WO2024190561A1 - Vinyl chloride paste resin, vinyl chloride paste resin composition containing same, and method for producing same - Google Patents
Vinyl chloride paste resin, vinyl chloride paste resin composition containing same, and method for producing same Download PDFInfo
- Publication number
- WO2024190561A1 WO2024190561A1 PCT/JP2024/008503 JP2024008503W WO2024190561A1 WO 2024190561 A1 WO2024190561 A1 WO 2024190561A1 JP 2024008503 W JP2024008503 W JP 2024008503W WO 2024190561 A1 WO2024190561 A1 WO 2024190561A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- vinyl chloride
- paste resin
- vinyl
- chloride paste
- mass
- Prior art date
Links
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 229920005989 resin Polymers 0.000 title claims abstract description 122
- 239000011347 resin Substances 0.000 title claims abstract description 122
- 239000011342 resin composition Substances 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 147
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 57
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 52
- -1 (meth)acrylic acid hydroxyalkyl ester Chemical class 0.000 claims description 73
- 238000006116 polymerization reaction Methods 0.000 claims description 71
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 30
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 21
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000012736 aqueous medium Substances 0.000 claims description 10
- 239000003973 paint Substances 0.000 claims description 8
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 claims description 5
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 239000000565 sealant Substances 0.000 claims description 4
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 claims description 3
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 claims description 3
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 claims description 3
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 claims description 3
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 abstract description 7
- 239000004014 plasticizer Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 20
- 235000014113 dietary fatty acids Nutrition 0.000 description 14
- 239000000194 fatty acid Substances 0.000 description 14
- 229930195729 fatty acid Natural products 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 238000000576 coating method Methods 0.000 description 12
- 229920001944 Plastisol Polymers 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 11
- 230000001070 adhesive effect Effects 0.000 description 11
- 239000004999 plastisol Substances 0.000 description 11
- 239000003999 initiator Substances 0.000 description 10
- 239000003381 stabilizer Substances 0.000 description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 9
- 239000003995 emulsifying agent Substances 0.000 description 9
- 239000004816 latex Substances 0.000 description 9
- 229920000126 latex Polymers 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 125000006850 spacer group Chemical group 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 238000010557 suspension polymerization reaction Methods 0.000 description 5
- 150000005215 alkyl ethers Chemical class 0.000 description 4
- 125000005037 alkyl phenyl group Chemical group 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- GOQYKNQRPGWPLP-UHFFFAOYSA-N heptadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000011362 coarse particle Substances 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000009408 flooring Methods 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- OMVSWZDEEGIJJI-UHFFFAOYSA-N 2,2,4-Trimethyl-1,3-pentadienol diisobutyrate Chemical compound CC(C)C(=O)OC(C(C)C)C(C)(C)COC(=O)C(C)C OMVSWZDEEGIJJI-UHFFFAOYSA-N 0.000 description 2
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 description 2
- 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-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
- 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
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 229960000541 cetyl alcohol Drugs 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 239000011928 denatured alcohol 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
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- BTFJIXJJCSYFAL-UHFFFAOYSA-N icosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCO BTFJIXJJCSYFAL-UHFFFAOYSA-N 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- XGFDHKJUZCCPKQ-UHFFFAOYSA-N nonadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCO XGFDHKJUZCCPKQ-UHFFFAOYSA-N 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000012934 organic peroxide initiator Substances 0.000 description 2
- WYURNTSHIVDZCO-SVYQBANQSA-N oxolane-d8 Chemical compound [2H]C1([2H])OC([2H])([2H])C([2H])([2H])C1([2H])[2H] WYURNTSHIVDZCO-SVYQBANQSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- REIUXOLGHVXAEO-UHFFFAOYSA-N pentadecan-1-ol Chemical compound CCCCCCCCCCCCCCCO REIUXOLGHVXAEO-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 2
- SROBQEVKVSDXFQ-KHPPLWFESA-N (z)-4-oxo-4-(1-phenylpentoxy)but-2-enoic acid Chemical compound OC(=O)\C=C/C(=O)OC(CCCC)C1=CC=CC=C1 SROBQEVKVSDXFQ-KHPPLWFESA-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
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- LAYAKLSFVAPMEL-UHFFFAOYSA-N 1-ethenoxydodecane Chemical compound CCCCCCCCCCCCOC=C LAYAKLSFVAPMEL-UHFFFAOYSA-N 0.000 description 1
- XXCVIFJHBFNFBO-UHFFFAOYSA-N 1-ethenoxyoctane Chemical compound CCCCCCCCOC=C XXCVIFJHBFNFBO-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- KESQFSZFUCZCEI-UHFFFAOYSA-N 2-(5-nitropyridin-2-yl)oxyethanol Chemical compound OCCOC1=CC=C([N+]([O-])=O)C=N1 KESQFSZFUCZCEI-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- 229940106004 2-ethylhexyl benzoate Drugs 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- HVWDBXFSHPDVHR-UHFFFAOYSA-I C(C=C/C(=O)[O-])(=O)[O-].S[Sn+](CCCC)CCCC.S[Sn+](CCCCCCCC)CCCCCCCC.S[Sn+](CCCC)CCCC.C[Sn+2]C Chemical compound C(C=C/C(=O)[O-])(=O)[O-].S[Sn+](CCCC)CCCC.S[Sn+](CCCCCCCC)CCCCCCCC.S[Sn+](CCCC)CCCC.C[Sn+2]C HVWDBXFSHPDVHR-UHFFFAOYSA-I 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Natural products OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FFSJSGNXYKUSCQ-UHFFFAOYSA-N [2,2,4-trimethyl-1-(2-methylpropanoyloxy)pentan-3-yl] benzoate Chemical compound CC(C)C(=O)OCC(C)(C)C(C(C)C)OC(=O)C1=CC=CC=C1 FFSJSGNXYKUSCQ-UHFFFAOYSA-N 0.000 description 1
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-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
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- SHLNMHIRQGRGOL-UHFFFAOYSA-N barium zinc Chemical compound [Zn].[Ba] SHLNMHIRQGRGOL-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid 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
- 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
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- PZGVVCOOWYSSGB-UHFFFAOYSA-L but-2-enedioate;dioctyltin(2+) Chemical compound CCCCCCCC[Sn]1(CCCCCCCC)OC(=O)C=CC(=O)O1 PZGVVCOOWYSSGB-UHFFFAOYSA-L 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical compound O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading 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
- UMKARVFXJJITLN-UHFFFAOYSA-N lead;phosphorous acid Chemical compound [Pb].OP(O)O UMKARVFXJJITLN-UHFFFAOYSA-N 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000314 lubricant 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
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-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
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 159000000001 potassium salts Chemical class 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
- 230000009257 reactivity Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000010378 sodium ascorbate Nutrition 0.000 description 1
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 1
- 229960005055 sodium ascorbate Drugs 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000010265 sodium sulphite 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
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 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
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 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
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229940087291 tridecyl alcohol Drugs 0.000 description 1
- 229940057402 undecyl alcohol Drugs 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/06—Vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/04—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C09D127/06—Homopolymers or copolymers of vinyl chloride
Definitions
- the present invention relates to a vinyl chloride paste resin that can be suitably used in automotive paints, a vinyl chloride paste resin composition containing the same, and a method for producing the same.
- Vinyl chloride paste resins are used in a variety of products, including wallpaper, flooring, carpets, electrical components, automobile parts, and leather.
- vinyl chloride paste resins are suitable for use as automobile paints, such as automobile sealants and automobile underbody coatings, due to their excellent weather resistance, scratch resistance, and thermal stability.
- Patent Document 1 proposes the use of a plastisol composition containing a vinyl chloride copolymer capable of forming a paste and having an average degree of polymerization of 300 to 1000 in the molecule as a coating for the underside of an automobile floor.
- Patent Document 2 proposes the use of hydroxyl-containing vinyl chloride copolymer composition particles for paste processing, which contain 1 to 10 mass% of hydroxyl-containing monomer residue units, 90 to 99 mass% of vinyl chloride monomer residue units, and 0.5 to 2.0 mass parts of linear alkylbenzene sulfonate per 100 mass parts of a vinyl chloride copolymer having an average degree of polymerization of 1000 to 2000, as an automobile underbody coating agent.
- Patent Documents 1 and 2 a vinyl chloride copolymer containing hydroxyl groups in the molecule is used, and when a plastisol containing a vinyl chloride copolymer containing hydroxyl groups in the molecule is processed at low temperatures, the shear properties are good, but the tensile strength and elongation may be poor.
- the present invention provides a vinyl chloride paste resin that has good shear and tensile properties during low-temperature processing, a vinyl chloride paste resin composition containing the same, and a method for producing the same.
- One or more embodiments of the present invention relate to a vinyl chloride paste resin in which vinyl chloride and other monomers are copolymerized, the other monomers including a hydroxyl group-containing monomer and a vinyl ester monomer, and the vinyl chloride paste resin includes 1 to 6 mass% of hydroxyl group-containing monomer units, 4 mass% or more of vinyl ester monomer units, and a total of 7.5 to 11 mass% of hydroxyl group-containing monomer units and vinyl ester monomer units.
- One or more embodiments of the present invention relate to a vinyl chloride paste resin composition containing the vinyl chloride paste resin.
- One or more embodiments of the present invention relate to a method for producing a vinyl chloride paste resin, the method comprising the step of polymerizing vinyl chloride and other monomers in a polymerization reactor in the presence of an aqueous medium, the other monomers including a hydroxyl group-containing monomer and a vinyl ester monomer, and continuously supplying the hydroxyl group-containing monomer to the polymerization reactor after polymerization initiation.
- the present invention it is possible to provide a vinyl chloride paste resin having good shear properties and tensile properties during low-temperature processing, and a vinyl chloride paste resin composition containing the same. Furthermore, according to the production method of the present invention, it is possible to obtain a vinyl chloride paste resin that has good shear properties and tensile properties during low-temperature processing.
- a paste resin composition containing the vinyl chloride paste resin has excellent shear properties and tensile properties when processed at a low temperature, for example, at 120°C.
- the term "monomer unit" in the vinyl chloride paste resin means a repeating unit derived from a monomer.
- a numerical range when a numerical range is indicated with “ ⁇ ”, the numerical range includes both end values (upper and lower limits).
- a numerical range of "X to Y” is a range that includes both end values X and Y, and is the same range as "X or more and Y or less”. Any number within that range and any range contained within that range are specifically disclosed.
- multiple numerical ranges are described in this specification, they are considered to include numerical ranges that appropriately combine the upper and lower limits of different numerical ranges.
- vinyl chloride paste resin is also referred to as PVC resin for paste, and is a resin processed by a paste processing method.
- the paste processing method is a processing method in which a paste resin is suspended in a liquid plasticizer to form a paste (sol), and then shaped by utilizing its fluidity, and then heated and solidified (gelled) to form a molded product.
- the particle size range of the primary particles of vinyl chloride paste resin is generally about 0.1 to 10 ⁇ m. In this specification, the particle size range of the primary particles of vinyl chloride paste resin can be confirmed by using a dispersion liquid in which vinyl chloride paste resin is dispersed in water and measuring the particle size distribution by dynamic light scattering.
- the vinyl chloride paste resin is a copolymer of vinyl chloride and other monomers, and the other monomers include hydroxyl group-containing monomers and vinyl ester monomers.
- the vinyl chloride paste resin contains 1 to 6 mass %, preferably 1.5 to 5 mass %, more preferably 2.0 to 4.7 mass %, and even more preferably 2.5 to 4.4 mass % of hydroxyl group-containing monomer units. If the content of hydroxyl group-containing monomer units in the vinyl chloride paste resin is less than 1 mass %, the shear properties of the coating film when processed at low temperatures are poor, specifically the shear adhesive strength is reduced. On the other hand, if the content of hydroxyl group-containing monomer units in the vinyl chloride paste resin exceeds 6 mass %, the tensile strength and elongation of the coating film when processed at low temperatures are poor.
- the vinyl chloride paste resin contains 4% by mass or more of vinyl ester monomer units, and preferably 4.5% by mass or more. If the content of vinyl ester monomer units in the vinyl chloride paste resin is less than 4% by mass, the tensile strength and elongation of the coating film when processed at low temperatures will be poor.
- the upper limit of the content of vinyl ester monomer units in the vinyl chloride paste resin may be in the range of 11% by mass or less, which is the upper limit of the total content of hydroxyl group-containing monomer units and vinyl ester monomer units, and is not particularly limited, but may be, for example, 10% by mass or less, 9% by mass or less, 8% by mass or less, or 7.5% by mass or less. More specifically, the vinyl chloride paste resin may contain 4 to 10% by mass, 4 to 9% by mass, 4.5 to 8% by mass, or 4.5 to 7.5% by mass of vinyl ester monomer units.
- the total content of the hydroxyl group-containing monomer units and the vinyl ester monomer units is 7.5 to 11 mass%, preferably 8 to 10.5 mass%, more preferably 8.5 to 10.5 mass%, and even more preferably 9 to 10.5 mass%. If the total content of the hydroxyl group-containing monomer units and the vinyl ester monomer units in the vinyl chloride paste resin is less than 7.5 mass%, the shear adhesive strength, tensile strength, and elongation are inferior.
- the shear properties of the coating film when processed at low temperatures are inferior, specifically the shear adhesive strength is reduced.
- the vinyl chloride paste resin preferably contains 89 to 92.5% by mass of vinyl chloride units, 1 to 6% by mass of hydroxyl-containing monomer units, 4% or more by mass of vinyl ester monomer units, and a total of 7.5 to 11% by mass of hydroxyl-containing monomer units and vinyl ester monomer units, more preferably 89.5 to 92% by mass of vinyl chloride units, 1 to 6% by mass of hydroxyl-containing monomer units, 4% or more by mass of vinyl ester monomer units, and a total of 8 to 10.5% by mass of hydroxyl-containing monomer units and vinyl ester monomer units, and even more preferably 89.5 to 91.5% by mass of vinyl chloride units, 1 to 6% by mass of hydroxyl-containing monomer units, 4% or more by mass of vinyl ester monomer units, and a total of 8.5 to 10.5% by mass of hydroxyl-containing monomer units and vinyl ester monomer units.
- the vinyl ester monomer is not particularly limited, but examples thereof include vinyl esters of carboxylic acids, and as vinyl esters of carboxylic acids, fatty acid vinyl esters are preferred.
- the fatty acid vinyl esters may have 1 to 22 carbon atoms, for example.
- Specific examples of the fatty acid vinyl esters include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl stearate, and from the viewpoint of cost, vinyl acetate is preferred.
- the vinyl ester monomers may be used alone or in combination of two or more.
- the hydroxyl group-containing monomer is not particularly limited, but examples thereof include (meth)acrylic acid hydroxyalkyl esters.
- the (meth)acrylic acid hydroxyalkyl ester is not particularly limited, but examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 8-hydroxyoctyl (meth)acrylate.
- (meth)acrylic acid includes one or more selected from the group consisting of methacrylic acid and acrylic acid
- (meth)acrylate includes one or more selected from the group consisting of methacrylate and acrylate.
- the vinyl chloride paste resin may be prepared by copolymerizing vinyl chloride with a third monomer other than the hydroxyl group-containing monomer and the vinyl ester monomer.
- the third monomer include olefin compounds such as ethylene, propylene, and butene; vinyl ether compounds having an alkyl group such as methyl vinyl ether, ethyl vinyl ether, octyl vinyl ether, and lauryl vinyl ether; vinylidene halide compounds such as vinylidene chloride; unsaturated carboxylic acids and their anhydrides such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, maleic anhydride, and itaconic anhydride; unsaturated carboxylic acid ester compounds such as methyl acrylate, ethyl acrylate, monomethyl maleate, dimethyl maleate, and butylbenzyl maleate; aromatic vinyl compounds such as styrene, ⁇ -methylstyrene,
- the vinyl chloride paste resin may contain 3% by mass or less, or 1% by mass or less, of a third monomer unit other than the hydroxyl group-containing monomer unit and the vinyl ester monomer unit.
- the content of each monomer unit in the polyvinyl chloride paste resin can be determined by measurement and analysis using nuclear magnetic resonance spectroscopy (NMR), and specifically, can be determined as described in the examples.
- NMR nuclear magnetic resonance spectroscopy
- the average degree of polymerization of the vinyl chloride paste resin is not particularly limited, but may be, for example, 1000 to 2000 or 1400 to 1900. In this specification, the average degree of polymerization of the vinyl chloride paste resin can be measured in accordance with JIS K 6720-2:1999.
- the method for producing a vinyl chloride paste resin may include a step of polymerizing vinyl chloride and other monomers in a polymerization reactor in the presence of an aqueous medium.
- the other monomers the hydroxyl group-containing monomers and vinyl ester monomers described in the description of the vinyl chloride paste resin may be appropriately used, and a third monomer or the like may be appropriately used as necessary.
- the polymerization reactor one that is usually used for polymerization of vinyl chloride paste resins may be appropriately used.
- the amount of the hydroxyl-containing monomer used per 100 parts by mass of the vinyl chloride is not particularly limited as long as a vinyl chloride paste resin containing hydroxyl-containing monomer units and vinyl ester monomer units within the above-mentioned ranges is obtained, but may be, for example, 0.7 to 6 parts by mass, or 1 to 5 parts by mass.
- the amount of vinyl ester monomer used per 100 parts by mass of vinyl chloride is not particularly limited as long as a vinyl chloride paste resin containing hydroxyl group-containing monomer units and vinyl ester monomer units within the above-mentioned ranges is obtained, but may be, for example, 5 to 15 parts by mass, or 6 to 13 parts by mass.
- the polymerization can be suitably carried out by a polymerization method carried out in the presence of an aqueous medium.
- a polymerization method include fine suspension polymerization, emulsion polymerization, sheet emulsion polymerization, and seed fine suspension polymerization.
- the fine suspension polymerization for example, the above-mentioned monomers (vinyl chloride and other monomers), an emulsifier, an oil-soluble initiator, and, if necessary, a dispersing aid are added to an aqueous medium to carry out polymerization.
- the above-mentioned monomers vinyl chloride and other monomers
- an emulsifier for example, an emulsifier, a water-soluble initiator, and, if necessary, a dispersing aid are added to an aqueous medium to carry out polymerization.
- a seed emulsion polymerization particles produced by emulsion polymerization are used as seeds, and in the seed fine suspension polymerization, seed particles obtained by the fine suspension polymerization are used as seeds.
- emulsifier examples include anionic surfactants and nonionic surfactants.
- anionic surfactant examples include salts of carboxylic acids, alkyl sulfonic acids, alkyl benzene sulfonic acids, ⁇ -olefin sulfonic acids, sulfosuccinic acids, alkyl sulfosuccinic acids, alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl allyl ether sulfates, alkyl phosphoric acids, polyoxyethylene alkyl ether phosphoric acids, and polyoxyethylene alkyl allyl ether phosphoric acids.
- the salts include metal salts such as potassium salts and sodium salts, and ammonium salts.
- nonionic surfactants include polyoxyalkylene alkyl ethers such as polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, and polyoxyethylene polyoxypropylene alkyl ether; polyoxyalkylene alkyl phenyl ethers such as polyoxyethylene alkyl phenyl ether, polyoxypropylene alkyl phenyl ether, and polyoxyethylene polyoxypropylene alkyl phenyl ether; polyoxyalkylene block copolymers such as polyoxyethylene polyoxypropylene block copolymer, and polyoxyethylene polyoxypropylene polyoxyethylene block copolymer; fatty acid ester compounds such as glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, and polyoxyethylene fatty acid ester; and silicone-based emulsifiers.
- polyoxyalkylene alkyl ethers such
- the emulsifier may be used alone or in combination of two or more.
- the amount of the emulsifier used may be 0.1 to 3 parts by mass, or 0.1 to 1 part by mass, per 100 parts by mass of the total amount of monomers used in the polymerization.
- oil-soluble initiator examples include organic peroxide initiators and azo initiators.
- organic peroxide initiator examples include diacyl peroxides such as dilauroyl peroxide and di-3,5,5-trimethylhexanoyl peroxide; peroxydicarbonates such as diisopropyl peroxydicarbonate and di-2-ethylhexyl peroxydicarbonate; and peroxyesters such as t-butyl peroxypivalate, t-butyl peroxyneodecanoate, and cumyl peroxyneodecanoate.
- azo initiator examples include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile).
- the oil-soluble initiator may be used alone or in combination of two or more.
- the amount of the oil-soluble initiator used may be 0.01 to 3 parts by mass per 100 parts by mass of the vinyl chloride monomer.
- water-soluble initiator examples include inorganic peroxides. Specific examples of the inorganic peroxides include ammonium persulfate, potassium persulfate, sodium persulfate, and hydrogen peroxide. If necessary, reducing agents such as sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate (Rongalite), ascorbic acid, and sodium ascorbate may be used in combination.
- the water-soluble initiators may be used alone or in combination of two or more. The amount of the water-soluble initiator used may be 0.01 to 3 parts by mass per 100 parts by mass of the total amount of monomers used in the polymerization.
- the dispersion aid may be, for example, a higher alcohol or a higher fatty acid.
- a higher alcohol an alcohol having 6 or more carbon atoms may be appropriately used, and specific examples thereof include hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, nonadecyl alcohol, and eicosyl alcohol.
- a fatty acid having 12 or more carbon atoms may be appropriately used, and specific examples thereof include lauric acid, myristic acid, palmitic acid, and stearic acid.
- the dispersion aid may be used alone or in combination of two or more.
- the amount of the dispersion aid used may be 0 to 5 parts by mass or 0.3 to 2 parts by mass per 100 parts by mass of the total amount of the monomers used in the polymerization.
- the monomers used in the polymerization may be added to the aqueous medium all at once, may be added in two or more separate portions, or may be added continuously at a constant rate.
- vinyl chloride and vinyl ester monomers may be added all at once before the start of polymerization, and the hydroxyl-containing monomer may be added all at once after the start of polymerization.
- the reaction rate of the hydroxyl-containing monomer is faster than that of other monomers, it is desirable to continuously supply the hydroxyl-containing monomer at a constant rate from the viewpoint of copolymerizing it with other monomers.
- the method of supplying the emulsifier, the polymerization initiator, and the dispersing aid used if necessary to the polymerization reactor is not particularly limited, and they may be supplied all at once or in two or more separate portions.
- 50% by mass or more of the total amount of vinyl chloride may be fed into the polymerization reactor to initiate polymerization, and the initial amount of vinyl chloride charged before the start of polymerization may be, for example, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, or the total amount.
- vinyl chloride, vinyl ester monomer, emulsifier, polymerization initiator, and, if necessary, a dispersing aid are added to the aqueous medium and homogenized, and then the temperature is adjusted to, for example, 30 to 80°C to start polymerization, and after polymerization has started, the hydroxyl group-containing monomer can be added continuously at a constant rate.
- the polymerization conversion rate also called the monomer conversion rate
- the polymerization conversion rate can be measured and calculated as described in the Examples.
- vinyl chloride, vinyl ester monomer, emulsifier, polymerization initiator, and, if necessary, dispersing aid are added to the aqueous medium and homogenized, and then the temperature is adjusted to, for example, 30 to 80°C to start polymerization, and once the polymerization conversion rate has reached 5% or more, but before it reaches 50%, it is preferable to continuously add the hydroxyl group-containing monomer at a constant rate.
- the method for producing the vinyl chloride paste resin may further include a drying step of drying the latex of the vinyl chloride paste resin obtained in the polymerization step described above.
- the drying of the latex of the vinyl chloride paste resin is not particularly limited, but is preferably spray drying.
- a single latex may be spray dried, or two or more types of latex may be mixed and then spray dried, as necessary.
- the latex of the vinyl chloride paste resin may be concentrated and then spray dried. Before drying, coarse particles in the latex of the vinyl chloride paste resin may be removed using a wet vibrating sieve, as necessary. After drying, coarse particles in the vinyl chloride paste resin may be removed, or the vinyl chloride paste resin may be pulverized, as necessary.
- a vinyl chloride-based paste resin composition (hereinafter, also simply referred to as a "resin composition") contains the vinyl chloride-based paste resin.
- the resin composition may be a paste sol.
- the paste sol may be a plastisol or an organosol.
- the resin composition may be molded by being gelled by heating.
- the resin composition may contain a plasticizer in addition to the vinyl chloride paste resin.
- the plasticizer is not particularly limited, and any plasticizer for vinyl chloride resins may be used as appropriate.
- phthalate ester plasticizers such as di-2-ethylhexyl phthalate (DOP), di-normal octyl phthalate, dibutyl phthalate, diisononyl phthalate (DINP), and butyl benzyl phthalate
- phosphate ester plasticizers such as tricresyl phosphate and tri-2-ethylhexyl phosphate
- adipate ester plasticizers such as di-2-ethylhexyl adipate
- sebacate ester plasticizers such as di-2-ethylhexyl sebacate
- azelaate ester plasticizers such as di-2-ethylhexyl azelate.
- trimellitic acid ester-based plasticizers such as tri-2-ethylhexyl trimellitate; polyester-based plasticizers; benzoic acid ester-based plasticizers such as di-2-ethylhexyl benzoate, diethylene glycol dibenzoate, and 2,2,4-trimethyl-1,3-pentanediol isobutyrate benzoate; citrate ester-based plasticizers such as acetyl tributyl citrate; glycolic acid ester-based plasticizers; chlorinated paraffin-based plasticizers; chlorinated fatty acid ester-based plasticizers; epoxy-based plasticizers; and texanol isobutyrate.
- the plasticizers may be used alone or in combination of two or more. Among them, phthalic acid ester-based plasticizers are preferred, and one or more selected from the group consisting of di-2-ethylhexyl phthalate and diisononyl phthalate are more preferred.
- the amount of plasticizer used per 100 parts by mass of the vinyl chloride paste resin may be 30 to 200 parts by mass, 40 to 150 parts by mass, or 50 to 100 parts by mass.
- the resin composition may contain other additives, such as stabilizers, fillers, adhesion promoters, diluents, viscosity reducers, fillers, antioxidants, reinforcing agents, UV absorbers, foaming agents, flame retardants, antistatic agents, lubricants, pigments, surface treatment agents, thixotropic agents, antifungal agents, and detergents, as necessary.
- additives such as stabilizers, fillers, adhesion promoters, diluents, viscosity reducers, fillers, antioxidants, reinforcing agents, UV absorbers, foaming agents, flame retardants, antistatic agents, lubricants, pigments, surface treatment agents, thixotropic agents, antifungal agents, and detergents, as necessary.
- the stabilizer may be, for example, an organic tin stabilizer such as dimethyltin mercapto, dibutyltin mercapto, dioctyltin mercapto, dibutyltin maleate, dioctyltin maleate, or dibutyltin laurate; a lead-based stabilizer such as lead stearate, dibasic lead phosphite, or tribasic lead sulfate; a zinc-based stabilizer such as a calcium-zinc-based stabilizer or a barium-zinc-based stabilizer; an epoxy-based stabilizer such as epoxidized soybean oil, epoxidized linseed oil, epoxidized tetrahydrophthalate, or epoxidized polybutadiene; or a phosphoric acid ester.
- the stabilizer may be used alone or in combination of two or more.
- the amount of stabilizer used per 100 parts by mass of the vinyl chloride paste resin may be
- the filler is not particularly limited, but examples thereof include calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, talc, silica, clay, calcium silicate, and titanium oxide.
- the filler may be used alone or in combination of two or more.
- the amount of filler used per 100 parts by mass of the polyvinyl chloride paste resin may be 0 to 100 parts by mass.
- the adhesion imparting agent is not particularly limited, and examples thereof include polyamide resins, polyethyleneimine resins, and isocyanate compounds.
- examples of the isocyanate compounds include oligomers of toluylene diisocyanate and blocked isocyanates in which the active isocyanate groups of urethane prepolymers are blocked.
- the adhesion imparting agent is preferably an isocyanate compound, and more preferably a blocked isocyanate.
- the adhesion imparting agent may be used alone or in combination of two or more types.
- the amount of adhesion imparting agent used per 100 parts by mass of the vinyl chloride paste resin may be 0 to 20 parts by mass.
- the diluent is not particularly limited, but examples thereof include 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (TXIB), normal paraffin, and isoparaffin. These may be used alone or in combination of two or more.
- TXIB 2,2,4-trimethyl-1,3-pentanediol diisobutyrate
- normal paraffin normal paraffin
- isoparaffin normal paraffin
- the amount of diluent used per 100 parts by mass of the vinyl chloride paste resin may be 0 to 200 parts by mass.
- the resin composition can be obtained by stirring and mixing a mixture of a vinyl chloride paste resin, a plasticizer, and, if necessary, other additives.
- a dissolver type stirrer for example, can be used.
- the resin composition is preferably such that a layer of the resin composition having a thickness of 1 m is formed between two electrocoated steel plates and heated at 120°C for 30 minutes, and the maximum adhesive strength of the obtained test piece in a shear test is preferably 1.65 MPa or more, more preferably 1.90 MPa or more, even more preferably 2.15 MPa or more, and particularly preferably 2.30 MPa or more.
- the resin composition has a tensile strength (breaking strength) of 2.6 MPa or more, preferably 2.8 MPa or more, and even more preferably 3.0 MPa or more, of a JIS No. 2 dumbbell-shaped test piece obtained from a sheet obtained by heating a 1 m thick coating of the resin composition at 120°C for 30 minutes.
- the resin composition is preferably such that the elongation of a JIS No. 2 dumbbell-shaped test piece obtained from a sheet obtained by heating a 1 m thick coating of the resin composition at 120°C for 30 minutes is 180% or more, more preferably 185% or more, even more preferably 190% or more, and particularly preferably 195% or more.
- the vinyl chloride paste resin composition can be used as an automobile paint, and can be particularly suitably used as an automobile sealant and/or an automobile underbody coating.
- the vinyl chloride paste resin composition can also be used for, for example, wallpaper, cushion flooring, carpet tile flooring, ceiling materials, leather, canvas, steel plates, automobile interior materials, marking films, tablecloths, toys, dolls, gloves, waterproof coating materials, insulating coating materials, medical supplies, cap seals, and food models.
- ⁇ Method for measuring the content of each monomer unit in polyvinyl chloride paste resin The content of each monomer unit in the vinyl chloride paste resin was determined by measurement and analysis using nuclear magnetic resonance spectroscopy (NMR) as follows. 10 mg of vinyl chloride-based paste resin was dissolved in 0.75 mL of deuterated THF (THF-d8), a solvent for NMR, at room temperature for 3 hours. The resulting solution was subjected to 1H measurement using a nuclear magnetic resonance apparatus (AVANCE III HD500 digital NMR apparatus, manufactured by BRUKER) at a magnetic field strength of 500 MHz.
- NMR nuclear magnetic resonance spectroscopy
- the integral value of the signal intensity at a chemical shift of 4.1 to 4.7 ppm for vinyl chloride, the integral value of the signal intensity at a chemical shift of 5.1 to 5.6 ppm for vinyl acetate, and the integral value of the signal intensity at a chemical shift of 1.1 to 1.3 ppm for 2-hydroxyethyl acrylate were used, and the contents of vinyl chloride units, vinyl acetate units, and 2-hydroxyethyl acrylate units in the vinyl chloride paste resin were calculated from the ratio of these integral values.
- a sheet was prepared by applying the paste sol (plastisol) to a thickness of about 1 mm on a glass plate and heating in an oven at 120° C. or 140° C. for 30 minutes. The obtained sheet was punched into a JIS No. 2 dumbbell, and marks were made at 20 mm intervals in the center of the test piece.
- a tensile test was carried out using a tensile tester (Shimadzu Corporation, AGS-1000A) at 23° C. and 50% (RH) in accordance with JIS K-6251:2017, with a check distance of 60 mm and a speed of 200 mm/min. The strength at break and the elongation between the marks were measured to determine the tensile strength and elongation percentage.
- a Teflon (registered trademark) spacer having a thickness of 1 mm and a width of 3 mm was placed on the long side edge of the degreased electrodeposition-coated steel sheet, and another Teflon (registered trademark) spacer having a thickness of 1 mm and a width of 3 mm was placed so that the distance between the spacers was 25 mm.
- the shear test was performed using a tensile tester (Shimadzu Corporation, AG-X) at 23°C and 50% (RH) in accordance with JIS K-6251:2017, with a check distance of 70 mm and a speed of 50 mm/min. The strength at break was measured and taken as the maximum adhesive strength.
- the amount of vinyl chloride is the total amount of vinyl chloride used in the polymerization reaction, and the amount of other monomers is the total amount of monomers other than vinyl chloride used in the polymerization reaction.
- Example 1 Preparation of vinyl chloride paste resin> A polymerization reactor (a stainless steel pressure-resistant vessel equipped with a stirrer) was charged with 80 parts by mass of ion-exchanged water, 0.80 parts by mass of sodium dodecylbenzenesulfonate, 0.40 parts by mass of cetyl alcohol, 0.3 parts by mass of stearyl alcohol, 0.1 parts by mass of cumyl peroxy neodecanoate, 0.05 parts by mass of t-butyl peroxy neodecanoate, 8.5 parts by mass of vinyl acetate monomer, and 89.7 parts by mass of vinyl chloride, and the mixture was homogenized.
- the temperature inside the pressure vessel was raised to 37.5°C to initiate polymerization.
- 1.8 parts by mass of 2-hydroxypropyl acrylate (hereinafter sometimes abbreviated as "HPA") was continuously added at a constant rate.
- HPA 2-hydroxypropyl acrylate
- the polymerization period from the start to the end of polymerization was 10.5 hours.
- the latex from which the coarse particles had been removed was spray-dried using a spray dryer (manufactured by Okawara Kakoki Co., Ltd.) under conditions of an inlet temperature of 105° C.
- the resulting mixture was kneaded at room temperature at 1000 rpm for 2 minutes using a dissolver type kneader (ROBO MICS, manufactured by Primix Corporation, dissolver blade diameter 5 cm). After kneading, 37 parts by mass of DINP were further added and mixed until uniform. The mixture was kneaded at room temperature for 1 minute at 1000 rpm using the dissolver type kneader described above. The mixture was transferred to an Ishikawa type crusher (manufactured by Ishikawa Kogyo Co., Ltd.) and subjected to a defoaming treatment to obtain a paste sol.
- Ishikawa type crusher manufactured by Ishikawa Kogyo Co., Ltd.
- Example 5 A vinyl chloride-based paste resin and a paste sol were obtained by the same operation as in Example 1, except that the amounts of vinyl acetate monomer, vinyl chloride and 2-hydroxypropyl acrylate were changed as shown in Table 1 below, and the polymerization temperature was changed to the temperature shown in Table 1 below.
- Example 6 A vinyl chloride paste resin was obtained in the same manner as in Example 1, except that the period of continuous addition of 2-hydroxypropyl acrylate was changed as shown in Table 1 below.
- Example 7 A vinyl chloride paste resin was obtained in the same manner as in Example 2, except that the period of continuous addition of 2-hydroxypropyl acrylate was changed as shown in Table 1 below.
- Example 1 A vinyl chloride-based paste resin and a paste sol were obtained by the same operation as in Example 1, except that the amount of vinyl acetate monomer charged was changed to 10.4 parts by mass, the amount of vinyl chloride charged was changed to 89.6 parts by mass, the polymerization temperature was changed to 37°C, and further, 2-hydroxypropyl acrylate was not added.
- Comparative Example 2 A vinyl chloride-based paste resin and a paste sol were obtained in the same manner as in Comparative Example 1, except that the amount of vinyl acetate monomer charged was changed to 11.6 parts by mass, the amount of vinyl chloride charged was changed to 88.4 parts by mass, and the polymerization temperature was changed to 36°C.
- Example 6 A vinyl chloride paste resin and a paste sol were obtained by the same operations as in Example 1, except that the charged amounts of vinyl acetate monomer, vinyl chloride, cumyl peroxy neodecanoate, cumyl peroxy neodecanoate, t-butyl peroxy neodecanoate, and t-butyl peroxy neodecanoate were changed to 0.05 parts by mass, 0.025 parts by mass, the polymerization temperature was changed to 42°C, and further the charged amount of 2-hydroxypropyl acrylate was changed to 5 parts by mass, and the continuous addition period was changed to from 1 hour to 6 hours after the start of polymerization.
- Example 7 A paste sol was obtained by the same procedure as in Example 1, except that the vinyl chloride paste resin used in preparing the paste sol was changed to a mixture of 70 parts by mass of the vinyl chloride paste resin obtained in Comparative Example 1 and 30 parts by mass of the vinyl chloride paste resin obtained in Comparative Example 6.
- Example 8 A paste sol was obtained in the same manner as in Example 1, except that the vinyl chloride paste resin used in preparing the paste sol was changed to PCH-72 (manufactured by Kaneka Corporation), a product sold for UBC.
- the paste sol containing the vinyl chloride paste resin of the Example had good maximum adhesive strength, tensile strength, and elongation in the shear test of the coating film when processed at low temperature (specifically 120°C). Furthermore, the data in Table 3 show that the viscosity of the paste sol containing the vinyl chloride paste resin of Example 6 or Example 7 after being left at 35°C for 7 days is lower than the viscosity of the paste sol containing the vinyl chloride paste resin of Example 1 or Example 2 after being left at 35°C for 7 days, and that the handleability over time is improved.
- the paste sols containing the vinyl chloride paste resins of Comparative Examples 1, 2 and 8, which contain vinyl acetate monomer units but no HPA units have low maximum adhesive strength in a shear test and poor low-temperature processability when processed at low temperature.
- the paste sol containing the vinyl chloride paste resin of Comparative Example 6, which contains HPA units but no vinyl acetate monomer units has low tensile strength and elongation when processed at low temperature and poor low-temperature processability.
- the paste sol containing the vinyl chloride paste resin of Comparative Example 3 which has a vinyl acetate monomer unit content of less than 4 mass% and an HPA unit content of more than 6 mass%, has low tensile strength and elongation when processed at low temperature and poor low-temperature processability.
- the paste sol containing the vinyl chloride paste resin of Comparative Example 4 which has a vinyl acetate monomer unit content of 4 mass% or more but an HPA unit content of more than 6 mass%, has low maximum adhesive strength in a shear test and poor low-temperature processability when processed at low temperature.
- the paste sol of Comparative Example 7, which contains both the vinyl chloride paste resin of Comparative Example 1, which contains vinyl acetate monomer units but does not contain HPA units, and the vinyl chloride paste resin of Comparative Example 6, which contains HPA units but does not contain vinyl acetate monomer units has a low maximum adhesive strength in a shear test and poor low-temperature processability when processed at low temperatures.
- the present invention is not particularly limited, but may include, for example, the following embodiments. It goes without saying that the present invention is not limited to the following embodiments, and various aspects are possible in terms of details.
- a vinyl chloride paste resin composition comprising the vinyl chloride paste resin according to any one of [1] to [6].
- the vinyl chloride paste resin composition according to [7] which is an automotive paint.
- the vinyl chloride paste resin composition according to [8], wherein the automotive paint is an automotive sealant or an automotive underbody coating agent.
- the method for producing a vinyl chloride paste resin according to [10] wherein the total amount of the hydroxyl group-containing monomer is continuously supplied to a polymerization reactor after the polymerization conversion rate has reached 5% or more and before the polymerization conversion rate reaches 50%.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
One or more embodiments of the present invention relate to a vinyl chloride paste resin as a copolymer of vinyl chloride and other monomers. The other monomers include a hydroxyl group-containing monomer and a vinyl ester monomer. The vinyl chloride paste resin contains 1 to 6 mass% of hydroxyl group-containing monomer units, 4 mass% or more of vinyl ester monomer units, and a total of 7.5 to 11 mass% of the hydroxyl group-containing monomer units and the vinyl ester monomer units. Thus provided are: a vinyl chloride paste resin having good shear characteristics and tensile characteristics when processed at low temperatures; a vinyl chloride paste resin composition containing said vinyl chloride paste resin; and a method for producing the same.
Description
本発明は、自動車塗料に好適に用いることができる塩化ビニル系ペースト樹脂、それを含む塩化ビニル系ペースト樹脂組成物、およびその製造方法に関する。
The present invention relates to a vinyl chloride paste resin that can be suitably used in automotive paints, a vinyl chloride paste resin composition containing the same, and a method for producing the same.
塩化ビニル系ペースト樹脂は、壁紙、床材、カーペット、電気部材、自動車部品、レザーなどの様々な製品に用いられている。特に、塩化ビニル系ペースト樹脂は、耐候性や耐傷付き性、および熱安定性などに優れていることから、自動車シーラント剤や自動車アンダーボディコート剤などの自動車塗料として好適に用いられている。例えば、特許文献１には、分子内に水酸基を有し、平均重合度が３００～１０００であるペースト形成可能な塩化ビニル共重合体を含有するプラスチゾル組成物を自動車の床裏コーティング用塗料に用いることが提案されている。特許文献２には、水酸基を含有するモノマー残基単位１～１０質量％、塩化ビニルモノマー残基単位９０～９９質量％を含み、平均重合度が１０００～２０００である塩化ビニル系共重合体１００質量部に対して、直鎖アルキルベンゼンスルホン酸塩０．５～２．０質量部を含有するペースト加工用水酸基含有塩化ビニル系共重合体組成物粒子を、自動車アンダーボディコート剤として用いることが提案されている。
Vinyl chloride paste resins are used in a variety of products, including wallpaper, flooring, carpets, electrical components, automobile parts, and leather. In particular, vinyl chloride paste resins are suitable for use as automobile paints, such as automobile sealants and automobile underbody coatings, due to their excellent weather resistance, scratch resistance, and thermal stability. For example, Patent Document 1 proposes the use of a plastisol composition containing a vinyl chloride copolymer capable of forming a paste and having an average degree of polymerization of 300 to 1000 in the molecule as a coating for the underside of an automobile floor. Patent Document 2 proposes the use of hydroxyl-containing vinyl chloride copolymer composition particles for paste processing, which contain 1 to 10 mass% of hydroxyl-containing monomer residue units, 90 to 99 mass% of vinyl chloride monomer residue units, and 0.5 to 2.0 mass parts of linear alkylbenzene sulfonate per 100 mass parts of a vinyl chloride copolymer having an average degree of polymerization of 1000 to 2000, as an automobile underbody coating agent.
しかしながら、特許文献１および２では、分子内に水酸基を含有する塩化ビニル共重合体を用いているが、分子内に水酸基を含有する塩化ビニル共重合体を含むプラスチゾルを低温加工した場合、せん断特性は良好であるものの、引張強度や伸び率が劣る場合がある。
However, in Patent Documents 1 and 2, a vinyl chloride copolymer containing hydroxyl groups in the molecule is used, and when a plastisol containing a vinyl chloride copolymer containing hydroxyl groups in the molecule is processed at low temperatures, the shear properties are good, but the tensile strength and elongation may be poor.
本発明は、前記問題を解決するため、低温加工時のせん断特性および引張特性が良好である塩化ビニル系ペースト樹脂、それを含む塩化ビニル系ペースト樹脂組成物、およびその製造方法を提供する。
In order to solve the above problems, the present invention provides a vinyl chloride paste resin that has good shear and tensile properties during low-temperature processing, a vinyl chloride paste resin composition containing the same, and a method for producing the same.
本発明の１以上の実施形態は、塩化ビニルおよび他のモノマーが共重合した塩化ビニル系ペースト樹脂であって、前記他のモノマーは、水酸基含有モノマーおよびビニルエステル系モノマーを含み、前記塩化ビニル系ペースト樹脂は、水酸基含有モノマー単位を１～６質量％、ビニルエステル系モノマー単位を４質量％以上、且つ、水酸基含有モノマー単位およびビニルエステル系モノマー単位を合計で７．５～１１質量％含む、塩化ビニル系ペースト樹脂に関する。
One or more embodiments of the present invention relate to a vinyl chloride paste resin in which vinyl chloride and other monomers are copolymerized, the other monomers including a hydroxyl group-containing monomer and a vinyl ester monomer, and the vinyl chloride paste resin includes 1 to 6 mass% of hydroxyl group-containing monomer units, 4 mass% or more of vinyl ester monomer units, and a total of 7.5 to 11 mass% of hydroxyl group-containing monomer units and vinyl ester monomer units.
本発明の１以上の実施形態は、前記塩化ビニル系ペースト樹脂を含む、塩化ビニル系ペースト樹脂組成物に関する。
One or more embodiments of the present invention relate to a vinyl chloride paste resin composition containing the vinyl chloride paste resin.
本発明の１以上の実施形態は、前記塩化ビニル系ペースト樹脂の製造方法であって、塩化ビニルおよび他のモノマーを、水系媒体の存在下、重合反応器中で重合する工程を含み、前記他のモノマーは、水酸基含有モノマーおよびビニルエステル系モノマーを含み、前記水酸基含有モノマーを、重合開始後に、連続的に重合反応器に供給する、塩化ビニル系ペースト樹脂の製造方法に関する。
One or more embodiments of the present invention relate to a method for producing a vinyl chloride paste resin, the method comprising the step of polymerizing vinyl chloride and other monomers in a polymerization reactor in the presence of an aqueous medium, the other monomers including a hydroxyl group-containing monomer and a vinyl ester monomer, and continuously supplying the hydroxyl group-containing monomer to the polymerization reactor after polymerization initiation.
本発明によれば、低温加工時のせん断特性および引張特性が良好である塩化ビニル系ペースト樹脂およびそれを含む塩化ビニル系ペースト樹脂組成物を提供することができる。
また、本発明の製造方法によれば、低温加工時のせん断特性および引張特性が良好である塩化ビニル系ペースト樹脂を得ることができる。 According to the present invention, it is possible to provide a vinyl chloride paste resin having good shear properties and tensile properties during low-temperature processing, and a vinyl chloride paste resin composition containing the same.
Furthermore, according to the production method of the present invention, it is possible to obtain a vinyl chloride paste resin that has good shear properties and tensile properties during low-temperature processing.
また、本発明の製造方法によれば、低温加工時のせん断特性および引張特性が良好である塩化ビニル系ペースト樹脂を得ることができる。 According to the present invention, it is possible to provide a vinyl chloride paste resin having good shear properties and tensile properties during low-temperature processing, and a vinyl chloride paste resin composition containing the same.
Furthermore, according to the production method of the present invention, it is possible to obtain a vinyl chloride paste resin that has good shear properties and tensile properties during low-temperature processing.
本発明の発明者らは、上述した問題を解決するために検討を重ねた。その結果、塩化ビニルを水酸基含有モノマーおよびビニルエステル系モノマーと共重合させた塩化ビニル系ペースト樹脂を用いるとともに、該塩化ビニル系ペースト樹脂における水酸基含有モノマー単位およびビニルエステル系モノマー単位のそれぞれの含有量および合計含有量を特定の範囲にすることで、該塩化ビニル系ペースト樹脂を含むペースト樹脂組成物を低温、例えば、１２０℃で加工した際、せん断特性および引張特性に優れることを見出した。本明細書において、塩化ビニル系ペースト樹脂における「モノマー単位」とは、モノマー由来の繰り返し単位を意味する。
The inventors of the present invention have conducted extensive research to solve the above-mentioned problems. As a result, they have found that by using a vinyl chloride paste resin in which vinyl chloride is copolymerized with a hydroxyl-containing monomer and a vinyl ester monomer, and by setting the respective contents and total contents of the hydroxyl-containing monomer units and the vinyl ester monomer units in the vinyl chloride paste resin within specific ranges, a paste resin composition containing the vinyl chloride paste resin has excellent shear properties and tensile properties when processed at a low temperature, for example, at 120°C. In this specification, the term "monomer unit" in the vinyl chloride paste resin means a repeating unit derived from a monomer.
本明細書において、数値範囲が「～」で示されている場合、該数値範囲は両端値（上限および下限）を含む。例えば、「Ｘ～Ｙ」という数値範囲は、ＸおよびＹという両端値を含む範囲であり、「Ｘ以上Ｙ以下」と同じ範囲である。また、その範囲内にある任意の数やその範囲内に含まれる任意の範囲が、具体的に開示される。また、本明細書において、数値範囲が複数記載されている場合、異なる数値範囲の上限および下限を適宜組み合わせた数値範囲を含むものとする。
In this specification, when a numerical range is indicated with "~", the numerical range includes both end values (upper and lower limits). For example, a numerical range of "X to Y" is a range that includes both end values X and Y, and is the same range as "X or more and Y or less". Any number within that range and any range contained within that range are specifically disclosed. In addition, when multiple numerical ranges are described in this specification, they are considered to include numerical ranges that appropriately combine the upper and lower limits of different numerical ranges.
（塩化ビニル系ペースト樹脂）
本明細書において、塩化ビニル系ペースト樹脂は、ペースト用塩ビ樹脂とも称されるものであり、ペースト加工法にて加工させる樹脂である。ペースト加工法は、ペースト樹脂を液体の可塑剤中に懸濁させてペースト状（ゾル）にし、その流動性を利用して賦形し、その後加熱固化（ゲル化）して成形する加工法である。塩化ビニル系ペースト樹脂は、一般的に、１次粒子の粒子径の範囲が０．１～１０μｍ程度である。本明細書において、塩化ビニル系ペースト樹脂の１次粒子の粒子径の範囲は、塩化ビニル系ペースト樹脂を水に分散させた分散液を用い、動的光散乱法で粒子径分布を測定することで確認することができる。 (Vinyl chloride paste resin)
In this specification, vinyl chloride paste resin is also referred to as PVC resin for paste, and is a resin processed by a paste processing method. The paste processing method is a processing method in which a paste resin is suspended in a liquid plasticizer to form a paste (sol), and then shaped by utilizing its fluidity, and then heated and solidified (gelled) to form a molded product. The particle size range of the primary particles of vinyl chloride paste resin is generally about 0.1 to 10 μm. In this specification, the particle size range of the primary particles of vinyl chloride paste resin can be confirmed by using a dispersion liquid in which vinyl chloride paste resin is dispersed in water and measuring the particle size distribution by dynamic light scattering.
本明細書において、塩化ビニル系ペースト樹脂は、ペースト用塩ビ樹脂とも称されるものであり、ペースト加工法にて加工させる樹脂である。ペースト加工法は、ペースト樹脂を液体の可塑剤中に懸濁させてペースト状（ゾル）にし、その流動性を利用して賦形し、その後加熱固化（ゲル化）して成形する加工法である。塩化ビニル系ペースト樹脂は、一般的に、１次粒子の粒子径の範囲が０．１～１０μｍ程度である。本明細書において、塩化ビニル系ペースト樹脂の１次粒子の粒子径の範囲は、塩化ビニル系ペースト樹脂を水に分散させた分散液を用い、動的光散乱法で粒子径分布を測定することで確認することができる。 (Vinyl chloride paste resin)
In this specification, vinyl chloride paste resin is also referred to as PVC resin for paste, and is a resin processed by a paste processing method. The paste processing method is a processing method in which a paste resin is suspended in a liquid plasticizer to form a paste (sol), and then shaped by utilizing its fluidity, and then heated and solidified (gelled) to form a molded product. The particle size range of the primary particles of vinyl chloride paste resin is generally about 0.1 to 10 μm. In this specification, the particle size range of the primary particles of vinyl chloride paste resin can be confirmed by using a dispersion liquid in which vinyl chloride paste resin is dispersed in water and measuring the particle size distribution by dynamic light scattering.
前記塩化ビニル系ペースト樹脂は、塩化ビニルおよび他のモノマーが共重合したものであり、他のモノマーは、水酸基含有モノマーおよびビニルエステル系モノマーを含む。
The vinyl chloride paste resin is a copolymer of vinyl chloride and other monomers, and the other monomers include hydroxyl group-containing monomers and vinyl ester monomers.
前記塩化ビニル系ペースト樹脂は、水酸基含有モノマー単位を１～６質量％含み、１．５～５質量％含むことが好ましく、２．０～４．７質量％含むことがより好ましく、２．５～４．４質量％含むことがさらに好ましい。前記塩化ビニル系ペースト樹脂における水酸基含有モノマー単位の含有量が１質量％未満であると、低温で加工した時の塗膜のせん断特性が劣り、具体的にはせん断接着強度が低下する。一方、前記塩化ビニル系ペースト樹脂における水酸基含有モノマー単位の含有量が６質量％を超えると、低温で加工した際の塗膜の引張強度や伸び率が劣る。
The vinyl chloride paste resin contains 1 to 6 mass %, preferably 1.5 to 5 mass %, more preferably 2.0 to 4.7 mass %, and even more preferably 2.5 to 4.4 mass % of hydroxyl group-containing monomer units. If the content of hydroxyl group-containing monomer units in the vinyl chloride paste resin is less than 1 mass %, the shear properties of the coating film when processed at low temperatures are poor, specifically the shear adhesive strength is reduced. On the other hand, if the content of hydroxyl group-containing monomer units in the vinyl chloride paste resin exceeds 6 mass %, the tensile strength and elongation of the coating film when processed at low temperatures are poor.
前記塩化ビニル系ペースト樹脂は、ビニルエステル系モノマー単位を４質量％以上含み、４．５質量％以上含むことが好ましい。前記塩化ビニル系ペースト樹脂におけるビニルエステル系モノマー単位の含有量が４質量％未満であると、低温で加工した際の塗膜の引張強度と伸びが劣る。前記塩化ビニル系ペースト樹脂におけるビニルエステル系モノマー単位の含有量の上限は、水酸基含有モノマー単位の含有量との合計が、水酸基含有モノマー単位およびビニルエステル系モノマー単位を合計含有量の上限である１１質量％以下の範囲であればよく、特に限定されないが、例えば、１０質量％以下でもよく、９質量％以下でもよく、８質量％以下でもよく、７．５質量％以下でもよい。より具体的には、前記塩化ビニル系ペースト樹脂は、ビニルエステル系モノマー単位を４～１０質量％、４～９質量％、４．５～８質量％、又は４．５～７．５質量％含んでもよい。
The vinyl chloride paste resin contains 4% by mass or more of vinyl ester monomer units, and preferably 4.5% by mass or more. If the content of vinyl ester monomer units in the vinyl chloride paste resin is less than 4% by mass, the tensile strength and elongation of the coating film when processed at low temperatures will be poor. The upper limit of the content of vinyl ester monomer units in the vinyl chloride paste resin may be in the range of 11% by mass or less, which is the upper limit of the total content of hydroxyl group-containing monomer units and vinyl ester monomer units, and is not particularly limited, but may be, for example, 10% by mass or less, 9% by mass or less, 8% by mass or less, or 7.5% by mass or less. More specifically, the vinyl chloride paste resin may contain 4 to 10% by mass, 4 to 9% by mass, 4.5 to 8% by mass, or 4.5 to 7.5% by mass of vinyl ester monomer units.
前記塩化ビニル系ペースト樹脂において、水酸基含有モノマー単位およびビニルエステル系モノマー単位の合計含有量は、７．５～１１質量％であり、好ましくは８～１０．５質量％であり、より好ましくは８．５～１０．５質量％であり、さらに好ましくは９～１０．５質量％である。前記塩化ビニル系ペースト樹脂における水酸基含有モノマー単位およびビニルエステル系モノマー単位の合計含有量が７．５質量％未満であると、せん断接着強度、引張強度、および伸び率が劣る。一方、前記塩化ビニル系ペースト樹脂における水酸基含有モノマー単位およびビニルエステル系モノマー単位の合計含有量が１１質量％を超えると、低温で加工した時の塗膜のせん断特性が劣り、具体的にはせん断接着強度が低下する。
In the vinyl chloride paste resin, the total content of the hydroxyl group-containing monomer units and the vinyl ester monomer units is 7.5 to 11 mass%, preferably 8 to 10.5 mass%, more preferably 8.5 to 10.5 mass%, and even more preferably 9 to 10.5 mass%. If the total content of the hydroxyl group-containing monomer units and the vinyl ester monomer units in the vinyl chloride paste resin is less than 7.5 mass%, the shear adhesive strength, tensile strength, and elongation are inferior. On the other hand, if the total content of the hydroxyl group-containing monomer units and the vinyl ester monomer units in the vinyl chloride paste resin exceeds 11 mass%, the shear properties of the coating film when processed at low temperatures are inferior, specifically the shear adhesive strength is reduced.
前記塩化ビニル系ペースト樹脂は、具体的には、好ましくは塩化ビニル単位を８９～９２．５質量％、水酸基含有モノマー単位を１～６質量％、ビニルエステル系モノマー単位を４質量％以上、且つ、水酸基含有モノマー単位およびビニルエステル系モノマー単位を合計で７．５～１１質量％含み、より好ましくは塩化ビニル単位を８９．５～９２質量％、水酸基含有モノマー単位を１～６質量％、ビニルエステル系モノマー単位を４質量％以上、且つ、水酸基含有モノマー単位およびビニルエステル系モノマー単位を合計で８～１０．５質量％含み、さらに好ましくは塩化ビニル単位を８９．５～９１．５質量％、水酸基含有モノマー単位を１～６質量％、ビニルエステル系モノマー単位を４質量％以上、且つ、水酸基含有モノマー単位およびビニルエステル系モノマー単位を合計で８．５～１０．５質量％含む。
Specifically, the vinyl chloride paste resin preferably contains 89 to 92.5% by mass of vinyl chloride units, 1 to 6% by mass of hydroxyl-containing monomer units, 4% or more by mass of vinyl ester monomer units, and a total of 7.5 to 11% by mass of hydroxyl-containing monomer units and vinyl ester monomer units, more preferably 89.5 to 92% by mass of vinyl chloride units, 1 to 6% by mass of hydroxyl-containing monomer units, 4% or more by mass of vinyl ester monomer units, and a total of 8 to 10.5% by mass of hydroxyl-containing monomer units and vinyl ester monomer units, and even more preferably 89.5 to 91.5% by mass of vinyl chloride units, 1 to 6% by mass of hydroxyl-containing monomer units, 4% or more by mass of vinyl ester monomer units, and a total of 8.5 to 10.5% by mass of hydroxyl-containing monomer units and vinyl ester monomer units.
前記ビニルエステル系モノマーは、特に限定されないが、例えば、カルボン酸のビニルエステルが挙げられ、カルボン酸のビニルエステルとしては脂肪酸ビニルエステルが好ましい。前記脂肪酸ビニルエステルにおいて、例えば、脂肪酸の炭素数が１～２２でもよい。前記脂肪酸ビニルエステルとしては、具体的には、蟻酸ビニル、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、およびステアリン酸ビニルなどが挙げられ、コストの観点から酢酸ビニルが好ましい。前記ビニルエステル系モノマーは、１種を単独で用いてもよく、２種以上を組合わせて用いてもよい。
The vinyl ester monomer is not particularly limited, but examples thereof include vinyl esters of carboxylic acids, and as vinyl esters of carboxylic acids, fatty acid vinyl esters are preferred. In the fatty acid vinyl esters, the fatty acid may have 1 to 22 carbon atoms, for example. Specific examples of the fatty acid vinyl esters include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl stearate, and from the viewpoint of cost, vinyl acetate is preferred. The vinyl ester monomers may be used alone or in combination of two or more.
前記水酸基含有モノマーは、特に限定されないが、例えば、（メタ）アクリル酸ヒドロキシアルキルエステルなどが挙げられる。前記（メタ）アクリル酸ヒドロキシアルキルエステルは、特に制限はないが、例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、３－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、６－ヒドロキシヘキシル（メタ）アクリレート、および８－ヒドロキシオクチル（メタ）アクリレートなどが挙げられる。中でも、コストの観点から、２－ヒドロキシエチル（メタ）アクリレートおよび/または２－ヒドロキシプロピル（メタ）アクリレートが好ましい。前記水酸基含有モノマーは、１種を単独で用いてもよく、２種以上を組合わせて用いてもよい。本明細書において、（メタ）アクリル酸は、メタクリ酸およびアクリル酸からなる群から選ばれる一種以上を含み、（メタ）アクリレートは、メタクリレートおよびアクリレートからなる群から選ばれる一種以上を含む。
The hydroxyl group-containing monomer is not particularly limited, but examples thereof include (meth)acrylic acid hydroxyalkyl esters. The (meth)acrylic acid hydroxyalkyl ester is not particularly limited, but examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 8-hydroxyoctyl (meth)acrylate. Among these, from the viewpoint of cost, 2-hydroxyethyl (meth)acrylate and/or 2-hydroxypropyl (meth)acrylate are preferred. The hydroxyl group-containing monomer may be used alone or in combination of two or more. In this specification, (meth)acrylic acid includes one or more selected from the group consisting of methacrylic acid and acrylic acid, and (meth)acrylate includes one or more selected from the group consisting of methacrylate and acrylate.
前記塩化ビニル系ペースト樹脂は、塩化ビニルに、水酸基含有モノマーおよびビニルエステル系モノマー以外の第３のモノマーを共重合してもよい。前記第３のモノマーとしては、例えばエチレン、プロピレン、およびブテンなどのオレフィン化合物；メチルビニルエーテル、エチルビニルエーテル、オクチルビニルエーテル、およびラウリルビニルエーテルなどのアルキル基を有するビニルエーテル化合物；塩化ビニリデンなどのハロゲン化ビニリデン化合物；アクリル酸、メタクリル酸、フマル酸、マレイン酸、イタコン酸、無水マレイン酸、および無水イタコン酸などの不飽和カルボン酸ならびにその酸無水物；アクリル酸メチル、アクリル酸エチル、マレイン酸モノメチル、マレイン酸ジメチル、およびマレイン酸ブチルベンジルなどの不飽和カルボン酸エステル化合物；スチレン、α－メチルスチレン、およびジビニルベンゼンなどの芳香族ビニル化合物；アクリロニトリルなどの不飽和ニトリル化合物；ならびにジアリルフタレートなどの架橋性モノマーなどが挙げられる。これらは１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。前記塩化ビニル系ペースト樹脂は、水酸基含有モノマー単位およびビニルエステル系モノマー単位以外の第３のモノマー単位を３質量％以下、又は１質量％以下含んでもよい。
The vinyl chloride paste resin may be prepared by copolymerizing vinyl chloride with a third monomer other than the hydroxyl group-containing monomer and the vinyl ester monomer. Examples of the third monomer include olefin compounds such as ethylene, propylene, and butene; vinyl ether compounds having an alkyl group such as methyl vinyl ether, ethyl vinyl ether, octyl vinyl ether, and lauryl vinyl ether; vinylidene halide compounds such as vinylidene chloride; unsaturated carboxylic acids and their anhydrides such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, maleic anhydride, and itaconic anhydride; unsaturated carboxylic acid ester compounds such as methyl acrylate, ethyl acrylate, monomethyl maleate, dimethyl maleate, and butylbenzyl maleate; aromatic vinyl compounds such as styrene, α-methylstyrene, and divinylbenzene; unsaturated nitrile compounds such as acrylonitrile; and crosslinking monomers such as diallyl phthalate. These may be used alone or in combination of two or more. The vinyl chloride paste resin may contain 3% by mass or less, or 1% by mass or less, of a third monomer unit other than the hydroxyl group-containing monomer unit and the vinyl ester monomer unit.
本明細書において、塩化ビニル系ペースト樹脂における各モノマー単位の含有量は、核磁気共鳴スペクトル測定（ＮＭＲ）による測定と解析により求めることができ、具体的には、実施例に記載のとおりに求めることができる。
In this specification, the content of each monomer unit in the polyvinyl chloride paste resin can be determined by measurement and analysis using nuclear magnetic resonance spectroscopy (NMR), and specifically, can be determined as described in the examples.
前記塩化ビニル系ペースト樹脂の平均重合度は、特に制限はないが、例えば、１０００～２０００でもよく、１４００～１９００でもよい。本明細書において、塩化ビニル系ペースト樹脂の平均重合度は、ＪＩＳ Ｋ ６７２０－２：１９９９に従って測定することができる。
The average degree of polymerization of the vinyl chloride paste resin is not particularly limited, but may be, for example, 1000 to 2000 or 1400 to 1900. In this specification, the average degree of polymerization of the vinyl chloride paste resin can be measured in accordance with JIS K 6720-2:1999.
（塩化ビニル系ペースト樹脂の製造方法）
本発明の１以上の実施形態の塩化ビニル系ペースト樹脂の製造方法は、塩化ビニルおよび他のモノマーを、水系媒体の存在下、重合反応器中で重合する工程を含んでもよい。前記他のモノマーとしては、塩化ビニル系ペースト樹脂の説明の欄に記載した水酸基含有モノマー、およびビニルエステル系モノマーを適宜用いることができ、必要に応じて第３のモノマー等を適宜用いてもよい。前記重合反応器は、通常、塩化ビニル系ペースト樹脂の重合に用いるものを適宜用いることができる。 (Method of producing vinyl chloride paste resin)
The method for producing a vinyl chloride paste resin according to one or more embodiments of the present invention may include a step of polymerizing vinyl chloride and other monomers in a polymerization reactor in the presence of an aqueous medium. As the other monomers, the hydroxyl group-containing monomers and vinyl ester monomers described in the description of the vinyl chloride paste resin may be appropriately used, and a third monomer or the like may be appropriately used as necessary. As the polymerization reactor, one that is usually used for polymerization of vinyl chloride paste resins may be appropriately used.
本発明の１以上の実施形態の塩化ビニル系ペースト樹脂の製造方法は、塩化ビニルおよび他のモノマーを、水系媒体の存在下、重合反応器中で重合する工程を含んでもよい。前記他のモノマーとしては、塩化ビニル系ペースト樹脂の説明の欄に記載した水酸基含有モノマー、およびビニルエステル系モノマーを適宜用いることができ、必要に応じて第３のモノマー等を適宜用いてもよい。前記重合反応器は、通常、塩化ビニル系ペースト樹脂の重合に用いるものを適宜用いることができる。 (Method of producing vinyl chloride paste resin)
The method for producing a vinyl chloride paste resin according to one or more embodiments of the present invention may include a step of polymerizing vinyl chloride and other monomers in a polymerization reactor in the presence of an aqueous medium. As the other monomers, the hydroxyl group-containing monomers and vinyl ester monomers described in the description of the vinyl chloride paste resin may be appropriately used, and a third monomer or the like may be appropriately used as necessary. As the polymerization reactor, one that is usually used for polymerization of vinyl chloride paste resins may be appropriately used.
前記塩化ビニル１００質量部に対し、水酸基含有モノマーの使用量は、水酸基含有モノマー単位およびビニルエステル系モノマー単位を上述した範囲内で含む塩化ビニル系ペースト樹脂が得られればよく特に限定されないが、例えば、０．７～６質量部、又は１～５質量部でもよい。
The amount of the hydroxyl-containing monomer used per 100 parts by mass of the vinyl chloride is not particularly limited as long as a vinyl chloride paste resin containing hydroxyl-containing monomer units and vinyl ester monomer units within the above-mentioned ranges is obtained, but may be, for example, 0.7 to 6 parts by mass, or 1 to 5 parts by mass.
前記塩化ビニル１００質量部に対し、ビニルエステル系モノマーの使用量は水酸基含有モノマー単位およびビニルエステル系モノマー単位を上述した範囲内で含む塩化ビニル系ペースト樹脂が得られればよく特に限定されないが、例えば、５～１５質量部、又は６～１３質量部でもよい。
The amount of vinyl ester monomer used per 100 parts by mass of vinyl chloride is not particularly limited as long as a vinyl chloride paste resin containing hydroxyl group-containing monomer units and vinyl ester monomer units within the above-mentioned ranges is obtained, but may be, for example, 5 to 15 parts by mass, or 6 to 13 parts by mass.
前記重合は、水系媒体の存在下で行う重合法で適宜行うことができる。このような重合法としては、例えば、微細懸濁重合法、乳化重合法、シート乳化重合法、およびシード微細懸濁重合法などが挙げられる。微細懸濁重合法では、例えば、水性媒体中に上述したモノマー（塩化ビニルおよび他のモノマー）、乳化剤および油溶性開始剤、並びに必要に応じて分散助剤を加えて重合を行う。乳化重合法では、例えば、水性媒体中に上述したモノマー（塩化ビニルおよび他のモノマー）、乳化剤および水溶性開始剤、並びに必要に応じて分散助剤を加えて重合を行う。シード乳化重合法では、乳化重合で作成した粒子をシードとして用い、シード微細懸濁重合法では、微細懸濁重合法により得られたシード粒子をシードとして用いる。
The polymerization can be suitably carried out by a polymerization method carried out in the presence of an aqueous medium. Examples of such polymerization methods include fine suspension polymerization, emulsion polymerization, sheet emulsion polymerization, and seed fine suspension polymerization. In the fine suspension polymerization, for example, the above-mentioned monomers (vinyl chloride and other monomers), an emulsifier, an oil-soluble initiator, and, if necessary, a dispersing aid are added to an aqueous medium to carry out polymerization. In the emulsion polymerization, for example, the above-mentioned monomers (vinyl chloride and other monomers), an emulsifier, a water-soluble initiator, and, if necessary, a dispersing aid are added to an aqueous medium to carry out polymerization. In the seed emulsion polymerization, particles produced by emulsion polymerization are used as seeds, and in the seed fine suspension polymerization, seed particles obtained by the fine suspension polymerization are used as seeds.
前記乳化剤としては、例えば、アニオン性界面活性剤、およびノニオン性界面活性剤などが挙げられる。
Examples of the emulsifier include anionic surfactants and nonionic surfactants.
前記アニオン性界面活性剤としては、例えば、カルボン酸、アルキルスルホン酸、アルキルベンゼンスルホン酸、α－オレフィンスルホン酸、スルホコハク酸、アルキルスルホコハク酸、アルキル硫酸、ポリオキシエチレンアルキルエーテル硫酸、ポリオキシエチレンアルキルアリルエーテル硫酸、アルキルリン酸、ポリオキシエチレンアルキルエーテルリン酸、ポリオキシエチレンアルキルアリルエーテルリン酸などの塩が挙げられる。当該塩としては、カリウム塩やナトリウム塩などの金属塩、およびアンモニウム塩などが挙げられる。
Examples of the anionic surfactant include salts of carboxylic acids, alkyl sulfonic acids, alkyl benzene sulfonic acids, α-olefin sulfonic acids, sulfosuccinic acids, alkyl sulfosuccinic acids, alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl allyl ether sulfates, alkyl phosphoric acids, polyoxyethylene alkyl ether phosphoric acids, and polyoxyethylene alkyl allyl ether phosphoric acids. Examples of the salts include metal salts such as potassium salts and sodium salts, and ammonium salts.
前記ノニオン性界面活性剤としては、例えば、ポリオキシエチレンアルキルエーテル、ポリオキシプロピレンアルキルエーテル、およびポリオキシエチレンポリオキシプロピレンアルキルエーテルなどのポリオキシアルキレンアルキルエーテル類；ポリオキシエチレンアルキルフェニルエーテル、ポリオキシプロピレンアルキルフェニルエーテル、およびポリオキシエチレンポリオキシプロピレンアルキルフェニルエーテルなどのポリオキシアルキレンアルキルフェニルエーテル類；ポリオキシエチレンポリオキシプロピレンブロックコポリマー、およびポリオキシエチレンポリオキシプロピレンポリオキシエチレンブロックコポリマーなどのポリオキシアルキレンブロックコポリマー類；グリセリン脂肪酸エステル、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンソルビトール脂肪酸エステル、およびポリオキシエチレン脂肪酸エステルなどの脂肪酸エステル化合物；並びにシリコン系乳化剤などが挙げられる。
Examples of the nonionic surfactants include polyoxyalkylene alkyl ethers such as polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, and polyoxyethylene polyoxypropylene alkyl ether; polyoxyalkylene alkyl phenyl ethers such as polyoxyethylene alkyl phenyl ether, polyoxypropylene alkyl phenyl ether, and polyoxyethylene polyoxypropylene alkyl phenyl ether; polyoxyalkylene block copolymers such as polyoxyethylene polyoxypropylene block copolymer, and polyoxyethylene polyoxypropylene polyoxyethylene block copolymer; fatty acid ester compounds such as glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, and polyoxyethylene fatty acid ester; and silicone-based emulsifiers.
前記乳化剤は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。前記乳化剤の使用量は、重合に用いたモノマー合計量１００質量部に対して０．１～３質量部でもよく、０．１～１質量部でもよい。
The emulsifier may be used alone or in combination of two or more. The amount of the emulsifier used may be 0.1 to 3 parts by mass, or 0.1 to 1 part by mass, per 100 parts by mass of the total amount of monomers used in the polymerization.
前記油溶性開始剤としては、例えば、有機過酸化物系開始剤、およびアゾ系開始剤などが挙げられる。前記有機過酸化物系開始剤としては、例えば、ジラウロイルパーオキサイド、およびジ－３，５，５－トリメチルヘキサノイルパーオキサイドなどのジアシルパーオキサイド類；ジイソプロピルペルオキシジカーボネート、およびジ－２－エチルヘキシルペルオキシジカーボネートなどのペルオキシジカーボネート類；ｔ－ブチルペルオキシピバレート、ｔ－ブチルペルオキシネオデカノエート、およびクミルペルオキシネオデカノエートなどのペルオキシエステル類などが挙げられる。アゾ系開始剤としては、２，２'－アゾビスイソブチロニトリル、２，２'－アゾビス（２，４－ジメチルバレロニトリル）、および２，２'－アゾビス（４－メトキシ－２，４－ジメチルバレロニトリル）などが挙げられる。前記油溶性開始剤は１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。前記油溶性開始剤の使用量は、塩化ビニル系単量体１００質量部に対して０．０１～３質量部であってもよい。
Examples of the oil-soluble initiator include organic peroxide initiators and azo initiators. Examples of the organic peroxide initiator include diacyl peroxides such as dilauroyl peroxide and di-3,5,5-trimethylhexanoyl peroxide; peroxydicarbonates such as diisopropyl peroxydicarbonate and di-2-ethylhexyl peroxydicarbonate; and peroxyesters such as t-butyl peroxypivalate, t-butyl peroxyneodecanoate, and cumyl peroxyneodecanoate. Examples of the azo initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile). The oil-soluble initiator may be used alone or in combination of two or more. The amount of the oil-soluble initiator used may be 0.01 to 3 parts by mass per 100 parts by mass of the vinyl chloride monomer.
前記水溶性開始剤としては、例えば、無機過酸化物が挙げられる。前記無機過酸化物としては、具体的には過硫酸アンモニウム、過硫酸カリウム、過硫酸ナトリウム、および過酸化水素などが挙げられる。必要に応じて亜硫酸ナトリウム、チオ硫酸ナトリウム、ナトリウム・ホルムアルデヒド・スルホキシレート（ロンガリット）、アスコルビン酸、およびアスコルビン酸ナトリウムなどの還元剤を併用してもよい。前記水溶性開始剤は単独で用いてもよく、２種以上を組み合わせて用いてもよい。前記水溶性開始剤の使用量は、重合に用いたモノマー合計量１００質量部に対して０．０１～３質量部であってもよい。
Examples of the water-soluble initiator include inorganic peroxides. Specific examples of the inorganic peroxides include ammonium persulfate, potassium persulfate, sodium persulfate, and hydrogen peroxide. If necessary, reducing agents such as sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate (Rongalite), ascorbic acid, and sodium ascorbate may be used in combination. The water-soluble initiators may be used alone or in combination of two or more. The amount of the water-soluble initiator used may be 0.01 to 3 parts by mass per 100 parts by mass of the total amount of monomers used in the polymerization.
前記分散助剤としては、例えば、高級アルコール、および高級脂肪酸などが挙げられる。高級アルコールとしては、例えば、炭素数が６以上のアルコールを適宜用いることができ、具体的には、ヘキシルアルコール、ヘプチルアルコール、オクチルアルコール、ノニルアルコール、デシルアルコール、ウンデシルアルコール、ラウリルアルコール、トリデシルアルコール、ミリスチルアルコール、ペンタデシルアルコール、セチルアルコール、ヘプタデシルアルコール、ステアリルアルコール、ノナデシルアルコール、およびエイコシルアルコールなどが挙げられる。高級脂肪酸としては、炭素数が１２以上の脂肪酸を適宜用いることができ、具体的には、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸などが挙げられる。前記分散助剤は１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。分散助剤の使用量は、重合に用いたモノマー合計量１００質量部に対して０～５質量部であってもよく、０．３～２質量部であってもよい。
The dispersion aid may be, for example, a higher alcohol or a higher fatty acid. As the higher alcohol, an alcohol having 6 or more carbon atoms may be appropriately used, and specific examples thereof include hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, nonadecyl alcohol, and eicosyl alcohol. As the higher fatty acid, a fatty acid having 12 or more carbon atoms may be appropriately used, and specific examples thereof include lauric acid, myristic acid, palmitic acid, and stearic acid. The dispersion aid may be used alone or in combination of two or more. The amount of the dispersion aid used may be 0 to 5 parts by mass or 0.3 to 2 parts by mass per 100 parts by mass of the total amount of the monomers used in the polymerization.
重合に用いるモノマーは、水系媒体に一括で加えてもよく、２回以上の複数回に分けて加えてもよく、一定の速度で連続的に加えてもよく。例えば、重合開始前に塩化ビニルおよびビニルエステル系モノマーを一括で投入し、重合を開始した後に、水酸基含有モノマーを一括で投入してもよいが、反応速度が他のモノマーと比べて早いため、他のモノマーと共重合させる観点から、水酸基含有モノマーを一定の速度で連続的に供給することが望ましい。
The monomers used in the polymerization may be added to the aqueous medium all at once, may be added in two or more separate portions, or may be added continuously at a constant rate. For example, vinyl chloride and vinyl ester monomers may be added all at once before the start of polymerization, and the hydroxyl-containing monomer may be added all at once after the start of polymerization. However, since the reaction rate of the hydroxyl-containing monomer is faster than that of other monomers, it is desirable to continuously supply the hydroxyl-containing monomer at a constant rate from the viewpoint of copolymerizing it with other monomers.
前記乳化剤、前記重合開始剤、および必要により用いる前記分散助剤の重合反応器への供給方法は、特に限定されず、一括供給でもよく、２回以上の複数回に分けて供給してもよい。
The method of supplying the emulsifier, the polymerization initiator, and the dispersing aid used if necessary to the polymerization reactor is not particularly limited, and they may be supplied all at once or in two or more separate portions.
前記塩化ビニルの全量の５０質量％以上を重合反応器中に供給し、重合を開始してもよく、前記塩化ビニルの重合開始前の初期仕込み量は、例えば、６０質量％以上、７０質量％以上、８０質量％以上、９０質量%以上、又は全量でもよい。
50% by mass or more of the total amount of vinyl chloride may be fed into the polymerization reactor to initiate polymerization, and the initial amount of vinyl chloride charged before the start of polymerization may be, for example, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, or the total amount.
より具体的には、重合開始前に、水系媒体中に、塩化ビニル、ビニルエステル系モノマー、乳化剤、重合開始剤、および必要により分散助剤を加えて均一化した後、温度を例えば、３０～８０℃に調整して重合を開始し、重合を開始した後に、水酸基含有モノマーを一定の速度で連続的に投入してもよい。
More specifically, before the start of polymerization, vinyl chloride, vinyl ester monomer, emulsifier, polymerization initiator, and, if necessary, a dispersing aid are added to the aqueous medium and homogenized, and then the temperature is adjusted to, for example, 30 to 80°C to start polymerization, and after polymerization has started, the hydroxyl group-containing monomer can be added continuously at a constant rate.
得られた塩化ビニル系ペースト樹脂を含むペーストゾルの取扱性を高める観点から、水酸基含有モノマーの全量を、重合転化率（モノマー転化率とも称される。）が５％以上になった後、かつ５０％になるまでの間に、連続的に重合反応器に供給することが好ましい。これにより、塩化ビニル系ペースト樹脂を含むペーストゾルの３５℃における７日間放置後の粘度を低くなり、経時後の取扱性が向上する。本明細書において、重合転化率は、実施例に記載のとおりに測定算出することができる。
In order to improve the handleability of the obtained paste sol containing a vinyl chloride paste resin, it is preferable to continuously supply the total amount of the hydroxyl group-containing monomer to the polymerization reactor after the polymerization conversion rate (also called the monomer conversion rate) becomes 5% or more and before it reaches 50%. This reduces the viscosity of the paste sol containing a vinyl chloride paste resin after being left at 35°C for 7 days, improving the handleability over time. In this specification, the polymerization conversion rate can be measured and calculated as described in the Examples.
より具体的には、重合開始前に、水系媒体中に、塩化ビニル、ビニルエステル系モノマー、乳化剤、重合開始剤、および必要により分散助剤を加えて均一化した後、温度を例えば、３０～８０℃に調整して重合を開始し、重合転化率が５％以上になった後、かつ５０％になるまでの間に、水酸基含有モノマーを一定の速度で連続的に投入することが好ましい。
More specifically, before the start of polymerization, vinyl chloride, vinyl ester monomer, emulsifier, polymerization initiator, and, if necessary, dispersing aid are added to the aqueous medium and homogenized, and then the temperature is adjusted to, for example, 30 to 80°C to start polymerization, and once the polymerization conversion rate has reached 5% or more, but before it reaches 50%, it is preferable to continuously add the hydroxyl group-containing monomer at a constant rate.
前記塩化ビニル系ペースト樹脂の製造方法は、さらに上述した重合工程で得られた塩化ビニル系ペースト樹脂のラテックスを乾燥する乾燥工程を含んでもよい。前記塩化ビニル系ペースト樹脂のラテックスの乾燥は、特に限定されないが、噴霧乾燥であることが好ましい。単一のラテックスを噴霧乾燥してもよく、必要に応じて、２種以上のラテックスを混合した後に噴霧乾燥してもよい。乾燥効率を上げるために、塩化ビニル系ペースト樹脂のラテックスを濃縮した後に噴霧乾燥してもよい。乾燥前に、必要に応じて、湿式振動篩などにより、塩化ビニル系ペースト樹脂のラテックス中の粗粒を除去してもよい。乾燥後に、必要に応じて、塩化ビニル系ペースト樹脂中の粗粒除去を行ってもよく、塩化ビニル系ペースト樹脂を粉砕してもよい。
The method for producing the vinyl chloride paste resin may further include a drying step of drying the latex of the vinyl chloride paste resin obtained in the polymerization step described above. The drying of the latex of the vinyl chloride paste resin is not particularly limited, but is preferably spray drying. A single latex may be spray dried, or two or more types of latex may be mixed and then spray dried, as necessary. In order to increase the drying efficiency, the latex of the vinyl chloride paste resin may be concentrated and then spray dried. Before drying, coarse particles in the latex of the vinyl chloride paste resin may be removed using a wet vibrating sieve, as necessary. After drying, coarse particles in the vinyl chloride paste resin may be removed, or the vinyl chloride paste resin may be pulverized, as necessary.
（塩化ビニル系ペースト樹脂組成物）
本発明の１以上の実施形態において、塩化ビニル系ペースト樹脂組成物（以下において、単に「樹脂組成物」とも記す。）は、前記塩化ビニル系ペースト樹脂を含有する。前記樹脂組成物は、ペーストゾルであり得る。前記ペーストゾルは、プラスチゾルでもよく、オルガノゾルでもよい。また、前記樹脂組成物は、加熱ゲル化することにより成形され得る。 (Vinyl chloride-based paste resin composition)
In one or more embodiments of the present invention, a vinyl chloride-based paste resin composition (hereinafter, also simply referred to as a "resin composition") contains the vinyl chloride-based paste resin. The resin composition may be a paste sol. The paste sol may be a plastisol or an organosol. In addition, the resin composition may be molded by being gelled by heating.
本発明の１以上の実施形態において、塩化ビニル系ペースト樹脂組成物（以下において、単に「樹脂組成物」とも記す。）は、前記塩化ビニル系ペースト樹脂を含有する。前記樹脂組成物は、ペーストゾルであり得る。前記ペーストゾルは、プラスチゾルでもよく、オルガノゾルでもよい。また、前記樹脂組成物は、加熱ゲル化することにより成形され得る。 (Vinyl chloride-based paste resin composition)
In one or more embodiments of the present invention, a vinyl chloride-based paste resin composition (hereinafter, also simply referred to as a "resin composition") contains the vinyl chloride-based paste resin. The resin composition may be a paste sol. The paste sol may be a plastisol or an organosol. In addition, the resin composition may be molded by being gelled by heating.
前記樹脂組成物は、前記塩化ビニル系ペースト樹脂に加えて可塑剤を含んでもよい。前記可塑剤としては、特に限定されず、塩化ビニル系樹脂用可塑剤を適宜用いることができる。具体的には、ジ－２－エチルヘキシルフタレート（ＤＯＰ）、ジノルマルオクチルフタレート、ジブチルフタレート、ジイソノニルフタレート（ＤＩＮＰ）、およびブチルベンジルフタレートなどのフタル酸エステル系可塑剤；トリクレジルホスフェート、およびトリ－２－エチルヘキシルホスフェートなどのリン酸エステル系可塑剤；ジ－２－エチルヘキシルアジペートなどのアジピン酸エステル系可塑剤；ジ－２－エチルヘキシルセバケートなどのセバシン酸エステル系可塑剤；ジ－２－エチルヘキシルアゼレートなどのアゼライン酸エステル系可塑剤；トリ－２－エチルヘキシルトリメリテートなどのトリメリット酸エステル系可塑剤；ポリエステル系可塑剤；ジ－２－エチルヘキシルベンゾエート、ジエチレングリコールジベンゾエート、および２，２，４－トリメチル－１，３－ペンタンジオールイソブチレートベンゾエートなどの安息香酸エステル系可塑剤；アセチルトリブチルシトレートなどのクエン酸エステル系可塑剤；グリコール酸エステル系可塑剤；塩素化パラフィン系可塑剤；塩素化脂肪酸エステル系可塑剤；エポキシ系可塑剤；ならびにテキサノールイソブチレートなどが挙げられる。前記可塑剤は１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。中でも、フタル酸エステル系可塑剤が好ましく、ジ－２－エチルヘキシルフタレートおよびジイソノニルフタレートからなる群から選ばれる１種以上がより好ましい。前記塩化ビニル系ペースト樹脂１００質量部に対する可塑剤の使用量は３０～２００質量部であってもよく、４０～１５０質量部であってもよく、５０～１００質量部であってもよい。
The resin composition may contain a plasticizer in addition to the vinyl chloride paste resin. The plasticizer is not particularly limited, and any plasticizer for vinyl chloride resins may be used as appropriate. Specifically, phthalate ester plasticizers such as di-2-ethylhexyl phthalate (DOP), di-normal octyl phthalate, dibutyl phthalate, diisononyl phthalate (DINP), and butyl benzyl phthalate; phosphate ester plasticizers such as tricresyl phosphate and tri-2-ethylhexyl phosphate; adipate ester plasticizers such as di-2-ethylhexyl adipate; sebacate ester plasticizers such as di-2-ethylhexyl sebacate; and azelaate ester plasticizers such as di-2-ethylhexyl azelate. ; trimellitic acid ester-based plasticizers such as tri-2-ethylhexyl trimellitate; polyester-based plasticizers; benzoic acid ester-based plasticizers such as di-2-ethylhexyl benzoate, diethylene glycol dibenzoate, and 2,2,4-trimethyl-1,3-pentanediol isobutyrate benzoate; citrate ester-based plasticizers such as acetyl tributyl citrate; glycolic acid ester-based plasticizers; chlorinated paraffin-based plasticizers; chlorinated fatty acid ester-based plasticizers; epoxy-based plasticizers; and texanol isobutyrate. The plasticizers may be used alone or in combination of two or more. Among them, phthalic acid ester-based plasticizers are preferred, and one or more selected from the group consisting of di-2-ethylhexyl phthalate and diisononyl phthalate are more preferred. The amount of plasticizer used per 100 parts by mass of the vinyl chloride paste resin may be 30 to 200 parts by mass, 40 to 150 parts by mass, or 50 to 100 parts by mass.
前記樹脂組成物は、必要に応じて、安定剤、充填剤、密着性付与剤、希釈剤、減粘剤、充填剤、酸化防止剤、補強剤、紫外線吸収剤、発泡剤、難燃剤、帯電防止剤、滑剤、顔料、表面処理剤、チキソトロープ剤、防カビ剤、および洗浄剤などの他の添加剤を含んでもよい。
The resin composition may contain other additives, such as stabilizers, fillers, adhesion promoters, diluents, viscosity reducers, fillers, antioxidants, reinforcing agents, UV absorbers, foaming agents, flame retardants, antistatic agents, lubricants, pigments, surface treatment agents, thixotropic agents, antifungal agents, and detergents, as necessary.
前記安定剤としては、例えばジメチル錫メルカプト、ジブチル錫メルカプト、ジオクチル錫メルカプト、ジブチル錫マレート、ジオクチル錫マレート、およびジブチル錫ラウレートなどの有機錫安定剤；ステアリン酸鉛、二塩基性亜燐酸鉛、および三塩基性硫酸鉛などの鉛系安定剤；カルシウム－亜鉛系安定剤、およびバリウム－亜鉛系安定剤などの亜鉛系安定剤；エポキシ化大豆油、エポキシ化アマニ油、エポキシ化テトラヒドロフタレート、およびエポキシ化ポリブタジエンなどのエポキシ系安定剤；ならびに燐酸エステルなどが挙げられる。前記安定剤は１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。前記塩化ビニル系ペースト樹脂１００質量部に対する安定剤の使用量は０～２０質量部であってもよく、１～１０質量部であってもよい。
The stabilizer may be, for example, an organic tin stabilizer such as dimethyltin mercapto, dibutyltin mercapto, dioctyltin mercapto, dibutyltin maleate, dioctyltin maleate, or dibutyltin laurate; a lead-based stabilizer such as lead stearate, dibasic lead phosphite, or tribasic lead sulfate; a zinc-based stabilizer such as a calcium-zinc-based stabilizer or a barium-zinc-based stabilizer; an epoxy-based stabilizer such as epoxidized soybean oil, epoxidized linseed oil, epoxidized tetrahydrophthalate, or epoxidized polybutadiene; or a phosphoric acid ester. The stabilizer may be used alone or in combination of two or more. The amount of stabilizer used per 100 parts by mass of the vinyl chloride paste resin may be 0 to 20 parts by mass, or may be 1 to 10 parts by mass.
前記充填剤としては、特に制限はないが、例えば、炭酸カルシウム、炭酸マグネシウム、水酸化アルミニウム、水酸化マグネシウム、タルク、シリカ、クレー、珪酸カルシウムおよび酸化チタンなどが挙げられる。前記充填剤は１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。前記塩化ビニル系ペースト樹脂１００質量部に対する充填剤の使用量は０～１００質量部であってもよい。
The filler is not particularly limited, but examples thereof include calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, talc, silica, clay, calcium silicate, and titanium oxide. The filler may be used alone or in combination of two or more. The amount of filler used per 100 parts by mass of the polyvinyl chloride paste resin may be 0 to 100 parts by mass.
前記密着性付与剤としては、特に制限はないが、例えば、ポリアミド樹脂、ポリエチレンイミン樹脂、およびイソシアネート化合物などが挙げられる。前記イソシアネート化合物としては、例えば、トルイレンジイソシアネートのオリゴマー、およびウレタンプレポリマーの活性イソシアネート基をブロックしたブロック化イソシアネートなどが挙げられる。前記密着性付与剤としては、水酸基との反応性の観点から、イソシアネート化合物が好ましく、ブロック化イソシアネートがより好ましい。前記密着性付与剤は１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。前記塩化ビニル系ペースト樹脂１００質量部に対する密着性付与剤の使用量は０～２０質量部であってもよい。
The adhesion imparting agent is not particularly limited, and examples thereof include polyamide resins, polyethyleneimine resins, and isocyanate compounds. Examples of the isocyanate compounds include oligomers of toluylene diisocyanate and blocked isocyanates in which the active isocyanate groups of urethane prepolymers are blocked. From the viewpoint of reactivity with hydroxyl groups, the adhesion imparting agent is preferably an isocyanate compound, and more preferably a blocked isocyanate. The adhesion imparting agent may be used alone or in combination of two or more types. The amount of adhesion imparting agent used per 100 parts by mass of the vinyl chloride paste resin may be 0 to 20 parts by mass.
前記希釈剤としては、特に制限はないが、例えば２，２，４－トリメチル－１，３－ペンタンジオールジイソブチレート（ＴＸＩＢ）、ノルマルパラフィン、およびイソパラフィンなどが挙げられる。これらは単独で用いてもよく、２種以上を組み合わせて用いてもよい。前記塩化ビニル系ペースト樹脂１００質量部に対する希釈剤の使用量は０～２００質量部であってもよい。
The diluent is not particularly limited, but examples thereof include 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (TXIB), normal paraffin, and isoparaffin. These may be used alone or in combination of two or more. The amount of diluent used per 100 parts by mass of the vinyl chloride paste resin may be 0 to 200 parts by mass.
前記樹脂組成物は、塩化ビニル系ペースト樹脂、可塑剤、および必要に応じて他の添加剤を配合したものを、撹拌混合することで得ることができる。撹拌混合には、例えば、ディゾルバー型撹拌機などを用いることができる。
The resin composition can be obtained by stirring and mixing a mixture of a vinyl chloride paste resin, a plasticizer, and, if necessary, other additives. For stirring and mixing, a dissolver type stirrer, for example, can be used.
前記樹脂組成物は、低温加工時のせん断接着強度に優れる観点から、２枚の電着塗装鋼板の間に１ｍの厚さの樹脂組成物の層を形成し、１２０℃で３０分加熱して得られた試験片のせん断試験における最大接着強度が１．６５ＭＰａ以上であることが好ましく、１．９０ＭＰａ以上であることがより好ましく、２．１５ＭＰａ以上であることがさらに好ましく、２．３０ＭＰａ以上であることが特に好ましい。
From the viewpoint of excellent shear adhesive strength during low-temperature processing, the resin composition is preferably such that a layer of the resin composition having a thickness of 1 m is formed between two electrocoated steel plates and heated at 120°C for 30 minutes, and the maximum adhesive strength of the obtained test piece in a shear test is preferably 1.65 MPa or more, more preferably 1.90 MPa or more, even more preferably 2.15 MPa or more, and particularly preferably 2.30 MPa or more.
前記樹脂組成物は、低温加工時の引張強度に優れる観点から、１ｍの厚さの樹脂組成物の塗膜を１２０℃で３０分加熱して得られたシートから得られたＪＩＳ２号ダンベル状試験片の引張強度（破断強度）が２．６ＭＰａ以上であることが好ましく、２．８ＭＰａ以上であることがより好ましく、３．０ＭＰａ以上であることがさらに好ましい。
From the viewpoint of excellent tensile strength during low-temperature processing, the resin composition has a tensile strength (breaking strength) of 2.6 MPa or more, preferably 2.8 MPa or more, and even more preferably 3.0 MPa or more, of a JIS No. 2 dumbbell-shaped test piece obtained from a sheet obtained by heating a 1 m thick coating of the resin composition at 120°C for 30 minutes.
前記樹脂組成物は、低温加工時の伸びに優れる観点から、１ｍの厚さの樹脂組成物の塗膜を１２０℃で３０分加熱して得られたシートから得られたＪＩＳ２号ダンベル状試験片の伸び率が１８０％以上であることが好ましく、１８５％以上であることがより好ましく、１９０％以上であることがさらに好ましく、１９５％以上であることが特に好ましい。
From the viewpoint of excellent elongation during low-temperature processing, the resin composition is preferably such that the elongation of a JIS No. 2 dumbbell-shaped test piece obtained from a sheet obtained by heating a 1 m thick coating of the resin composition at 120°C for 30 minutes is 180% or more, more preferably 185% or more, even more preferably 190% or more, and particularly preferably 195% or more.
前記塩化ビニル系ペースト樹脂組成物は、自動車用塗料として用いることでき、特に自動車シーラント剤および／又は自動車アンダーボディコート剤として好適に用いることができる。前記塩化ビニル系ペースト樹脂組成物は、自動車用塗料以外に、例えば壁紙、床材クッションフロア、床材カーペットタイル、天井材、レザー、帆布、鋼板、自動車内装材、マーキングフィルム、テーブルクロス、玩具、人形、手袋、防水用被覆材、絶縁用被覆材、医療用品、キャップシール、および食品模型などにも用いることができる。
The vinyl chloride paste resin composition can be used as an automobile paint, and can be particularly suitably used as an automobile sealant and/or an automobile underbody coating. In addition to automobile paint, the vinyl chloride paste resin composition can also be used for, for example, wallpaper, cushion flooring, carpet tile flooring, ceiling materials, leather, canvas, steel plates, automobile interior materials, marking films, tablecloths, toys, dolls, gloves, waterproof coating materials, insulating coating materials, medical supplies, cap seals, and food models.
以下、実施例にて本発明の１以上の実施形態を説明するが、本発明は下記の実施例に限定されるものではない。
The following examples will explain one or more embodiments of the present invention, but the present invention is not limited to the following examples.
実施例および比較例で用いた測定方法および評価方法は下記のとおりである。
The measurement and evaluation methods used in the examples and comparative examples are as follows.
＜塩化ビニル系ペースト樹脂における各モノマー単位の含有量の測定方法＞
塩化ビニル系ペースト樹脂における各モノマー単位の含有量は、以下のように、核磁気共鳴スペクトル測定（ＮＭＲ）による測定と解析により求めた。
塩化ビニル系ペースト樹脂１０ｍｇを、ＮＭＲ用溶媒である重水素化ＴＨＦ（ＴＨＦ－ｄ８）０．７５ｍＬに室温で３時間溶解した。
核磁気共鳴装置（ＡＶＡＮＣＥ ＩＩＩ ＨＤ５００型デジタルＮＭＲ装置、ＢＲＵＫＥＲ社製）を用いて、磁場強度５００ＭＨｚの条件にて、得られた溶解液に関する1Ｈ測定を行った。塩化ビニルではケミカルシフト４．１～４．７ｐｐｍでのシグナル強度の積分値、酢酸ビニルでは５．１～５．６ｐｐｍでのシグナル強度の積分値、２－ヒドロキシエチルアクリレートでは１．１～１．３ｐｐｍでのシグナル強度の積分値を用い、これら積分値の比により、塩化ビニル系ペースト樹脂における塩化ビニル単位、酢酸ビニル単位および２－ヒドロキシエチルアクリレート単位の含有量を算出した。 <Method for measuring the content of each monomer unit in polyvinyl chloride paste resin>
The content of each monomer unit in the vinyl chloride paste resin was determined by measurement and analysis using nuclear magnetic resonance spectroscopy (NMR) as follows.
10 mg of vinyl chloride-based paste resin was dissolved in 0.75 mL of deuterated THF (THF-d8), a solvent for NMR, at room temperature for 3 hours.
The resulting solution was subjected to 1H measurement using a nuclear magnetic resonance apparatus (AVANCE III HD500 digital NMR apparatus, manufactured by BRUKER) at a magnetic field strength of 500 MHz. The integral value of the signal intensity at a chemical shift of 4.1 to 4.7 ppm for vinyl chloride, the integral value of the signal intensity at a chemical shift of 5.1 to 5.6 ppm for vinyl acetate, and the integral value of the signal intensity at a chemical shift of 1.1 to 1.3 ppm for 2-hydroxyethyl acrylate were used, and the contents of vinyl chloride units, vinyl acetate units, and 2-hydroxyethyl acrylate units in the vinyl chloride paste resin were calculated from the ratio of these integral values.
塩化ビニル系ペースト樹脂における各モノマー単位の含有量は、以下のように、核磁気共鳴スペクトル測定（ＮＭＲ）による測定と解析により求めた。
塩化ビニル系ペースト樹脂１０ｍｇを、ＮＭＲ用溶媒である重水素化ＴＨＦ（ＴＨＦ－ｄ８）０．７５ｍＬに室温で３時間溶解した。
核磁気共鳴装置（ＡＶＡＮＣＥ ＩＩＩ ＨＤ５００型デジタルＮＭＲ装置、ＢＲＵＫＥＲ社製）を用いて、磁場強度５００ＭＨｚの条件にて、得られた溶解液に関する1Ｈ測定を行った。塩化ビニルではケミカルシフト４．１～４．７ｐｐｍでのシグナル強度の積分値、酢酸ビニルでは５．１～５．６ｐｐｍでのシグナル強度の積分値、２－ヒドロキシエチルアクリレートでは１．１～１．３ｐｐｍでのシグナル強度の積分値を用い、これら積分値の比により、塩化ビニル系ペースト樹脂における塩化ビニル単位、酢酸ビニル単位および２－ヒドロキシエチルアクリレート単位の含有量を算出した。 <Method for measuring the content of each monomer unit in polyvinyl chloride paste resin>
The content of each monomer unit in the vinyl chloride paste resin was determined by measurement and analysis using nuclear magnetic resonance spectroscopy (NMR) as follows.
10 mg of vinyl chloride-based paste resin was dissolved in 0.75 mL of deuterated THF (THF-d8), a solvent for NMR, at room temperature for 3 hours.
The resulting solution was subjected to 1H measurement using a nuclear magnetic resonance apparatus (AVANCE III HD500 digital NMR apparatus, manufactured by BRUKER) at a magnetic field strength of 500 MHz. The integral value of the signal intensity at a chemical shift of 4.1 to 4.7 ppm for vinyl chloride, the integral value of the signal intensity at a chemical shift of 5.1 to 5.6 ppm for vinyl acetate, and the integral value of the signal intensity at a chemical shift of 1.1 to 1.3 ppm for 2-hydroxyethyl acrylate were used, and the contents of vinyl chloride units, vinyl acetate units, and 2-hydroxyethyl acrylate units in the vinyl chloride paste resin were calculated from the ratio of these integral values.
＜引張物性評価＞
ペーストゾル（プラスチゾル）を、ガラス板上に約１ｍｍの厚みに塗布し、オーブンにて１２０℃又は１４０℃で３０分間加熱することによりシートを作成した。得られたシートをＪＩＳ２号ダンベルに打ち抜き、試験片中央に２０ｍｍ間隔の標線をつけ、引張試験機（株式会社島津製作所製、ＡＧＳ－１０００Ａ）を用いて、２３℃且つ５０％（ＲＨ）条件下において、ＪＩＳ Ｋ－６２５１：２０１７に準じて、チェック間距離６０ｍｍ、速度２００ｍｍ／分の条件にて引張試験を実施し、破断時の強度および標線間の伸びを測定し、引張強度および伸び率を求めた。 <Tensile property evaluation>
A sheet was prepared by applying the paste sol (plastisol) to a thickness of about 1 mm on a glass plate and heating in an oven at 120° C. or 140° C. for 30 minutes. The obtained sheet was punched into a JIS No. 2 dumbbell, and marks were made at 20 mm intervals in the center of the test piece. A tensile test was carried out using a tensile tester (Shimadzu Corporation, AGS-1000A) at 23° C. and 50% (RH) in accordance with JIS K-6251:2017, with a check distance of 60 mm and a speed of 200 mm/min. The strength at break and the elongation between the marks were measured to determine the tensile strength and elongation percentage.
ペーストゾル（プラスチゾル）を、ガラス板上に約１ｍｍの厚みに塗布し、オーブンにて１２０℃又は１４０℃で３０分間加熱することによりシートを作成した。得られたシートをＪＩＳ２号ダンベルに打ち抜き、試験片中央に２０ｍｍ間隔の標線をつけ、引張試験機（株式会社島津製作所製、ＡＧＳ－１０００Ａ）を用いて、２３℃且つ５０％（ＲＨ）条件下において、ＪＩＳ Ｋ－６２５１：２０１７に準じて、チェック間距離６０ｍｍ、速度２００ｍｍ／分の条件にて引張試験を実施し、破断時の強度および標線間の伸びを測定し、引張強度および伸び率を求めた。 <Tensile property evaluation>
A sheet was prepared by applying the paste sol (plastisol) to a thickness of about 1 mm on a glass plate and heating in an oven at 120° C. or 140° C. for 30 minutes. The obtained sheet was punched into a JIS No. 2 dumbbell, and marks were made at 20 mm intervals in the center of the test piece. A tensile test was carried out using a tensile tester (Shimadzu Corporation, AGS-1000A) at 23° C. and 50% (RH) in accordance with JIS K-6251:2017, with a check distance of 60 mm and a speed of 200 mm/min. The strength at break and the elongation between the marks were measured to determine the tensile strength and elongation percentage.
＜せん断試験評価＞
電着塗装板（三木コーティング株式会社製、長辺７５ｍｍ×短辺２５ｍｍ×厚み０．８ｍｍ）の表面に、変性アルコール（三協化学株式会社製、エタコール７）を塗布した。その後、当該変性アルコールを布でふき取ることによって、脱脂処理を行った。
脱脂後の電着塗装鋼板の長辺側端部に、厚さ１ｍｍ×幅３ｍｍのテフロン（登録商標）製スペーサーを設置し、スペーサー間の距離が２５ｍｍになるように、もう一つの厚さ１ｍｍ×幅３ｍｍのテフロン（登録商標）製スペーサーを設置した。両スペーサー間にプラスチゾルを塗布後、別の脱脂後の電着塗装鋼板を長辺側端部がスペーサーに掛かるよう乗せてプラスチゾルを挟み込み、はみ出たプラスチゾルの余剰分を除去することにより、２枚の電着塗装鋼板の間に２５ｍｍ×２５ｍｍ×厚み１ｍｍのプラスチゾル層を形成した。
プラスチゾル層を挟み込んだ２枚の電着塗装鋼板を上下から挟んで固定した後に、オーブンを用いて、１２０℃又は１４０℃で３０分間加熱して、せん断試験用試験片を作成した。せん断試験は、引張試験機（島津製作所製、ＡＧ－Ｘ）を用いて、２３℃かつ５０％（ＲＨ）条件下において、ＪＩＳ Ｋ―６２５１：２０１７に準じて、チェック間距離７０ｍｍ、速度５０ｍｍ／分の速度で実施し、破断時の強度を測定し、最大接着強度とした。 <Shear test evaluation>
Denatured alcohol (Ethacol 7, manufactured by Sankyo Chemical Industry Co., Ltd.) was applied to the surface of an electrodeposition-coated plate (manufactured by Miki Coating Co., Ltd., long side 75 mm × short side 25 mm × thickness 0.8 mm). The denatured alcohol was then wiped off with a cloth to perform a degreasing treatment.
A Teflon (registered trademark) spacer having a thickness of 1 mm and a width of 3 mm was placed on the long side edge of the degreased electrodeposition-coated steel sheet, and another Teflon (registered trademark) spacer having a thickness of 1 mm and a width of 3 mm was placed so that the distance between the spacers was 25 mm. After applying plastisol between the two spacers, another degreased electrodeposition-coated steel sheet was placed on the spacer so that the long side edge was overlapped by the spacer, sandwiching the plastisol, and the excess plastisol that protruded was removed, thereby forming a plastisol layer having a size of 25 mm x 25 mm x 1 mm between the two electrodeposition-coated steel sheets.
Two electrocoated steel sheets sandwiching the plastisol layer were clamped from above and below, and then heated in an oven at 120°C or 140°C for 30 minutes to prepare a test piece for a shear test. The shear test was performed using a tensile tester (Shimadzu Corporation, AG-X) at 23°C and 50% (RH) in accordance with JIS K-6251:2017, with a check distance of 70 mm and a speed of 50 mm/min. The strength at break was measured and taken as the maximum adhesive strength.
電着塗装板（三木コーティング株式会社製、長辺７５ｍｍ×短辺２５ｍｍ×厚み０．８ｍｍ）の表面に、変性アルコール（三協化学株式会社製、エタコール７）を塗布した。その後、当該変性アルコールを布でふき取ることによって、脱脂処理を行った。
脱脂後の電着塗装鋼板の長辺側端部に、厚さ１ｍｍ×幅３ｍｍのテフロン（登録商標）製スペーサーを設置し、スペーサー間の距離が２５ｍｍになるように、もう一つの厚さ１ｍｍ×幅３ｍｍのテフロン（登録商標）製スペーサーを設置した。両スペーサー間にプラスチゾルを塗布後、別の脱脂後の電着塗装鋼板を長辺側端部がスペーサーに掛かるよう乗せてプラスチゾルを挟み込み、はみ出たプラスチゾルの余剰分を除去することにより、２枚の電着塗装鋼板の間に２５ｍｍ×２５ｍｍ×厚み１ｍｍのプラスチゾル層を形成した。
プラスチゾル層を挟み込んだ２枚の電着塗装鋼板を上下から挟んで固定した後に、オーブンを用いて、１２０℃又は１４０℃で３０分間加熱して、せん断試験用試験片を作成した。せん断試験は、引張試験機（島津製作所製、ＡＧ－Ｘ）を用いて、２３℃かつ５０％（ＲＨ）条件下において、ＪＩＳ Ｋ―６２５１：２０１７に準じて、チェック間距離７０ｍｍ、速度５０ｍｍ／分の速度で実施し、破断時の強度を測定し、最大接着強度とした。 <Shear test evaluation>
Denatured alcohol (Ethacol 7, manufactured by Sankyo Chemical Industry Co., Ltd.) was applied to the surface of an electrodeposition-coated plate (manufactured by Miki Coating Co., Ltd., long side 75 mm × short side 25 mm × thickness 0.8 mm). The denatured alcohol was then wiped off with a cloth to perform a degreasing treatment.
A Teflon (registered trademark) spacer having a thickness of 1 mm and a width of 3 mm was placed on the long side edge of the degreased electrodeposition-coated steel sheet, and another Teflon (registered trademark) spacer having a thickness of 1 mm and a width of 3 mm was placed so that the distance between the spacers was 25 mm. After applying plastisol between the two spacers, another degreased electrodeposition-coated steel sheet was placed on the spacer so that the long side edge was overlapped by the spacer, sandwiching the plastisol, and the excess plastisol that protruded was removed, thereby forming a plastisol layer having a size of 25 mm x 25 mm x 1 mm between the two electrodeposition-coated steel sheets.
Two electrocoated steel sheets sandwiching the plastisol layer were clamped from above and below, and then heated in an oven at 120°C or 140°C for 30 minutes to prepare a test piece for a shear test. The shear test was performed using a tensile tester (Shimadzu Corporation, AG-X) at 23°C and 50% (RH) in accordance with JIS K-6251:2017, with a check distance of 70 mm and a speed of 50 mm/min. The strength at break was measured and taken as the maximum adhesive strength.
＜塩化ビニル系ペースト樹脂の平均重合度＞
ＪＩＳ Ｋ ６７２０－２：１９９９に従って、平均重合度を求めた。 <Average Degree of Polymerization of Vinyl Chloride-Based Paste Resin>
The average degree of polymerization was determined according to JIS K 6720-2:1999.
ＪＩＳ Ｋ ６７２０－２：１９９９に従って、平均重合度を求めた。 <Average Degree of Polymerization of Vinyl Chloride-Based Paste Resin>
The average degree of polymerization was determined according to JIS K 6720-2:1999.
（ペーストゾルの粘度測定方法）
得られたペーストゾルを速やかに５０ｃｃガラス管瓶に入れて栓をし、３５℃恒温水槽で保管した。２時間後および１週間後にペーストゾを取出し、スパチュラで５０回攪拌を行った後に、ＶＩＳＣＯＭＥＴＥＲ ＴＶ１０（ＴＯＫＩ ＳＡＮＧＹＯ ＣＯ． ＬＴＤ）を用い、ＳＰＩＮＤＬＥ Ｎｏ．Ｈ７、ＳＰＥＥＤ ２０ ｒｐｍの条件で測定を開始し、１分後の値を読み取り、粘度とした。 (Method of measuring viscosity of paste sol)
The obtained paste sol was quickly placed in a 50 cc glass tube, which was then stoppered and stored in a thermostatic water bath at 35° C. After 2 hours and 1 week, the paste sol was taken out and stirred 50 times with a spatula, and then measurement was started using a VISCOMETER TV10 (TOKI SANGYO CO. LTD) under conditions of SPINDLE No. H7 and SPEED 20 rpm. The value after 1 minute was read and recorded as the viscosity.
得られたペーストゾルを速やかに５０ｃｃガラス管瓶に入れて栓をし、３５℃恒温水槽で保管した。２時間後および１週間後にペーストゾを取出し、スパチュラで５０回攪拌を行った後に、ＶＩＳＣＯＭＥＴＥＲ ＴＶ１０（ＴＯＫＩ ＳＡＮＧＹＯ ＣＯ． ＬＴＤ）を用い、ＳＰＩＮＤＬＥ Ｎｏ．Ｈ７、ＳＰＥＥＤ ２０ ｒｐｍの条件で測定を開始し、１分後の値を読み取り、粘度とした。 (Method of measuring viscosity of paste sol)
The obtained paste sol was quickly placed in a 50 cc glass tube, which was then stoppered and stored in a thermostatic water bath at 35° C. After 2 hours and 1 week, the paste sol was taken out and stirred 50 times with a spatula, and then measurement was started using a VISCOMETER TV10 (TOKI SANGYO CO. LTD) under conditions of SPINDLE No. H7 and SPEED 20 rpm. The value after 1 minute was read and recorded as the viscosity.
（重合転化率の算出方法）
重合転化率は、以下のように算出した。
まず、重合反応器内の重合途中のラテックスを採取し、該ラテックスを２ｇ（Ｗ０）アルミ皿に採り、１２０℃のオーブンで３０分間乾燥して、乾燥後の固形分の質量（Ｗ１）を測定した。次に、下記式Ｉにより固形分濃度を算出した。
［式Ｉ］
固形分濃度［％］＝１００×Ｗ１［ｇ］／Ｗ０［ｇ］
次に、上記固形分濃度から、下記式（ＩＩ）により重合中に消費されたモノマー量を算出し、これを重合転化率とした。なお、下記式（ＩＩ）において、塩化ビニルの量は該当重合反応に使用する塩化ビニルの総量とし、他のモノマーの量は、該当重合反応に使用する塩化ビニル以外の他のモノマーの総量とする。
［式ＩＩ］
重合転化率［％］＝１００×｛固形分濃度［％］／（１００－固形分濃度［％］）｝×｛水の量［質量部］／（塩化ビニルの量［質量部］＋他のモノマーの量［質量部］）｝ (Method of calculating polymerization conversion rate)
The polymerization conversion rate was calculated as follows.
First, the latex during polymerization in the polymerization reactor was sampled, 2 g (W0) of the latex was placed in an aluminum dish, and dried in an oven at 120° C. for 30 minutes to measure the mass (W1) of the solid content after drying. Next, the solid content concentration was calculated by the following formula I.
Formula I
Solid content concentration [%] = 100 x W1 [g] / W0 [g]
Next, the amount of monomer consumed during polymerization was calculated from the solid content concentration according to the following formula (II), and this was taken as the polymerization conversion rate. In the following formula (II), the amount of vinyl chloride is the total amount of vinyl chloride used in the polymerization reaction, and the amount of other monomers is the total amount of monomers other than vinyl chloride used in the polymerization reaction.
Formula II
Polymerization conversion rate [%] = 100 × {solid concentration [%] / (100 - solid concentration [%])} × {amount of water [parts by mass] / (amount of vinyl chloride [parts by mass] + amount of other monomers [parts by mass])}
重合転化率は、以下のように算出した。
まず、重合反応器内の重合途中のラテックスを採取し、該ラテックスを２ｇ（Ｗ０）アルミ皿に採り、１２０℃のオーブンで３０分間乾燥して、乾燥後の固形分の質量（Ｗ１）を測定した。次に、下記式Ｉにより固形分濃度を算出した。
［式Ｉ］
固形分濃度［％］＝１００×Ｗ１［ｇ］／Ｗ０［ｇ］
次に、上記固形分濃度から、下記式（ＩＩ）により重合中に消費されたモノマー量を算出し、これを重合転化率とした。なお、下記式（ＩＩ）において、塩化ビニルの量は該当重合反応に使用する塩化ビニルの総量とし、他のモノマーの量は、該当重合反応に使用する塩化ビニル以外の他のモノマーの総量とする。
［式ＩＩ］
重合転化率［％］＝１００×｛固形分濃度［％］／（１００－固形分濃度［％］）｝×｛水の量［質量部］／（塩化ビニルの量［質量部］＋他のモノマーの量［質量部］）｝ (Method of calculating polymerization conversion rate)
The polymerization conversion rate was calculated as follows.
First, the latex during polymerization in the polymerization reactor was sampled, 2 g (W0) of the latex was placed in an aluminum dish, and dried in an oven at 120° C. for 30 minutes to measure the mass (W1) of the solid content after drying. Next, the solid content concentration was calculated by the following formula I.
Formula I
Solid content concentration [%] = 100 x W1 [g] / W0 [g]
Next, the amount of monomer consumed during polymerization was calculated from the solid content concentration according to the following formula (II), and this was taken as the polymerization conversion rate. In the following formula (II), the amount of vinyl chloride is the total amount of vinyl chloride used in the polymerization reaction, and the amount of other monomers is the total amount of monomers other than vinyl chloride used in the polymerization reaction.
Formula II
Polymerization conversion rate [%] = 100 × {solid concentration [%] / (100 - solid concentration [%])} × {amount of water [parts by mass] / (amount of vinyl chloride [parts by mass] + amount of other monomers [parts by mass])}
（実施例１）
＜塩化ビニル系ペースト樹脂の作製＞
重合反応器（ステンレス製攪拌装置付耐圧容器）に、イオン交換水８０質量部、ドデシルベンゼンスルホン酸ナトリウム０．８０質量部、セチルアルコール０．４０質量部、ステアリルアルコール０．３質量部、クミルペルオキシネオデカノエート０．１質量部、ｔ－ブチルペルオキシネオデカノエート０．０５質量部、酢酸ビニルモノマー８．５質量部、および塩化ビニル８９．７質量部を仕込み、均一化した。
その後、耐圧容器内の温度を３７．５℃に昇温させて、重合を開始した。重合開始１時間後から７時間後までにかけて２－ヒドロキシプロピルアクリレート（以降、「ＨＰＡ」と略す場合がある。）１．８質量部を一定速度で連続追加した。重合圧力が降下した時点で、未反応のモノマーを除去して重合を終了させた。重合開始から重合終了までの重合期間は１０．５時間であった。
粗粒を除去したラテックスを、スプレー乾燥機（大河原化工機株式会社製）を用い、入口温度１０５℃、出口温度５０℃の条件で噴霧乾燥することにより、塩化ビニル系ペースト樹脂を得た。
＜ペーストゾルの作製＞
５００ｍＬのＳＵＳカップに、乾燥後の塩化ビニル系ペースト樹脂１００質量部、ジイソノニルフタレート（ＤＩＮＰ）７４質量部、炭酸カルシウム（神島化学工業株式会社製、ＰＬ－１０）５２質量部、炭酸カルシウム（Ｖｉｓｃｏｌｉｔｅ－ＯＳ、白石工業株式会社製）２６質量部、ブロックドイソシアネート（株式会社ＡＤＥＫＡ製、ＱＲ－９４０１－１)５質量部、およびポリアミド樹脂（Ｅｖｏｎｉｋ社製、ＮＯＵＲＹＢＯＮＤ２７６）２質量部を加えて、均一になるまで混合した。得られた混合物を、ディゾルバー型混練機（プライミクス社製「ＲＯＢＯ ＭＩＣＳ」、ディゾルバー翼の直径５ｃｍ）を用い、室温下、１０００ｒｐｍで２分間混練した。混練後、さらにＤＩＮＰ３７質量部を加えて均一になるまで混合した。得られた混合物を、上述したディゾルバー型混練機を用いて、室温下、１０００ｒｐｍで１分間混練した。得られた混合物を石川式擂潰機（株式会社石川工業製）に移し、脱泡処理を行うことにより、ペーストゾルを得た。 Example 1
<Preparation of vinyl chloride paste resin>
A polymerization reactor (a stainless steel pressure-resistant vessel equipped with a stirrer) was charged with 80 parts by mass of ion-exchanged water, 0.80 parts by mass of sodium dodecylbenzenesulfonate, 0.40 parts by mass of cetyl alcohol, 0.3 parts by mass of stearyl alcohol, 0.1 parts by mass of cumyl peroxy neodecanoate, 0.05 parts by mass of t-butyl peroxy neodecanoate, 8.5 parts by mass of vinyl acetate monomer, and 89.7 parts by mass of vinyl chloride, and the mixture was homogenized.
Thereafter, the temperature inside the pressure vessel was raised to 37.5°C to initiate polymerization. From 1 hour to 7 hours after the start of polymerization, 1.8 parts by mass of 2-hydroxypropyl acrylate (hereinafter sometimes abbreviated as "HPA") was continuously added at a constant rate. When the polymerization pressure dropped, the unreacted monomer was removed to terminate the polymerization. The polymerization period from the start to the end of polymerization was 10.5 hours.
The latex from which the coarse particles had been removed was spray-dried using a spray dryer (manufactured by Okawara Kakoki Co., Ltd.) under conditions of an inlet temperature of 105° C. and an outlet temperature of 50° C., thereby obtaining a vinyl chloride paste resin.
<Preparation of paste sol>
In a 500 mL SUS cup, 100 parts by mass of the dried vinyl chloride paste resin, 74 parts by mass of diisononyl phthalate (DINP), 52 parts by mass of calcium carbonate (PL-10, manufactured by Konoshima Chemical Co., Ltd.), 26 parts by mass of calcium carbonate (Viscolite-OS, manufactured by Shiraishi Kogyo Co., Ltd.), 5 parts by mass of blocked isocyanate (QR-9401-1, manufactured by ADEKA Corporation), and 2 parts by mass of polyamide resin (NOURYBOND276, manufactured by Evonik Corporation) were added and mixed until uniform. The resulting mixture was kneaded at room temperature at 1000 rpm for 2 minutes using a dissolver type kneader (ROBO MICS, manufactured by Primix Corporation, dissolver blade diameter 5 cm). After kneading, 37 parts by mass of DINP were further added and mixed until uniform. The mixture was kneaded at room temperature for 1 minute at 1000 rpm using the dissolver type kneader described above. The mixture was transferred to an Ishikawa type crusher (manufactured by Ishikawa Kogyo Co., Ltd.) and subjected to a defoaming treatment to obtain a paste sol.
＜塩化ビニル系ペースト樹脂の作製＞
重合反応器（ステンレス製攪拌装置付耐圧容器）に、イオン交換水８０質量部、ドデシルベンゼンスルホン酸ナトリウム０．８０質量部、セチルアルコール０．４０質量部、ステアリルアルコール０．３質量部、クミルペルオキシネオデカノエート０．１質量部、ｔ－ブチルペルオキシネオデカノエート０．０５質量部、酢酸ビニルモノマー８．５質量部、および塩化ビニル８９．７質量部を仕込み、均一化した。
その後、耐圧容器内の温度を３７．５℃に昇温させて、重合を開始した。重合開始１時間後から７時間後までにかけて２－ヒドロキシプロピルアクリレート（以降、「ＨＰＡ」と略す場合がある。）１．８質量部を一定速度で連続追加した。重合圧力が降下した時点で、未反応のモノマーを除去して重合を終了させた。重合開始から重合終了までの重合期間は１０．５時間であった。
粗粒を除去したラテックスを、スプレー乾燥機（大河原化工機株式会社製）を用い、入口温度１０５℃、出口温度５０℃の条件で噴霧乾燥することにより、塩化ビニル系ペースト樹脂を得た。
＜ペーストゾルの作製＞
５００ｍＬのＳＵＳカップに、乾燥後の塩化ビニル系ペースト樹脂１００質量部、ジイソノニルフタレート（ＤＩＮＰ）７４質量部、炭酸カルシウム（神島化学工業株式会社製、ＰＬ－１０）５２質量部、炭酸カルシウム（Ｖｉｓｃｏｌｉｔｅ－ＯＳ、白石工業株式会社製）２６質量部、ブロックドイソシアネート（株式会社ＡＤＥＫＡ製、ＱＲ－９４０１－１)５質量部、およびポリアミド樹脂（Ｅｖｏｎｉｋ社製、ＮＯＵＲＹＢＯＮＤ２７６）２質量部を加えて、均一になるまで混合した。得られた混合物を、ディゾルバー型混練機（プライミクス社製「ＲＯＢＯ ＭＩＣＳ」、ディゾルバー翼の直径５ｃｍ）を用い、室温下、１０００ｒｐｍで２分間混練した。混練後、さらにＤＩＮＰ３７質量部を加えて均一になるまで混合した。得られた混合物を、上述したディゾルバー型混練機を用いて、室温下、１０００ｒｐｍで１分間混練した。得られた混合物を石川式擂潰機（株式会社石川工業製）に移し、脱泡処理を行うことにより、ペーストゾルを得た。 Example 1
<Preparation of vinyl chloride paste resin>
A polymerization reactor (a stainless steel pressure-resistant vessel equipped with a stirrer) was charged with 80 parts by mass of ion-exchanged water, 0.80 parts by mass of sodium dodecylbenzenesulfonate, 0.40 parts by mass of cetyl alcohol, 0.3 parts by mass of stearyl alcohol, 0.1 parts by mass of cumyl peroxy neodecanoate, 0.05 parts by mass of t-butyl peroxy neodecanoate, 8.5 parts by mass of vinyl acetate monomer, and 89.7 parts by mass of vinyl chloride, and the mixture was homogenized.
Thereafter, the temperature inside the pressure vessel was raised to 37.5°C to initiate polymerization. From 1 hour to 7 hours after the start of polymerization, 1.8 parts by mass of 2-hydroxypropyl acrylate (hereinafter sometimes abbreviated as "HPA") was continuously added at a constant rate. When the polymerization pressure dropped, the unreacted monomer was removed to terminate the polymerization. The polymerization period from the start to the end of polymerization was 10.5 hours.
The latex from which the coarse particles had been removed was spray-dried using a spray dryer (manufactured by Okawara Kakoki Co., Ltd.) under conditions of an inlet temperature of 105° C. and an outlet temperature of 50° C., thereby obtaining a vinyl chloride paste resin.
<Preparation of paste sol>
In a 500 mL SUS cup, 100 parts by mass of the dried vinyl chloride paste resin, 74 parts by mass of diisononyl phthalate (DINP), 52 parts by mass of calcium carbonate (PL-10, manufactured by Konoshima Chemical Co., Ltd.), 26 parts by mass of calcium carbonate (Viscolite-OS, manufactured by Shiraishi Kogyo Co., Ltd.), 5 parts by mass of blocked isocyanate (QR-9401-1, manufactured by ADEKA Corporation), and 2 parts by mass of polyamide resin (NOURYBOND276, manufactured by Evonik Corporation) were added and mixed until uniform. The resulting mixture was kneaded at room temperature at 1000 rpm for 2 minutes using a dissolver type kneader (ROBO MICS, manufactured by Primix Corporation, dissolver blade diameter 5 cm). After kneading, 37 parts by mass of DINP were further added and mixed until uniform. The mixture was kneaded at room temperature for 1 minute at 1000 rpm using the dissolver type kneader described above. The mixture was transferred to an Ishikawa type crusher (manufactured by Ishikawa Kogyo Co., Ltd.) and subjected to a defoaming treatment to obtain a paste sol.
（実施例２～５）
酢酸ビニルモノマー、塩化ビニルおよび２－ヒドロキシプロピルアクリレートの仕込み量を下記表１に記載のとおりに変更し、重合温度を下記表１に記載の温度に変更した以外は、実施例１と同様の操作により、塩化ビニル系ペースト樹脂およびペーストゾルを得た。 (Examples 2 to 5)
A vinyl chloride-based paste resin and a paste sol were obtained by the same operation as in Example 1, except that the amounts of vinyl acetate monomer, vinyl chloride and 2-hydroxypropyl acrylate were changed as shown in Table 1 below, and the polymerization temperature was changed to the temperature shown in Table 1 below.
酢酸ビニルモノマー、塩化ビニルおよび２－ヒドロキシプロピルアクリレートの仕込み量を下記表１に記載のとおりに変更し、重合温度を下記表１に記載の温度に変更した以外は、実施例１と同様の操作により、塩化ビニル系ペースト樹脂およびペーストゾルを得た。 (Examples 2 to 5)
A vinyl chloride-based paste resin and a paste sol were obtained by the same operation as in Example 1, except that the amounts of vinyl acetate monomer, vinyl chloride and 2-hydroxypropyl acrylate were changed as shown in Table 1 below, and the polymerization temperature was changed to the temperature shown in Table 1 below.
（実施例６）
２－ヒドロキシプロピルアクリレートの連続追加期間を下記表１に示すとおりに変更した以外は、実施例１と同様の操作により、塩化ビニル系ペースト樹脂を得た。 Example 6
A vinyl chloride paste resin was obtained in the same manner as in Example 1, except that the period of continuous addition of 2-hydroxypropyl acrylate was changed as shown in Table 1 below.
２－ヒドロキシプロピルアクリレートの連続追加期間を下記表１に示すとおりに変更した以外は、実施例１と同様の操作により、塩化ビニル系ペースト樹脂を得た。 Example 6
A vinyl chloride paste resin was obtained in the same manner as in Example 1, except that the period of continuous addition of 2-hydroxypropyl acrylate was changed as shown in Table 1 below.
（実施例７）
２－ヒドロキシプロピルアクリレートの連続追加期間を下記表１に示すとおりに変更した以外は、実施例２と同様の操作により、塩化ビニル系ペースト樹脂を得た。 (Example 7)
A vinyl chloride paste resin was obtained in the same manner as in Example 2, except that the period of continuous addition of 2-hydroxypropyl acrylate was changed as shown in Table 1 below.
２－ヒドロキシプロピルアクリレートの連続追加期間を下記表１に示すとおりに変更した以外は、実施例２と同様の操作により、塩化ビニル系ペースト樹脂を得た。 (Example 7)
A vinyl chloride paste resin was obtained in the same manner as in Example 2, except that the period of continuous addition of 2-hydroxypropyl acrylate was changed as shown in Table 1 below.
（比較例１）
酢酸ビニルモノマーの仕込み量を１０．４質量部、塩化ビニルの仕込み量を８９．６質量部、重合温度を３７℃に変更し、さらに、２－ヒドロキシプロピルアクリレートを追加しない以外は、実施例１と同様の操作により、塩化ビニル系ペースト樹脂およびペーストゾルを得た。 (Comparative Example 1)
A vinyl chloride-based paste resin and a paste sol were obtained by the same operation as in Example 1, except that the amount of vinyl acetate monomer charged was changed to 10.4 parts by mass, the amount of vinyl chloride charged was changed to 89.6 parts by mass, the polymerization temperature was changed to 37°C, and further, 2-hydroxypropyl acrylate was not added.
酢酸ビニルモノマーの仕込み量を１０．４質量部、塩化ビニルの仕込み量を８９．６質量部、重合温度を３７℃に変更し、さらに、２－ヒドロキシプロピルアクリレートを追加しない以外は、実施例１と同様の操作により、塩化ビニル系ペースト樹脂およびペーストゾルを得た。 (Comparative Example 1)
A vinyl chloride-based paste resin and a paste sol were obtained by the same operation as in Example 1, except that the amount of vinyl acetate monomer charged was changed to 10.4 parts by mass, the amount of vinyl chloride charged was changed to 89.6 parts by mass, the polymerization temperature was changed to 37°C, and further, 2-hydroxypropyl acrylate was not added.
（比較例２）
酢酸ビニルモノマーの仕込み量を１１．６質量部、塩化ビニルの仕込み量を８８．４質量部、重合温度を３６℃に変更した以外は、比較例１と同様の操作により、塩化ビニル系ペースト樹脂およびペーストゾルを得た。 (Comparative Example 2)
A vinyl chloride-based paste resin and a paste sol were obtained in the same manner as in Comparative Example 1, except that the amount of vinyl acetate monomer charged was changed to 11.6 parts by mass, the amount of vinyl chloride charged was changed to 88.4 parts by mass, and the polymerization temperature was changed to 36°C.
酢酸ビニルモノマーの仕込み量を１１．６質量部、塩化ビニルの仕込み量を８８．４質量部、重合温度を３６℃に変更した以外は、比較例１と同様の操作により、塩化ビニル系ペースト樹脂およびペーストゾルを得た。 (Comparative Example 2)
A vinyl chloride-based paste resin and a paste sol were obtained in the same manner as in Comparative Example 1, except that the amount of vinyl acetate monomer charged was changed to 11.6 parts by mass, the amount of vinyl chloride charged was changed to 88.4 parts by mass, and the polymerization temperature was changed to 36°C.
（比較例３～５）
酢酸ビニルモノマーの仕込み量、塩化ビニルの仕込み量および２－ヒドロキシプロピルアクリレートの仕込み量を下記表１に記載の量に変更し、重合温度を下記表１に記載の温度に変更した以外は、実施例１と同様の操作により、塩化ビニル系ペースト樹脂およびペーストゾルを得た。 (Comparative Examples 3 to 5)
A vinyl chloride-based paste resin and a paste sol were obtained by the same operation as in Example 1, except that the amounts of vinyl acetate monomer, vinyl chloride, and 2-hydroxypropyl acrylate were changed to those shown in Table 1 below, and the polymerization temperature was changed to those shown in Table 1 below.
酢酸ビニルモノマーの仕込み量、塩化ビニルの仕込み量および２－ヒドロキシプロピルアクリレートの仕込み量を下記表１に記載の量に変更し、重合温度を下記表１に記載の温度に変更した以外は、実施例１と同様の操作により、塩化ビニル系ペースト樹脂およびペーストゾルを得た。 (Comparative Examples 3 to 5)
A vinyl chloride-based paste resin and a paste sol were obtained by the same operation as in Example 1, except that the amounts of vinyl acetate monomer, vinyl chloride, and 2-hydroxypropyl acrylate were changed to those shown in Table 1 below, and the polymerization temperature was changed to those shown in Table 1 below.
（比較例６）
酢酸ビニルモノマーの仕込み量を０質量部、塩化ビニルの仕込み量を９５．０質量部、クミルペルオキシネオデカノエートの仕込み量を０．０５質量部、ｔ－ブチルペルオキシネオデカノエートの仕込み量を０．０２５質量部、重合温度を４２℃に変更し、さらに、２－ヒドロキシプロピルアクリレートの仕込み量を５質量部に、および連続追加期間を重合開始1時間後から６時間後までに変更した以外は、実施例１と同様の操作により、塩化ビニル系ペースト樹脂およびペーストゾルを得た。 (Comparative Example 6)
A vinyl chloride paste resin and a paste sol were obtained by the same operations as in Example 1, except that the charged amounts of vinyl acetate monomer, vinyl chloride, cumyl peroxy neodecanoate, cumyl peroxy neodecanoate, t-butyl peroxy neodecanoate, and t-butyl peroxy neodecanoate were changed to 0.05 parts by mass, 0.025 parts by mass, the polymerization temperature was changed to 42°C, and further the charged amount of 2-hydroxypropyl acrylate was changed to 5 parts by mass, and the continuous addition period was changed to from 1 hour to 6 hours after the start of polymerization.
酢酸ビニルモノマーの仕込み量を０質量部、塩化ビニルの仕込み量を９５．０質量部、クミルペルオキシネオデカノエートの仕込み量を０．０５質量部、ｔ－ブチルペルオキシネオデカノエートの仕込み量を０．０２５質量部、重合温度を４２℃に変更し、さらに、２－ヒドロキシプロピルアクリレートの仕込み量を５質量部に、および連続追加期間を重合開始1時間後から６時間後までに変更した以外は、実施例１と同様の操作により、塩化ビニル系ペースト樹脂およびペーストゾルを得た。 (Comparative Example 6)
A vinyl chloride paste resin and a paste sol were obtained by the same operations as in Example 1, except that the charged amounts of vinyl acetate monomer, vinyl chloride, cumyl peroxy neodecanoate, cumyl peroxy neodecanoate, t-butyl peroxy neodecanoate, and t-butyl peroxy neodecanoate were changed to 0.05 parts by mass, 0.025 parts by mass, the polymerization temperature was changed to 42°C, and further the charged amount of 2-hydroxypropyl acrylate was changed to 5 parts by mass, and the continuous addition period was changed to from 1 hour to 6 hours after the start of polymerization.
（比較例７）
ペーストゾルを作成する際に用いる塩化ビニル系ペースト樹脂を、比較例１で得られた塩化ビニル系ペースト樹脂７０質量部および比較例６で得られた塩化ビニル系ペースト樹脂３０質量部の混合物に変更した以外は、実施例１と同様の操作により、ペーストゾルを得た。 (Comparative Example 7)
A paste sol was obtained by the same procedure as in Example 1, except that the vinyl chloride paste resin used in preparing the paste sol was changed to a mixture of 70 parts by mass of the vinyl chloride paste resin obtained in Comparative Example 1 and 30 parts by mass of the vinyl chloride paste resin obtained in Comparative Example 6.
ペーストゾルを作成する際に用いる塩化ビニル系ペースト樹脂を、比較例１で得られた塩化ビニル系ペースト樹脂７０質量部および比較例６で得られた塩化ビニル系ペースト樹脂３０質量部の混合物に変更した以外は、実施例１と同様の操作により、ペーストゾルを得た。 (Comparative Example 7)
A paste sol was obtained by the same procedure as in Example 1, except that the vinyl chloride paste resin used in preparing the paste sol was changed to a mixture of 70 parts by mass of the vinyl chloride paste resin obtained in Comparative Example 1 and 30 parts by mass of the vinyl chloride paste resin obtained in Comparative Example 6.
（比較例８）
ペーストゾルを作成する際に用いる塩化ビニル系ペースト樹脂を、ＵＢＣ用に販売使用されている製品ＰＣＨ－７２（株式会社カネカ製）に変更した以外は、実施例1と同様の操作により、ペーストゾルを得た。 (Comparative Example 8)
A paste sol was obtained in the same manner as in Example 1, except that the vinyl chloride paste resin used in preparing the paste sol was changed to PCH-72 (manufactured by Kaneka Corporation), a product sold for UBC.
ペーストゾルを作成する際に用いる塩化ビニル系ペースト樹脂を、ＵＢＣ用に販売使用されている製品ＰＣＨ－７２（株式会社カネカ製）に変更した以外は、実施例1と同様の操作により、ペーストゾルを得た。 (Comparative Example 8)
A paste sol was obtained in the same manner as in Example 1, except that the vinyl chloride paste resin used in preparing the paste sol was changed to PCH-72 (manufactured by Kaneka Corporation), a product sold for UBC.
実施例および比較例の塩化ビニル系ペースト樹脂における各モノマー単位の含有量、並びに塩化ビニル系ペースト樹脂の重合度を上述したとおりに測定した。また、実施例および比較例の塩化ビニル系ペースト樹脂を含むペーストゾル（プラスチゾル）のせん断特性および引張特性を上述したとおりに測定した。これらの結果を下記表１および表２に示した。また、実施例１、２、６および７塩化ビニル系ペースト樹脂を含むペーストゾル（プラスチゾル）の粘度を上述したとおりに測定し、その結果を下記表３に示した。Ｖ２０ａは、２時間後のペーストゾルの粘度であり、Ｖ２０ｂは、１週間後のペーストゾルの粘度である。
The content of each monomer unit in the vinyl chloride paste resin of the Examples and Comparative Examples, and the degree of polymerization of the vinyl chloride paste resin were measured as described above. In addition, the shear properties and tensile properties of the paste sols (plastisols) containing the vinyl chloride paste resins of the Examples and Comparative Examples were measured as described above. These results are shown in Tables 1 and 2 below. In addition, the viscosity of the paste sols (plastisols) containing the vinyl chloride paste resins of Examples 1, 2, 6 and 7 was measured as described above, and the results are shown in Table 3 below. V20a is the viscosity of the paste sol after 2 hours, and V20b is the viscosity of the paste sol after 1 week.
前記表１から分かるように、実施例の塩化ビニル系ペースト樹脂を含むペーストゾルは、低温（具体的には１２０℃）で加工した際の塗膜のせん断試験における最大接着強度、並びに引張強度および伸び率のいずれも良好であった。また、表３のデータから、実施例６又は実施例７の塩化ビニル系ペースト樹脂を含むペーストゾルの３５℃における７日間放置後の粘度が、実施例１又は実施例２の塩化ビニル系ペースト樹脂を含むペーストゾルの３５℃における７日間放置後の粘度より低く、経時後の取扱性が向上することが分かる。
As can be seen from Table 1 above, the paste sol containing the vinyl chloride paste resin of the Example had good maximum adhesive strength, tensile strength, and elongation in the shear test of the coating film when processed at low temperature (specifically 120°C). Furthermore, the data in Table 3 show that the viscosity of the paste sol containing the vinyl chloride paste resin of Example 6 or Example 7 after being left at 35°C for 7 days is lower than the viscosity of the paste sol containing the vinyl chloride paste resin of Example 1 or Example 2 after being left at 35°C for 7 days, and that the handleability over time is improved.
一方、酢酸ビニルモノマー単位を含むが、ＨＰＡ単位を含まない比較例１、２および８の塩化ビニル系ペースト樹脂を含むペーストゾルは、低温加工した際、せん断試験における最大接着強度が低く、低温加工性が劣る。また、ＨＰＡ単位を含むが、酢酸ビニルモノマー単位を含まない比較例６の塩化ビニル系ペースト樹脂を含むペーストゾルは、低温加工した際、引張強度および伸び率が低く、低温加工性が劣る。また、酢酸ビニルモノマー単位の含有量が４質量％未満であり、ＨＰＡ単位の含有量が６質量％を超える比較例３の塩化ビニル系ペースト樹脂を含むペーストゾルは、低温加工した際、引張強度および伸び率が低く、低温加工性が劣る。酢酸ビニルモノマー単位の含有量が４質量％以上であるが、ＨＰＡ単位の含有量が６質量％を超える比較例４の塩化ビニル系ペースト樹脂を含むペーストゾルは、低温加工した際、せん断試験における最大接着強度が低く、低温加工性が劣る。酢酸ビニルモノマー単位およびＨＰＡ単位の合計含有量が７．５質量％未満である比較例５の塩化ビニル系ペースト樹脂を含むペーストゾルは、低温加工した際、せん断試験における最大接着強度が低く、低温加工性が劣る。また、酢酸ビニルモノマー単位を含むが、ＨＰＡ単位を含まない比較例１の塩化ビニル系ペースト樹脂、およびＨＰＡ単位を含むが、酢酸ビニルモノマー単位を含まない比較例６の塩化ビニル系ペースト樹脂の両方を含む比較例７のペーストゾルは、低温加工した際、せん断試験における最大接着強度が低く、低温加工性が劣る。
On the other hand, the paste sols containing the vinyl chloride paste resins of Comparative Examples 1, 2 and 8, which contain vinyl acetate monomer units but no HPA units, have low maximum adhesive strength in a shear test and poor low-temperature processability when processed at low temperature. Also, the paste sol containing the vinyl chloride paste resin of Comparative Example 6, which contains HPA units but no vinyl acetate monomer units, has low tensile strength and elongation when processed at low temperature and poor low-temperature processability. Also, the paste sol containing the vinyl chloride paste resin of Comparative Example 3, which has a vinyl acetate monomer unit content of less than 4 mass% and an HPA unit content of more than 6 mass%, has low tensile strength and elongation when processed at low temperature and poor low-temperature processability. The paste sol containing the vinyl chloride paste resin of Comparative Example 4, which has a vinyl acetate monomer unit content of 4 mass% or more but an HPA unit content of more than 6 mass%, has low maximum adhesive strength in a shear test and poor low-temperature processability when processed at low temperature. The paste sol containing the vinyl chloride paste resin of Comparative Example 5, in which the total content of vinyl acetate monomer units and HPA units is less than 7.5% by mass, has a low maximum adhesive strength in a shear test and poor low-temperature processability when processed at low temperatures. Also, the paste sol of Comparative Example 7, which contains both the vinyl chloride paste resin of Comparative Example 1, which contains vinyl acetate monomer units but does not contain HPA units, and the vinyl chloride paste resin of Comparative Example 6, which contains HPA units but does not contain vinyl acetate monomer units, has a low maximum adhesive strength in a shear test and poor low-temperature processability when processed at low temperatures.
本発明は、特に限定されないが、例えば、下記の実施形態を含んでもよい。本発明は以下の実施形態に限定されるものではなく、細部については様々な態様が可能であることはいうまでもない。
The present invention is not particularly limited, but may include, for example, the following embodiments. It goes without saying that the present invention is not limited to the following embodiments, and various aspects are possible in terms of details.
［１］塩化ビニルおよび他のモノマーが共重合した塩化ビニル系ペースト樹脂であって、
前記他のモノマーは、水酸基含有モノマーおよびビニルエステル系モノマーを含み、
前記塩化ビニル系ペースト樹脂は、水酸基含有モノマー単位を１～６質量％、ビニルエステル系モノマー単位を４質量％以上、且つ、水酸基含有モノマー単位およびビニルエステル系モノマー単位を合計で７．５～１１質量％含む、塩化ビニル系ペースト樹脂。
［２］前記水酸基含有モノマーは、（メタ）アクリル酸ヒドロキシアルキルエステルである、［１］に記載の塩化ビニル系ペースト樹脂。
［３］前記（メタ）アクリル酸ヒドロキシアルキルエステルは、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、３－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、６－ヒドロキシヘキシル（メタ）アクリレート、および８－ヒドロキシオクチル（メタ）アクリレートからなる群から選ばれる一つ以上である、［２］に記載の塩化ビニル系ペースト樹脂。
［４］前記（メタ）アクリル酸ヒドロキシアルキルエステルは、２－ヒドロキシプロピル（メタ）アクリレートである、［２］又は［３］に記載の塩化ビニル系ペースト樹脂。
［５］前記ビニルエステル系モノマーは、蟻酸ビニル、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、およびステアリン酸ビニルからなる群から選ばれる一つ以上である、［１］～［４］のいずれかに記載の塩化ビニル系ペースト樹脂。
［６］前記ビニルエステル系モノマーは、酢酸ビニルである、［１］～［５］のいずれかに記載の塩化ビニル系ペースト樹脂。
［７］［１］～［６］のいずれかに記載の塩化ビニル系ペースト樹脂を含む、塩化ビニル系ペースト樹脂組成物。
［８］自動車用塗料である、［７］に記載の塩化ビニル系ペースト樹脂組成物。
［９］前記自動車用塗料は、自動車シーラント剤又は自動車アンダーボディコート剤である、［８］に記載の塩化ビニル系ペースト樹脂組成物。
［１０］ ［１］～［６］のいずれかに記載の塩化ビニル系ペースト樹脂の製造方法であって、
塩化ビニルおよび他のモノマーを、水系媒体の存在下、重合反応器中で重合する工程を含み、
前記他のモノマーは、水酸基含有モノマーおよびビニルエステル系モノマーを含み、
前記水酸基含有モノマーを、重合開始後に、連続的に重合反応器に供給する、塩化ビニル系ペースト樹脂の製造方法。
［１１］ 前記水酸基含有モノマーの全量を、重合転化率が５％以上になった後、かつ５０％になるまでの間に、連続的に重合反応器に供給する、［１０］に記載の塩化ビニル系ペースト樹脂の製造方法。 [1] A vinyl chloride-based paste resin in which vinyl chloride and other monomers are copolymerized,
The other monomers include a hydroxyl group-containing monomer and a vinyl ester monomer,
The vinyl chloride paste resin contains 1 to 6 mass% of hydroxyl group-containing monomer units, 4 mass% or more of vinyl ester monomer units, and a total of 7.5 to 11 mass% of hydroxyl group-containing monomer units and vinyl ester monomer units.
[2] The vinyl chloride paste resin according to [1], wherein the hydroxyl group-containing monomer is a (meth)acrylic acid hydroxyalkyl ester.
[3] The vinyl chloride paste resin according to [2], wherein the (meth)acrylic acid hydroxyalkyl ester is at least one selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 8-hydroxyoctyl (meth)acrylate.
[4] The vinyl chloride paste resin according to [2] or [3], wherein the (meth)acrylic acid hydroxyalkyl ester is 2-hydroxypropyl (meth)acrylate.
[5] The vinyl chloride paste resin according to any one of [1] to [4], wherein the vinyl ester monomer is at least one selected from the group consisting of vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl stearate.
[6] The vinyl chloride paste resin according to any one of [1] to [5], wherein the vinyl ester monomer is vinyl acetate.
[7] A vinyl chloride paste resin composition comprising the vinyl chloride paste resin according to any one of [1] to [6].
[8] The vinyl chloride paste resin composition according to [7], which is an automotive paint.
[9] The vinyl chloride paste resin composition according to [8], wherein the automotive paint is an automotive sealant or an automotive underbody coating agent.
[10] A method for producing the vinyl chloride paste resin according to any one of [1] to [6],
The process comprises the steps of polymerizing vinyl chloride and other monomers in a polymerization reactor in the presence of an aqueous medium,
The other monomers include a hydroxyl group-containing monomer and a vinyl ester monomer,
the hydroxyl group-containing monomer is continuously supplied to a polymerization reactor after polymerization is initiated.
[11] The method for producing a vinyl chloride paste resin according to [10], wherein the total amount of the hydroxyl group-containing monomer is continuously supplied to a polymerization reactor after the polymerization conversion rate has reached 5% or more and before the polymerization conversion rate reaches 50%.
前記他のモノマーは、水酸基含有モノマーおよびビニルエステル系モノマーを含み、
前記塩化ビニル系ペースト樹脂は、水酸基含有モノマー単位を１～６質量％、ビニルエステル系モノマー単位を４質量％以上、且つ、水酸基含有モノマー単位およびビニルエステル系モノマー単位を合計で７．５～１１質量％含む、塩化ビニル系ペースト樹脂。
［２］前記水酸基含有モノマーは、（メタ）アクリル酸ヒドロキシアルキルエステルである、［１］に記載の塩化ビニル系ペースト樹脂。
［３］前記（メタ）アクリル酸ヒドロキシアルキルエステルは、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、３－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、６－ヒドロキシヘキシル（メタ）アクリレート、および８－ヒドロキシオクチル（メタ）アクリレートからなる群から選ばれる一つ以上である、［２］に記載の塩化ビニル系ペースト樹脂。
［４］前記（メタ）アクリル酸ヒドロキシアルキルエステルは、２－ヒドロキシプロピル（メタ）アクリレートである、［２］又は［３］に記載の塩化ビニル系ペースト樹脂。
［５］前記ビニルエステル系モノマーは、蟻酸ビニル、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、およびステアリン酸ビニルからなる群から選ばれる一つ以上である、［１］～［４］のいずれかに記載の塩化ビニル系ペースト樹脂。
［６］前記ビニルエステル系モノマーは、酢酸ビニルである、［１］～［５］のいずれかに記載の塩化ビニル系ペースト樹脂。
［７］［１］～［６］のいずれかに記載の塩化ビニル系ペースト樹脂を含む、塩化ビニル系ペースト樹脂組成物。
［８］自動車用塗料である、［７］に記載の塩化ビニル系ペースト樹脂組成物。
［９］前記自動車用塗料は、自動車シーラント剤又は自動車アンダーボディコート剤である、［８］に記載の塩化ビニル系ペースト樹脂組成物。
［１０］ ［１］～［６］のいずれかに記載の塩化ビニル系ペースト樹脂の製造方法であって、
塩化ビニルおよび他のモノマーを、水系媒体の存在下、重合反応器中で重合する工程を含み、
前記他のモノマーは、水酸基含有モノマーおよびビニルエステル系モノマーを含み、
前記水酸基含有モノマーを、重合開始後に、連続的に重合反応器に供給する、塩化ビニル系ペースト樹脂の製造方法。
［１１］ 前記水酸基含有モノマーの全量を、重合転化率が５％以上になった後、かつ５０％になるまでの間に、連続的に重合反応器に供給する、［１０］に記載の塩化ビニル系ペースト樹脂の製造方法。 [1] A vinyl chloride-based paste resin in which vinyl chloride and other monomers are copolymerized,
The other monomers include a hydroxyl group-containing monomer and a vinyl ester monomer,
The vinyl chloride paste resin contains 1 to 6 mass% of hydroxyl group-containing monomer units, 4 mass% or more of vinyl ester monomer units, and a total of 7.5 to 11 mass% of hydroxyl group-containing monomer units and vinyl ester monomer units.
[2] The vinyl chloride paste resin according to [1], wherein the hydroxyl group-containing monomer is a (meth)acrylic acid hydroxyalkyl ester.
[3] The vinyl chloride paste resin according to [2], wherein the (meth)acrylic acid hydroxyalkyl ester is at least one selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 8-hydroxyoctyl (meth)acrylate.
[4] The vinyl chloride paste resin according to [2] or [3], wherein the (meth)acrylic acid hydroxyalkyl ester is 2-hydroxypropyl (meth)acrylate.
[5] The vinyl chloride paste resin according to any one of [1] to [4], wherein the vinyl ester monomer is at least one selected from the group consisting of vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl stearate.
[6] The vinyl chloride paste resin according to any one of [1] to [5], wherein the vinyl ester monomer is vinyl acetate.
[7] A vinyl chloride paste resin composition comprising the vinyl chloride paste resin according to any one of [1] to [6].
[8] The vinyl chloride paste resin composition according to [7], which is an automotive paint.
[9] The vinyl chloride paste resin composition according to [8], wherein the automotive paint is an automotive sealant or an automotive underbody coating agent.
[10] A method for producing the vinyl chloride paste resin according to any one of [1] to [6],
The process comprises the steps of polymerizing vinyl chloride and other monomers in a polymerization reactor in the presence of an aqueous medium,
The other monomers include a hydroxyl group-containing monomer and a vinyl ester monomer,
the hydroxyl group-containing monomer is continuously supplied to a polymerization reactor after polymerization is initiated.
[11] The method for producing a vinyl chloride paste resin according to [10], wherein the total amount of the hydroxyl group-containing monomer is continuously supplied to a polymerization reactor after the polymerization conversion rate has reached 5% or more and before the polymerization conversion rate reaches 50%.
Claims (11)
- 塩化ビニルおよび他のモノマーが共重合した塩化ビニル系ペースト樹脂であって、
前記他のモノマーは、水酸基含有モノマーおよびビニルエステル系モノマーを含み、
前記塩化ビニル系ペースト樹脂は、水酸基含有モノマー単位を１～６質量％、ビニルエステル系モノマー単位を４質量％以上、且つ、水酸基含有モノマー単位およびビニルエステル系モノマー単位を合計で７．５～１１質量％含む、塩化ビニル系ペースト樹脂。 A vinyl chloride paste resin in which vinyl chloride and other monomers are copolymerized,
The other monomers include a hydroxyl group-containing monomer and a vinyl ester monomer,
The vinyl chloride paste resin contains 1 to 6 mass% of hydroxyl group-containing monomer units, 4 mass% or more of vinyl ester monomer units, and a total of 7.5 to 11 mass% of hydroxyl group-containing monomer units and vinyl ester monomer units. - 前記水酸基含有モノマーは、（メタ）アクリル酸ヒドロキシアルキルエステルである、請求項１に記載の塩化ビニル系ペースト樹脂。 The vinyl chloride paste resin according to claim 1, wherein the hydroxyl group-containing monomer is a (meth)acrylic acid hydroxyalkyl ester.
- 前記（メタ）アクリル酸ヒドロキシアルキルエステルは、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、３－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、６－ヒドロキシヘキシル（メタ）アクリレート、および８－ヒドロキシオクチル（メタ）アクリレートからなる群から選ばれる一つ以上である、請求項２に記載の塩化ビニル系ペースト樹脂。 The vinyl chloride paste resin according to claim 2, wherein the (meth)acrylic acid hydroxyalkyl ester is one or more selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 8-hydroxyoctyl (meth)acrylate.
- 前記（メタ）アクリル酸ヒドロキシアルキルエステルは、２－ヒドロキシプロピル（メタ）アクリレートである、請求項２に記載の塩化ビニル系ペースト樹脂。 The vinyl chloride paste resin according to claim 2, wherein the (meth)acrylic acid hydroxyalkyl ester is 2-hydroxypropyl (meth)acrylate.
- 前記ビニルエステル系モノマーは、蟻酸ビニル、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、およびステアリン酸ビニルからなる群から選ばれる一つ以上である、請求項１に記載の塩化ビニル系ペースト樹脂。 The vinyl chloride paste resin according to claim 1, wherein the vinyl ester monomer is at least one selected from the group consisting of vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl stearate.
- 前記ビニルエステル系モノマーは、酢酸ビニルである、請求項１に記載の塩化ビニル系ペースト樹脂。 The vinyl chloride paste resin according to claim 1, wherein the vinyl ester monomer is vinyl acetate.
- 請求項１～６のいずれかに記載の塩化ビニル系ペースト樹脂を含む、塩化ビニル系ペースト樹脂組成物。 A vinyl chloride paste resin composition comprising the vinyl chloride paste resin according to any one of claims 1 to 6.
- 自動車用塗料である、請求項７に記載の塩化ビニル系ペースト樹脂組成物。 The vinyl chloride paste resin composition according to claim 7, which is an automotive paint.
- 前記自動車用塗料は、自動車シーラント剤又は自動車アンダーボディコート剤である、請求項８に記載の塩化ビニル系ペースト樹脂組成物。 The vinyl chloride paste resin composition according to claim 8, wherein the automotive paint is an automotive sealant or an automotive underbody coating agent.
- 請求項１～６のいずれかに記載の塩化ビニル系ペースト樹脂の製造方法であって、
塩化ビニルおよび他のモノマーを、水系媒体の存在下、重合反応器中で重合する工程を含み、
前記他のモノマーは、水酸基含有モノマーおよびビニルエステル系モノマーを含み、
前記水酸基含有モノマーを、重合開始後に、連続的に重合反応器に供給する、塩化ビニル系ペースト樹脂の製造方法。 A method for producing the vinyl chloride paste resin according to any one of claims 1 to 6,
The process comprises the steps of polymerizing vinyl chloride and other monomers in a polymerization reactor in the presence of an aqueous medium,
The other monomers include a hydroxyl group-containing monomer and a vinyl ester monomer,
the hydroxyl group-containing monomer is continuously supplied to a polymerization reactor after polymerization is initiated. - 前記水酸基含有モノマーの全量を、重合転化率が５％以上になった後、かつ５０％になるまでの間に、連続的に重合反応器に供給する、請求項１０に記載の塩化ビニル系ペースト樹脂の製造方法。 The method for producing a vinyl chloride paste resin according to claim 10, wherein the total amount of the hydroxyl group-containing monomer is continuously supplied to the polymerization reactor after the polymerization conversion rate reaches 5% or more and before it reaches 50%.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2023-038005 | 2023-03-10 | ||
| JP2023038005 | 2023-03-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2024190561A1 true WO2024190561A1 (en) | 2024-09-19 |
Family
ID=92755098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2024/008503 WO2024190561A1 (en) | 2023-03-10 | 2024-03-06 | Vinyl chloride paste resin, vinyl chloride paste resin composition containing same, and method for producing same |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2024190561A1 (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04239513A (en) * | 1991-01-23 | 1992-08-27 | Sekisui Chem Co Ltd | Production of vinyl chloride-based resin |
| JPH06234827A (en) * | 1993-02-09 | 1994-08-23 | Mitsubishi Kasei Vinyl Co | Plastisol composition |
| JPH06287481A (en) * | 1993-03-31 | 1994-10-11 | Nippon Zeon Co Ltd | Magnetic coating and magnetic recording medium |
| WO2006095611A1 (en) * | 2005-03-11 | 2006-09-14 | Toyo Ink Mfg. Co., Ltd. | Electrically conductive ink, electrically conductive circuit, and noncontact-type medium |
| WO2009119255A1 (en) * | 2008-03-28 | 2009-10-01 | ダイキン工業株式会社 | Vinyl chloride polymer |
| JP2021116328A (en) * | 2020-01-23 | 2021-08-10 | 東ソー株式会社 | Hydroxy group-containing vinyl chloride copolymer composition particle |
-
2024
- 2024-03-06 WO PCT/JP2024/008503 patent/WO2024190561A1/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04239513A (en) * | 1991-01-23 | 1992-08-27 | Sekisui Chem Co Ltd | Production of vinyl chloride-based resin |
| JPH06234827A (en) * | 1993-02-09 | 1994-08-23 | Mitsubishi Kasei Vinyl Co | Plastisol composition |
| JPH06287481A (en) * | 1993-03-31 | 1994-10-11 | Nippon Zeon Co Ltd | Magnetic coating and magnetic recording medium |
| WO2006095611A1 (en) * | 2005-03-11 | 2006-09-14 | Toyo Ink Mfg. Co., Ltd. | Electrically conductive ink, electrically conductive circuit, and noncontact-type medium |
| WO2009119255A1 (en) * | 2008-03-28 | 2009-10-01 | ダイキン工業株式会社 | Vinyl chloride polymer |
| JP2021116328A (en) * | 2020-01-23 | 2021-08-10 | 東ソー株式会社 | Hydroxy group-containing vinyl chloride copolymer composition particle |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH04216850A (en) | Polyvinyl chloride plastisol composition | |
| KR20180047361A (en) | Vinyl chloride polymer and preparation method thereof | |
| KR101768284B1 (en) | Paste vinyl chloride resin and preparing method thereof | |
| US20050131176A1 (en) | Process for production of polymer dispersions containing an acetoacetate moiety | |
| KR101404828B1 (en) | Method for producing vinyl chloridebased resin paste having reduced change of elapsed time in viscosity | |
| EP3404051B1 (en) | Vinyl chloride-based polymer composition and preparation method therefor | |
| CN107614547B (en) | Vinyl chloride-based polymer, method for preparing same, and plastisol comprising same | |
| WO2024190561A1 (en) | Vinyl chloride paste resin, vinyl chloride paste resin composition containing same, and method for producing same | |
| KR101633230B1 (en) | Preparation method of vinylchloride polymer and vinyl chloride polymer produced by the same | |
| EP4029885A1 (en) | Method for preparing vinyl chloride-based polymer | |
| JP3469377B2 (en) | Method for producing vinyl chloride polymer | |
| JP4529430B2 (en) | Vinyl chloride resin for paste, method for producing the same, and vinyl chloride resin composition for paste | |
| KR102342102B1 (en) | Vinyl chloride polymer, preparation method thereof and plastisol comprising the same | |
| KR100682210B1 (en) | Method for preparing of paste vinyl chloride resin | |
| JP2533797B2 (en) | Process for producing vinyl chloride polymer composition for paste dispersion | |
| KR101755079B1 (en) | Vinyl chloride polymer and preparing method thereof | |
| JP2756995B2 (en) | Method for producing vinyl chloride copolymer | |
| JP5003692B2 (en) | Method for producing vinyl chloride resin for paste | |
| JP7556259B2 (en) | Vinyl chloride resin composition for paste processing | |
| JP4588915B2 (en) | Acrylic resin plastisol and acrylic resin molded products | |
| WO2023095825A1 (en) | Vinyl chloride-based paste resin and resin composition for automobile undercoating | |
| JP2022151172A (en) | Polyvinyl chloride-based paste resin and resin composition for automobile primer | |
| JP2005330408A (en) | Vinyl chloride-based paste resin | |
| EP3865526B1 (en) | Composition for polymerizing vinyl chloride-based polymer, and method for preparing vinyl chloride-based polymer using same | |
| EP3715387B1 (en) | Vinyl chloride-based polymer and preparation method thereof |