６７２１（１９９７年）に準じて、測定した。
（３）引張強さ
２３℃、相対湿度５０％の雰囲気で、ペースト加工用塩化ビニル系樹脂１００重量部及びジ−２−エチルヘキシルフタレート６０重量部を擂漬機にて混練して得られたプラスチゾルを真空脱泡した後、ガラス板上に厚み１ｍｍのシートをギアオープンで加熱成形し、測定はＪＩＳ−Ｋ７１１３に準じて行った。
（試験片：２号試験片、試験速度：１００ｍｍ／ｍｉｎ）
Hereinafter, although an example etc. are given and the present invention is explained still in detail, the present invention is not limited to these.
The (1) average particle diameter, (2) average degree of polymerization, and (3) tensile strength of the vinyl chloride polymers in Examples and the like were measured based on the following measurement methods.
(1) Average particle size Using a forced centrifugal simultaneous sedimentation particle size distribution analyzer [BROOKHAVEN INSTRUMENT CORP., BI-DCP], a disk rotating at 1200 ppm was charged with 15 ml of ion-exchanged water as a spin solution, and then buffered Inject 1 ml of methanol as the liquid, and then add 0.25 ml of the 1% by weight aqueous dispersion of the sample concentration, and measure the cumulative particle size of the particles of the aqueous vinyl chloride polymer dispersion or the granules obtained by drying for 2 hours. The distribution was measured, and the particle size corresponding to 50% by weight was defined as the average particle size.
(2) Average polymerization degree It measured according to JIS-K6721 (1997).
(3) A plastisol obtained by kneading 100 parts by weight of a vinyl chloride resin for paste processing and 60 parts by weight of di-2-ethylhexyl phthalate in an atmosphere of 23 ° C. and 50% relative humidity in a pickling machine. After vacuum defoaming, a sheet having a thickness of 1 mm was thermoformed with a gear open on a glass plate, and the measurement was performed according to JIS-K7113.
(Test piece: No. 2 test piece, test speed: 100 mm / min)
１．塩化ビニル重合体Ａの製造
（製造例１）
１０リットルのステンレス製の攪拌機及びジャケット付き耐圧反応器に、脱イオン水１５０重量部、過硫酸カリウム０．０５重量部及びラウリル硫酸ナトリウム０．０５重量部を仕込み、窒素置換、減圧脱気を各２回繰り返した。その後、塩化ビニル１００重量部を仕込み、攪拌しながら昇温し、６１℃にて乳化重合を開始した。重合転化率１０〜８５重量％の期間に、ドデシルベンゼンスルホン酸ナトリウム５重量％水溶液を一定速度で１５重量部注入した。
重合転化率が９０重量％になった時点で冷却し、未反応単量体を除去した。スケールが殆どない状態で安定な重合体粒子水性分散液Ａを得た。
重合体の平均粒径は０．２μｍであり、平均重合度は９００であった。
1. Production of vinyl chloride polymer A (Production Example 1)
A 10 liter stainless steel stirrer and jacketed pressure-resistant reactor were charged with 150 parts by weight of deionized water, 0.05 parts by weight of potassium persulfate and 0.05 parts by weight of sodium lauryl sulfate, and each was purged with nitrogen and degassed under reduced pressure. Repeated twice. Thereafter, 100 parts by weight of vinyl chloride was charged, the temperature was increased while stirring, and emulsion polymerization was started at 61 ° C. 15 parts by weight of a 5% by weight aqueous solution of sodium dodecylbenzenesulfonate was injected at a constant rate during a polymerization conversion rate of 10 to 85% by weight.
When the polymerization conversion rate reached 90% by weight, the system was cooled to remove unreacted monomers. Stable polymer particle aqueous dispersion A was obtained with almost no scale.
The average particle size of the polymer was 0.2 μm, and the average degree of polymerization was 900.
（製造例２）
１０リットルのステンレス製の攪拌機及びジャケット付き耐圧反応器に、脱イオン水１５０重量部、過硫酸カリウム０．０５重量部及びラウリル硫酸ナトリウム０．０５重量部を仕込み、窒素置換、減圧脱気を各２回繰り返した。その後、塩化ビニル１００重量部を仕込み、攪拌しながら昇温し、５８．５℃にて乳化重合を開始した。重合転化率１０〜８５重量％の期間に、ドデシルベンゼンスルホン酸ナトリウム５重量％水溶液を一定速度で１５重量部注入した。
重合転化率が９０重量％になった時点で冷却し、未反応単量体を除去した。スケールが殆どない状態で安定な重合体粒子水性分散液Ｂを得た。
重合体の平均粒径は０．２μｍであり、平均重合度は１０００であった。
(Production Example 2)
A 10 liter stainless steel stirrer and jacketed pressure-resistant reactor were charged with 150 parts by weight of deionized water, 0.05 parts by weight of potassium persulfate and 0.05 parts by weight of sodium lauryl sulfate, and each was purged with nitrogen and degassed under reduced pressure. Repeated twice. Thereafter, 100 parts by weight of vinyl chloride was charged, the temperature was increased while stirring, and emulsion polymerization was started at 58.5 ° C. 15 parts by weight of a 5% by weight aqueous solution of sodium dodecylbenzenesulfonate was injected at a constant rate during a polymerization conversion rate of 10 to 85% by weight.
When the polymerization conversion rate reached 90% by weight, the system was cooled to remove unreacted monomers. Stable polymer particle aqueous dispersion B was obtained with almost no scale.
The average particle size of the polymer was 0.2 μm, and the average degree of polymerization was 1000.
（製造例３）
１０リットルのステンレス製の攪拌機及びジャケット付き耐圧反応器に、脱イオン水１５０重量部、過硫酸カリウム０．０５重量部及びラウリル硫酸ナトリウム０．０５重量部を仕込み、窒素置換、減圧脱気を各２回繰り返した。その後、塩化ビニル１００重量部を仕込み、攪拌しながら昇温し、５４℃にて乳化重合を開始した。重合転化率１０〜８５重量％の期間に、ドデシルベンゼンスルホン酸ナトリウム５重量％水溶液を一定速度で１５重量部注入した。
重合転化率が９０重量％になった時点で冷却し、未反応単量体を除去した。スケールが殆どない状態で安定な重合体粒子水性分散液Ｃを得た。
重合体の平均粒径は０．２μｍであり、平均重合度は１２００であった。
(Production Example 3)
A 10 liter stainless steel stirrer and jacketed pressure-resistant reactor were charged with 150 parts by weight of deionized water, 0.05 parts by weight of potassium persulfate and 0.05 parts by weight of sodium lauryl sulfate, and each was purged with nitrogen and degassed under reduced pressure. Repeated twice. Thereafter, 100 parts by weight of vinyl chloride was charged, the temperature was increased while stirring, and emulsion polymerization was started at 54 ° C. 15 parts by weight of a 5% by weight aqueous solution of sodium dodecylbenzenesulfonate was injected at a constant rate during a polymerization conversion rate of 10 to 85% by weight.
When the polymerization conversion rate reached 90% by weight, the system was cooled to remove unreacted monomers. Stable polymer particle aqueous dispersion C was obtained with almost no scale.
The average particle size of the polymer was 0.2 μm, and the average degree of polymerization was 1200.
（製造例４）
１０リットルのステンレス製の攪拌機及びジャケット付き耐圧反応器に、脱イオン水１５０重量部、過硫酸カリウム０．０５重量部及びラウリル硫
酸ナトリウム０．０５重量部を仕込み、窒素置換、減圧脱気を各２回繰り返した。その後、塩化ビニル１００重量部を仕込み、攪拌しながら昇温し、５０℃にて乳化重合を開始した。重合転化率１０〜８５重量％の期間に、ドデシルベンゼンスルホン酸ナトリウム５重量％水溶液を一定速度で１５重量部注入した。
重合転化率が９０重量％になった時点で冷却し、未反応単量体を除去した。スケールが殆どない状態で安定な重合体粒子水性分散液Ｄを得た。
重合体の平均粒径は０．２μｍであり、平均重合度は１４００であった。
(Production Example 4)
A 10 liter stainless steel stirrer and jacketed pressure-resistant reactor were charged with 150 parts by weight of deionized water, 0.05 parts by weight of potassium persulfate and 0.05 parts by weight of sodium lauryl sulfate, and each was purged with nitrogen and degassed under reduced pressure. Repeated twice. Thereafter, 100 parts by weight of vinyl chloride was charged, the temperature was increased while stirring, and emulsion polymerization was started at 50 ° C. 15 parts by weight of a 5% by weight aqueous solution of sodium dodecylbenzenesulfonate was injected at a constant rate during a polymerization conversion rate of 10 to 85% by weight.
When the polymerization conversion rate reached 90% by weight, the system was cooled to remove unreacted monomers. Stable polymer particle aqueous dispersion D was obtained with almost no scale.
The average particle size of the polymer was 0.2 μm, and the average degree of polymerization was 1400.
（製造例５）
１０リットルのステンレス製の攪拌機及びジャケット付き耐圧反応器に、脱イオン水１５０重量部、過硫酸カリウム０．０５重量部及びラウリル硫酸ナトリウム０．０５重量部を仕込み、窒素置換、減圧脱気を各２回繰り返した。その後、塩化ビニル１００重量部を仕込み、攪拌しながら昇温し、４８℃にて乳化重合を開始した。重合転化率１０〜８５重量％の期間に、ドデシルベンゼンスルホン酸ナトリウム５重量％水溶液を一定速度で１５重量部注入した。
重合転化率が９０重量％になった時点で冷却し、未反応単量体を除去した。スケールが殆どない状態で安定な重合体粒子水性分散液Ｅを得た。
重合体の平均粒径は０．２μｍであり、平均重合度は１６００であった。
(Production Example 5)
A 10 liter stainless steel stirrer and jacketed pressure-resistant reactor were charged with 150 parts by weight of deionized water, 0.05 parts by weight of potassium persulfate and 0.05 parts by weight of sodium lauryl sulfate, and each was purged with nitrogen and degassed under reduced pressure. Repeated twice. Thereafter, 100 parts by weight of vinyl chloride was charged, the temperature was increased while stirring, and emulsion polymerization was started at 48 ° C. 15 parts by weight of a 5% by weight aqueous solution of sodium dodecylbenzenesulfonate was injected at a constant rate during a polymerization conversion rate of 10 to 85% by weight.
When the polymerization conversion rate reached 90% by weight, the system was cooled to remove unreacted monomers. Stable polymer particle aqueous dispersion E was obtained with almost no scale.
The average particle size of the polymer was 0.2 μm, and the average degree of polymerization was 1600.
（製造例６）
１０リットルのステンレス製の攪拌機及びジャケット付き耐圧反応器に、脱イオン水１５０重量部、過硫酸カリウム０．０５重量部及びラウリル硫酸ナトリウム０．３０重量部を仕込み、窒素置換、減圧脱気を各２回繰り返した。その後、塩化ビニル１００重量部を仕込み、攪拌しながら昇温し、５０℃にて乳化重合を開始した。重合転化率１０〜８５重量％の期間に、ドデシルベンゼンスルホン酸ナトリウム５重量％水溶液を一定速度で１５重量部注入した。
重合転化率が９０重量％になった時点で冷却し、未反応単量体を除去した。スケールが殆どない状態で安定な重合体粒子水性分散液Ｆを得た。
重合体の平均粒径は０．１μｍであり、平均重合度は１４００であった。
(Production Example 6)
A 10-liter stainless steel stirrer and jacketed pressure-resistant reactor were charged with 150 parts by weight of deionized water, 0.05 part by weight of potassium persulfate and 0.30 part by weight of sodium lauryl sulfate, and each was purged with nitrogen and degassed under reduced pressure. Repeated twice. Thereafter, 100 parts by weight of vinyl chloride was charged, the temperature was increased while stirring, and emulsion polymerization was started at 50 ° C. 15 parts by weight of a 5% by weight aqueous solution of sodium dodecylbenzenesulfonate was injected at a constant rate during a polymerization conversion rate of 10 to 85% by weight.
When the polymerization conversion rate reached 90% by weight, the system was cooled to remove unreacted monomers. Stable polymer particle aqueous dispersion F was obtained with almost no scale.
The average particle size of the polymer was 0.1 μm, and the average degree of polymerization was 1400.
（製造例７）
１０リットルのステンレス製の攪拌機及びジャケット付き耐圧反応器に、脱イオン水１５０重量部、過硫酸カリウム０．０５重量部及びラウリル硫酸ナトリウム０．０２重量部を仕込み、窒素置換、減圧脱気を各２回繰り返した。その後、塩化ビニル１００重量部を仕込み、攪拌しながら昇温し、５０℃にて乳化重合を開始した。重合転化率１０〜８５重量％の期間に、ドデシルベンゼンスルホン酸ナトリウム５重量％水溶液を一定速度で１５重量部注入した。
重合転化率が９０重量％になった時点で冷却し、未反応単量体を除去した。スケールが殆どない状態で安定な重合体粒子水性分散液Ｇを得た。
重合体の平均粒径は０．３μｍであり、平均重合度は１４００であった。
(Production Example 7)
A 10-liter stainless steel stirrer and jacketed pressure-resistant reactor were charged with 150 parts by weight of deionized water, 0.05 part by weight of potassium persulfate and 0.02 part by weight of sodium lauryl sulfate, and each was subjected to nitrogen substitution and vacuum degassing. Repeated twice. Thereafter, 100 parts by weight of vinyl chloride was charged, the temperature was increased while stirring, and emulsion polymerization was started at 50 ° C. 15 parts by weight of a 5% by weight aqueous solution of sodium dodecylbenzenesulfonate was injected at a constant rate during a polymerization conversion rate of 10 to 85% by weight.
When the polymerization conversion rate reached 90% by weight, the system was cooled to remove unreacted monomers. A stable polymer particle aqueous dispersion G was obtained with almost no scale.
The average particle size of the polymer was 0.3 μm, and the average degree of polymerization was 1400.
（製造例８）
１０リットルのステンレス製の攪拌機及びジャケット付き耐圧反応器に、脱イオン水１５０重量部、過硫酸カリウム０．０５重量部及びラウリル硫酸ナトリウム０．０１重量部を仕込み、窒素置換、減圧脱気を各２回繰り返した。その後、塩化ビニル１００重量部を仕込み、攪拌しながら昇温し、５０℃にて乳化重合を開始した。重合転化率１０〜８５重量％の期間に、ドデシルベンゼンスルホン酸ナトリウム５重量％水溶液を一定速度で１５重量部注入した。
重合転化率が９０重量％になった時点で冷却し、未反応単量体を除去した。スケールが殆どない状態で安定な重合体粒子水性分散液Ｈを得た。
重合体の平均粒径は０．４μｍであり、平均重合度は１４００であった。
(Production Example 8)
A 10-liter stainless steel stirrer and jacketed pressure-resistant reactor were charged with 150 parts by weight of deionized water, 0.05 parts by weight of potassium persulfate and 0.01 parts by weight of sodium lauryl sulfate, followed by nitrogen substitution and vacuum degassing. Repeated twice. Thereafter, 100 parts by weight of vinyl chloride was charged, the temperature was increased while stirring, and emulsion polymerization was started at 50 ° C. 15 parts by weight of a 5% by weight aqueous solution of sodium dodecylbenzenesulfonate was injected at a constant rate during a polymerization conversion rate of 10 to 85% by weight.
When the polymerization conversion rate reached 90% by weight, the system was cooled to remove unreacted monomers. Stable polymer particle aqueous dispersion H was obtained with almost no scale.
The average particle size of the polymer was 0.4 μm, and the average degree of polymerization was 1400.
２．塩化ビニル重合体Ｂの製造
（製造例９）
１０リットルのステンレス製の攪拌機及びジャケット付き耐圧反応器に、脱イオン水１２０重量部、微細懸濁重合によって得られたラウリルパーオキサイドを重合体に対して２重量％を含有する平均粒径０．７μｍ粒子の３０重量％の水性分散液１２重量部及びドデシルベンゼンスルホン酸ナトリウム０．７重量部を仕込み、窒素置換、減圧脱気を各２回繰り返した。その後、塩化ビニル１００重量部を仕込み、攪拌しながら、昇温し、６２℃にて播種微細懸濁重合を行った。
重合転化率が９０重量％になった時点で冷却し、未反応単量体を除去した。スケールが殆どない状態で安定な重合体粒子水性分散液Ｉを得た。
重合体の平均粒径は1．４μｍであり、平均重合度は９００であった。
2. Production of vinyl chloride polymer B (Production Example 9)
In a 10-liter stainless steel stirrer and jacketed pressure-resistant reactor, 120 parts by weight of deionized water and an average particle size of 2% by weight of lauryl peroxide obtained by fine suspension polymerization, based on the polymer, were obtained. 12 parts by weight of an aqueous dispersion of 30% by weight of 7 μm particles and 0.7 parts by weight of sodium dodecylbenzenesulfonate were charged, and nitrogen substitution and vacuum degassing were repeated twice. Thereafter, 100 parts by weight of vinyl chloride was added, the temperature was increased while stirring, and seeding fine suspension polymerization was performed at 62 ° C.
When the polymerization conversion rate reached 90% by weight, the system was cooled to remove unreacted monomers. Stable polymer particle aqueous dispersion I was obtained with almost no scale.
The average particle size of the polymer was 1.4 μm, and the average degree of polymerization was 900.
（製造例１０）
１０リットルのステンレス製の攪拌機及びジャケット付き耐圧反応器に、脱イオン水１２０重量部、微細懸濁重合によって得られたラウリルパーオキサイドを重合体に対して２重量％を含有する平均粒径０．７μｍ粒子の３０重量％の水性分散液１２重量部及びドデシルベンゼンスルホン酸ナトリウム０．７重量部を仕込み、窒素置換、減圧脱気を各２回繰り返した。その後、塩化ビニル１００重量部を仕込み、攪拌しながら、昇温し、６６℃にて播種微細懸濁重合を行った。
重合転化率が９０重量％になった時点で冷却し、未反応単量体を除去した。スケールが殆どない状態で安定な重合体粒子水性分散液Ｊを得た。
重合体の平均粒径は1．４μｍであり、平均重合度は７７０であった。
(Production Example 10)
In a 10-liter stainless steel stirrer and jacketed pressure-resistant reactor, 120 parts by weight of deionized water and an average particle size of 2% by weight of lauryl peroxide obtained by fine suspension polymerization, based on the polymer, were obtained. 12 parts by weight of an aqueous dispersion of 30% by weight of 7 μm particles and 0.7 parts by weight of sodium dodecylbenzenesulfonate were charged, and nitrogen substitution and vacuum degassing were repeated twice. Thereafter, 100 parts by weight of vinyl chloride was charged, the temperature was increased while stirring, and seeding fine suspension polymerization was performed at 66 ° C.
When the polymerization conversion rate reached 90% by weight, the system was cooled to remove unreacted monomers. Stable polymer particle aqueous dispersion J was obtained with almost no scale.
The average particle size of the polymer was 1.4 μm, and the average degree of polymerization was 770.
（製造例１１）
１０リットルのステンレス製の攪拌機及びジャケット付き耐圧反応器に、脱イオン水１２０重量部、微細懸濁重合によって得られたラウリルパーオキサイドを重合体に対して２重量％を含有する平均粒径０．７μｍ粒子の３０重量％の水性分散液１２重量部及びドデシルベンゼンスルホン酸ナトリウム０．７重量部、チオグリコール酸２−エチルヘキシル０．０５重量部を仕込み、窒素置換、減圧脱気を各２回繰り返した。その後、塩化ビニル１００重量部を仕込み、攪拌しながら、昇温し、６６℃にて播種微細懸濁重合を行った。
重合転化率が９０重量％になった時点で冷却し、未反応単量体を除去した。スケールが殆どない状態で安定な重合体粒子水性分散液Ｋを得た。
重合体の平均粒径は1．４μｍであり、平均重合度は６９０であった。
(Production Example 11)
In a 10-liter stainless steel stirrer and jacketed pressure-resistant reactor, 120 parts by weight of deionized water and an average particle size of 2% by weight of lauryl peroxide obtained by fine suspension polymerization, based on the polymer, were obtained. Charge 12 parts by weight of an aqueous dispersion of 30% by weight of 7 μm particles, 0.7 parts by weight of sodium dodecylbenzenesulfonate and 0.05 parts by weight of 2-ethylhexyl thioglycolate, and repeat nitrogen substitution and vacuum degassing twice each. It was. Thereafter, 100 parts by weight of vinyl chloride was charged, the temperature was increased while stirring, and seeding fine suspension polymerization was performed at 66 ° C.
When the polymerization conversion rate reached 90% by weight, the system was cooled to remove unreacted monomers. Stable polymer particle aqueous dispersion K was obtained with almost no scale.
The average particle size of the polymer was 1.4 μm, and the average degree of polymerization was 690.
（製造例１２）
１０リットルのステンレス製の攪拌機及びジャケット付き耐圧反応器に、脱イオン水１２０重量部、微細懸濁重合によって得られたラウリルパーオキサイドを重合体に対して２重量％を含有する平均粒径０．７μｍ粒子の３０重量％の水性分散液１２重量部及びドデシルベンゼンスルホン酸ナトリウム０．７重量部、チオグリコール酸２−エチルヘキシルを０．２重量部仕込み、窒素置換、減圧脱気を各２回繰り返した。その後、塩化ビニル１００重量部を仕込み、攪拌しながら、昇温し、６６℃にて播種微細懸濁重合を行った。
重合転化率が９０重量％になった時点で冷却し、未反応単量体を除去した。スケールが殆どない状態で安定な重合体粒子水性分散液Ｌを得た。
重合体の平均粒径は1．４μｍであり、平均重合度は６００であった。
(Production Example 12)
In a 10-liter stainless steel stirrer and jacketed pressure-resistant reactor, 120 parts by weight of deionized water and an average particle size of 2% by weight of lauryl peroxide obtained by fine suspension polymerization, based on the polymer, were obtained. Charge 12 parts by weight of an aqueous dispersion of 30% by weight of 7 μm particles, 0.7 parts by weight of sodium dodecylbenzenesulfonate, and 0.2 parts by weight of 2-ethylhexyl thioglycolate. Repeat nitrogen replacement and vacuum degassing twice each. It was. Thereafter, 100 parts by weight of vinyl chloride was charged, the temperature was increased while stirring, and seeding fine suspension polymerization was performed at 66 ° C.
When the polymerization conversion rate reached 90% by weight, the system was cooled to remove unreacted monomers. Stable polymer particle aqueous dispersion L was obtained with almost no scale.
The average particle size of the polymer was 1.4 μm, and the average degree of polymerization was 600.
３．ペースト用塩化ビニル系樹脂の製造
（実施例１）
製造例３で得られた重合体粒子水性分散液Ｃ及び製造例１０で得られた重合体粒子水性分散液Ｊを、固形分重量比で３０／７０の比率で混合し、重合体Ａと重合体Ｂの平均重合度の差が４３０の重合体粒子混合水性分散液を得た。
次いで、得られた重合体粒子混合水性分散液を噴霧乾燥機にて乾燥後、ハンマーミルにて粉砕して、ペースト用塩化ビニル樹脂を得た。
得られた塩化ビニル樹脂の引張強さは、１２０℃×５ｍｉｎでは２．８１Ｎ／ｍｍ２、１６０℃×５ｍｉｎでは１４．６１Ｎ／ｍｍ２であった。
3. Production of vinyl chloride resin for paste (Example 1)
The aqueous polymer particle dispersion C obtained in Production Example 3 and the aqueous polymer particle dispersion J obtained in Production Example 10 were mixed at a solid content weight ratio of 30/70, and the polymer A A polymer particle mixed aqueous dispersion having a difference in average polymerization degree of the combined B of 430 was obtained.
Next, the obtained polymer particle mixed aqueous dispersion was dried with a spray dryer and pulverized with a hammer mill to obtain a vinyl chloride resin for paste.
The resulting tensile strength of vinyl chloride resin was 120 ° C. × In 5min 2.81N / mm 2, 160 ℃ × In 5min 14.61N / mm 2.
（実施例２）
製造例４で得られた重合体粒子水性分散液Ｄ及び製造例１１で得られた重合体粒子水性分散液Ｋを、固形分重量比で３０／７０の比率で混合し、重合体Ａと重合体Ｂの平均重合度の差が７１０の重合体粒子混合水性分散液を得た。
次いで、得られた重合体粒子混合水性分散液を噴霧乾燥機にて乾燥後、ハンマーミルにて粉砕して、ペースト用塩化ビニル樹脂を得た。
得られた塩化ビニル樹脂の引張強さは、１２０℃×５ｍｉｎでは２．８９Ｎ／ｍｍ２、１６０℃×５ｍｉｎでは１４．８１Ｎ／ｍｍ２であった。
(Example 2)
The aqueous polymer particle dispersion D obtained in Production Example 4 and the aqueous polymer particle dispersion K obtained in Production Example 11 were mixed at a solid content weight ratio of 30/70, and the polymer A A polymer particle mixed aqueous dispersion having a difference in the average degree of polymerization of the polymer B of 710 was obtained.
Next, the obtained polymer particle mixed aqueous dispersion was dried with a spray dryer and pulverized with a hammer mill to obtain a vinyl chloride resin for paste.
The resulting tensile strength of vinyl chloride resin was 120 ° C. × In 5min 2.89N / mm 2, 160 ℃ × In 5min 14.81N / mm 2.
（実施例３）
製造例６で得られた重合体粒子水性分散液Ｆ及び製造例１１で得られた重合体粒子水性分散液Ｋを、固形分重量比で３０／７０の比率で混合し、重合体Ａと重合体Ｂの平均重合度の差が７１０の重合体粒子混合水性分散液を得た。
次いで、得られた重合体粒子混合水性分散液を噴霧乾燥機にて乾燥後、ハンマーミルにて粉砕して、ペースト用塩化ビニル樹脂を得た。
得られた塩化ビニル樹脂の引張強さは、１２０℃×５ｍｉｎでは２．９９Ｎ／ｍｍ２、１６０℃×５ｍｉｎでは１４．８３Ｎ／ｍｍ２であった。
(Example 3)
The aqueous polymer particle dispersion F obtained in Production Example 6 and the aqueous polymer particle dispersion K obtained in Production Example 11 were mixed at a solid content weight ratio of 30/70, and the polymer A A polymer particle mixed aqueous dispersion having a difference in the average degree of polymerization of the polymer B of 710 was obtained.
Next, the obtained polymer particle mixed aqueous dispersion was dried with a spray dryer and pulverized with a hammer mill to obtain a vinyl chloride resin for paste.
The resulting tensile strength of vinyl chloride resin was 120 ° C. × In 5min 2.99N / mm 2, 160 ℃ × In 5min 14.83N / mm 2.
（実施例４）
製造例４で得られた重合体粒子水性分散液Ｄ及び製造例１１で得られた重合体粒子水性分散液Ｋを、固形分重量比で２０／８０の比率で混合し、重合体Ａと重合体Ｂの平均重合度の差が７１０の重合体粒子混合水性分散液を得た。
次いで、得られた重合体粒子混合水性分散液を噴霧乾燥機にて乾燥後、ハンマーミルにて粉砕して、ペースト用塩化ビニル樹脂を得た。
得られた塩化ビニル樹脂の引張強さは、１２０℃×５ｍｉｎでは２．７８Ｎ／ｍｍ２、１６０℃×５ｍｉｎでは１４．５９Ｎ／ｍｍ２であった。
Example 4
The aqueous polymer particle dispersion D obtained in Production Example 4 and the aqueous polymer particle dispersion K obtained in Production Example 11 were mixed at a solid content weight ratio of 20/80, and the polymer A A polymer particle mixed aqueous dispersion having a difference in the average degree of polymerization of the polymer B of 710 was obtained.
Next, the obtained polymer particle mixed aqueous dispersion was dried with a spray dryer and pulverized with a hammer mill to obtain a vinyl chloride resin for paste.
The resulting tensile strength of vinyl chloride resin was 120 ° C. × In 5min 2.78N / mm 2, 160 ℃ × In 5min 14.59N / mm 2.
（実施例５）
製造例４で得られた重合体粒子水性分散液Ｄ及び製造例１１で得られた重合体粒子水性分散液Ｋを、固形分重量比で４０／６０の比率で混合し、重合体Ａと重合体Ｂの平均重合度の差が７１０の重合体粒子混合水性分散液を得た。
次いで、得られた重合体粒子混合水性分散液を噴霧乾燥機にて乾燥後、ハンマーミルにて粉砕して、ペースト用塩化ビニル樹脂を得た。
得られた塩化ビニル樹脂の引張強さは、１２０℃×５ｍｉｎでは２．８１Ｎ／ｍｍ２、１６０℃×５ｍｉｎでは１４．８７Ｎ／ｍｍ２であった。
(Example 5)
The polymer particle aqueous dispersion D obtained in Production Example 4 and the polymer particle aqueous dispersion K obtained in Production Example 11 were mixed at a solid content weight ratio of 40/60, and the polymer A A polymer particle mixed aqueous dispersion having a difference in the average degree of polymerization of the polymer B of 710 was obtained.
Next, the obtained polymer particle mixed aqueous dispersion was dried with a spray dryer and pulverized with a hammer mill to obtain a vinyl chloride resin for paste.
The resulting tensile strength of vinyl chloride resin was 120 ° C. × In 5min 2.81N / mm 2, 160 ℃ × In 5min 14.87N / mm 2.
（比較例１）
製造例１で得られた重合体粒子水性分散液Ａ及び製造例９で得られた重合体粒子水性分散液Ｉを、固形分重量比で３０／７０の比率で混合し、重合体Ａと重合体Ｂの平均重合度の差が０の重合体粒子混合水性分散液を得た。
次いで、得られた重合体粒子混合水性分散液を噴霧乾燥機にて乾燥後、ハンマーミルにて粉砕して、ペースト用塩化ビニル樹脂を得た。
得られた塩化ビニル樹脂の引張強さは、１２０℃×５ｍｉｎでは２．５８Ｎ／ｍｍ２、１６０℃×５ｍｉｎでは１３．６８Ｎ／ｍｍ２であった。
(Comparative Example 1)
The polymer particle aqueous dispersion A obtained in Production Example 1 and the polymer particle aqueous dispersion I obtained in Production Example 9 were mixed at a solid content weight ratio of 30/70, and the polymer A A polymer particle mixed aqueous dispersion in which the difference in the average degree of polymerization of the polymer B was 0 was obtained.
Next, the obtained polymer particle mixed aqueous dispersion was dried with a spray dryer and pulverized with a hammer mill to obtain a vinyl chloride resin for paste.
The resulting tensile strength of vinyl chloride resin was 120 ° C. × In 5min 2.58N / mm 2, 160 ℃ × In 5min 13.68N / mm 2.
（比較例２）
製造例２で得られた重合体粒子水性分散液Ｂ及び製造例９で得られた重合体粒子水性分散液Ｉを、固形分重量比で３０／７０の比率で混合し、重合体Ａと重合体Ｂの平均重合度の差が１００の重合体粒子混合水性分散液を得た。
次いで、得られた重合体粒子混合水性分散液を噴霧乾燥機にて乾燥後、ハンマーミルにて粉砕して、ペースト用塩化ビニル樹脂を得た。
得られた塩化ビニル樹脂の引張強さは、１２０℃×５ｍｉｎでは２．６１Ｎ／ｍｍ２、１６０℃×５ｍｉｎでは１３．９８Ｎ／ｍｍ２であった。
(Comparative Example 2)
The polymer particle aqueous dispersion B obtained in Production Example 2 and the polymer particle aqueous dispersion I obtained in Production Example 9 were mixed at a solid content weight ratio of 30/70, and the polymer A A polymer particle mixed aqueous dispersion having an average polymerization degree difference of 100 was obtained.
Next, the obtained polymer particle mixed aqueous dispersion was dried with a spray dryer and pulverized with a hammer mill to obtain a vinyl chloride resin for paste.
The resulting tensile strength of vinyl chloride resin was 120 ° C. × In 5min 2.61N / mm 2, 160 ℃ × In 5min 13.98N / mm 2.
（比較例３）
製造例５で得られた重合体粒子水性分散液Ｅ及び製造例１２で得られた重合体粒子水性分散液Ｌを、固形分重量比で３０／７０の比率で混合し、重合体Ａと重合体Ｂの平均重合度の差が１０００の重合体粒子混合水性分散液を得た。
次いで、得られた重合体粒子混合水性分散液を噴霧乾燥機にて乾燥後、ハンマーミルにて粉砕して、ペースト用塩化ビニル樹脂を得た。
得られた塩化ビニル樹脂の引張強さは、１２０℃×５ｍｉｎでは２．６８Ｎ／ｍｍ２、１６０℃×５ｍｉｎでは１３．０２Ｎ／ｍｍ２であった。
(Comparative Example 3)
The aqueous polymer particle dispersion E obtained in Production Example 5 and the aqueous polymer particle dispersion L obtained in Production Example 12 were mixed at a solid content weight ratio of 30/70, and the polymer A A polymer particle mixed aqueous dispersion having a difference in the average degree of polymerization of the polymer B of 1000 was obtained.
Next, the obtained polymer particle mixed aqueous dispersion was dried with a spray dryer and pulverized with a hammer mill to obtain a vinyl chloride resin for paste.
The resulting tensile strength of vinyl chloride resin was 120 ° C. × In 5min 2.68N / mm 2, 160 ℃ × In 5min 13.02N / mm 2.
（比較例４）
製造例５で得られた重合体粒子水性分散液Ｅ及び製造例９で得られた重合体粒子水性分散液Ｊを、固形分重量比で３０／７０の比率で混合した。
次いで、この混合重合体粒子水性分散液を噴霧乾燥機にて乾燥後、ハンマーミルにて粉砕して、ペースト用塩化ビニル樹脂を得た。
得られた塩化ビニル樹脂の引張強さは、１２０℃×５ｍｉｎでは２．３６Ｎ／ｍｍ２、１６０℃×５ｍｉｎでは１４．５８Ｎ／ｍｍ２であった。
(Comparative Example 4)
The polymer particle aqueous dispersion E obtained in Production Example 5 and the polymer particle aqueous dispersion J obtained in Production Example 9 were mixed at a solid weight ratio of 30/70.
Next, this mixed polymer particle aqueous dispersion was dried with a spray dryer and pulverized with a hammer mill to obtain a vinyl chloride resin for paste.
The resulting tensile strength of vinyl chloride resin was 120 ° C. × In 5min 2.36N / mm 2, 160 ℃ × In 5min 14.58N / mm 2.
（比較例５）
製造例７で得られた重合体粒子水性分散液Ｇ及び製造例１１で得られた重合体粒子水性分散液Ｋを、固形分重量比で３０／７０の比率で混合し、重合体Ａと重合体Ｂの平均重合度の差が７１０の重合体粒子混合水性分散液を得た。
次いで、得られた重合体粒子混合水性分散液を噴霧乾燥機にて乾燥後、ハンマーミルにて粉砕して、ペースト用塩化ビニル樹脂を得た。
得られた塩化ビニル樹脂の引張強さは、１２０℃×５ｍｉｎでは２．７１Ｎ／ｍｍ２、１６０℃×５ｍｉｎでは１４．４６Ｎ／ｍｍ２であった。
(Comparative Example 5)
The aqueous polymer particle dispersion G obtained in Production Example 7 and the aqueous polymer particle dispersion K obtained in Production Example 11 were mixed at a solid content weight ratio of 30/70, and the polymer A A polymer particle mixed aqueous dispersion having a difference in the average degree of polymerization of the polymer B of 710 was obtained.
Next, the obtained polymer particle mixed aqueous dispersion was dried with a spray dryer and pulverized with a hammer mill to obtain a vinyl chloride resin for paste.
The resulting tensile strength of vinyl chloride resin was 120 ° C. × In 5min 2.71N / mm 2, 160 ℃ × In 5min 14.46N / mm 2.
（比較例６）
製造例８で得られた重合体粒子水性分散液Ｈ及び製造例１１で得られた重合体粒子水性分散液Ｋを、固形分重量比で３０／７０の比率で混合し、重合体Ａと重合体Ｂの平均重合度の差が７１０の重合体粒子混合水性分散液を得た。
次いで、得られた重合体粒子混合水性分散液を噴霧乾燥機にて乾燥後、ハンマーミルにて粉砕して、ペースト用塩化ビニル樹脂を得た。
得られた塩化ビニル樹脂の引張強さは、１２０℃×５ｍｉｎでは２．６１Ｎ／ｍｍ２、１６０℃×５ｍｉｎでは１３．８７Ｎ／ｍｍ２であった。
(Comparative Example 6)
The aqueous polymer particle dispersion H obtained in Production Example 8 and the aqueous polymer particle dispersion K obtained in Production Example 11 were mixed at a solid content weight ratio of 30/70, and the polymer A A polymer particle mixed aqueous dispersion having a difference in the average degree of polymerization of the polymer B of 710 was obtained.
Next, the obtained polymer particle mixed aqueous dispersion was dried with a spray dryer and pulverized with a hammer mill to obtain a vinyl chloride resin for paste.
The resulting tensile strength of vinyl chloride resin was 120 ° C. × In 5min 2.61N / mm 2, 160 ℃ × In 5min 13.87N / mm 2.
以上の結果に基づいて、塩化ビニル系重合体Ａ及び塩化ビニル系重合体Ｂの平均重合度の影響は表１に、塩化ビニル系重合体Ａの平均粒径の影響は表２に、塩化ビニル系重合体Ａと塩化ビニル系重合体Ｂの割合の影響は表３に、それぞれ示す。 Based on the above results, the influence of the average polymerization degree of the vinyl chloride polymer A and the vinyl chloride polymer B is shown in Table 1, the influence of the average particle diameter of the vinyl chloride polymer A is shown in Table 2, and the vinyl chloride. Table 3 shows the influence of the proportions of the polymer A and the vinyl chloride polymer B.
上記の表１〜３の結果から、以下のことがいえる。
（１）要件２と３を満足しても、要件１を満足しないと、１２０〜１６０℃の強度、特に１２０℃の強度はよくない（比較例３、５、６）。
（２）要件１と３を満足しても、要件２を満足しないと、１２０〜１６０℃の強度、特に１２０℃の強度はよくない（比較例２）。
（３）要件１と２を満足しても、要件３を満足しないと、１２０〜１６０℃の強度、特に１２０℃の強度はよくない（比較例７）。
（４）これに対して、要件１〜３の全てを満足すると、１２０〜１６０℃の強度、特に１２０℃の強度は優れている（実施例１〜６）
以上のことから、本発明の要件１〜３の全てを満足しないと、所期の目的が達成できないことが分かる。
From the results shown in Tables 1 to 3, the following can be said.
(1) Even if the requirements 2 and 3 are satisfied, if the requirement 1 is not satisfied, the strength at 120 to 160 ° C., particularly the strength at 120 ° C. is not good (Comparative Examples 3, 5, and 6).
(2) Even if the requirements 1 and 3 are satisfied, if the requirement 2 is not satisfied, the strength at 120 to 160 ° C., particularly the strength at 120 ° C. is not good (Comparative Example 2).
(3) Even if the requirements 1 and 2 are satisfied, if the requirement 3 is not satisfied, the strength at 120 to 160 ° C., particularly the strength at 120 ° C. is not good (Comparative Example 7).
(4) On the other hand, when all the requirements 1 to 3 are satisfied, the strength of 120 to 160 ° C., particularly the strength of 120 ° C. is excellent (Examples 1 to 6).
From the above, it can be seen that the intended purpose cannot be achieved unless all of the requirements 1 to 3 of the present invention are satisfied.
強度（耐久性、反り防止、寸法安定性等）が要求される用途、例えば、パイルカーペット等に最適である。
It is optimal for applications that require strength (durability, warpage prevention, dimensional stability, etc.), such as pile carpets.
Claims (4)
要件１：塩化ビニル系重合体Ａ
平均粒径０．１〜０．２５μｍ、
平均重合度１０００〜１４００
要件２：塩化ビニル系重合体Ｂ
平均粒径１．０〜２．５μｍ、
平均重合度６００〜８００
要件３：塩化ビニル系重合体Ａと塩化ビニル系重合体Ｂの割合
塩化ビニル系重合体Ａ１５〜４０重量％、
塩化ビニル系重合体Ｂ６０〜８５重量％ The vinyl chloride resin is composed of a vinyl chloride polymer A satisfying the following requirement 1 and a vinyl chloride polymer B satisfying the requirement 2, and the relationship between the polymer A and the polymer B is as follows: A vinyl chloride resin for paste, which satisfies the requirement 3 of the above.
Requirement 1: Vinyl chloride polymer A
Average particle size 0.1-0.25 μm,
Average degree of polymerization 1000-1400
Requirement 2: Vinyl chloride polymer B
Average particle size 1.0-2.5 μm,
Average polymerization degree 600-800
Requirement 3: Ratio of vinyl chloride polymer A and vinyl chloride polymer B
Vinyl chloride polymer A 15 to 40% by weight,
Vinyl chloride polymer B60-85% by weight
4. The vinyl chloride resin composition for paste according to claim 3, wherein the compounding agent contains one or more components of the group consisting of a stabilizer, a filler, or a foaming agent.
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| US20180039170A1 (en) * | 2015-02-27 | 2018-02-08 | Canon Kabushiki Kaisha | Nanonimprint liquid material, method for manufacturing nanoimprint liquid material, method for manufacturing cured product pattern, method for manufacturing optical component, and method for manufacturing circuit board |
| JP2021100989A (en) * | 2019-12-24 | 2021-07-08 | 東ソー株式会社 | Paste vinyl chloride-based resin |
| JP2021116328A (en) * | 2020-01-23 | 2021-08-10 | 東ソー株式会社 | Hydroxy group-containing vinyl chloride copolymer composition particle |
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