WO2023021946A1 - Composition de latex pour moulage par immersion, et corps moulé par immersion - Google Patents
Composition de latex pour moulage par immersion, et corps moulé par immersion Download PDFInfo
- Publication number
- WO2023021946A1 WO2023021946A1 PCT/JP2022/028816 JP2022028816W WO2023021946A1 WO 2023021946 A1 WO2023021946 A1 WO 2023021946A1 JP 2022028816 W JP2022028816 W JP 2022028816W WO 2023021946 A1 WO2023021946 A1 WO 2023021946A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- compound
- latex
- polymer
- dip
- latex composition
- Prior art date
Links
- 239000004816 latex Substances 0.000 title claims abstract description 326
- 229920000126 latex Polymers 0.000 title claims abstract description 326
- 239000000203 mixture Substances 0.000 title claims abstract description 184
- 238000000465 moulding Methods 0.000 title claims abstract description 173
- 229920000642 polymer Polymers 0.000 claims abstract description 242
- 150000001875 compounds Chemical class 0.000 claims abstract description 197
- 125000000129 anionic group Chemical group 0.000 claims abstract description 38
- 125000003118 aryl group Chemical group 0.000 claims abstract description 34
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 25
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 20
- 150000001993 dienes Chemical class 0.000 claims description 34
- -1 alkylbenzene sulfonate Chemical class 0.000 claims description 30
- 125000002560 nitrile group Chemical group 0.000 claims description 21
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 8
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 2
- 239000003814 drug Substances 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 239000000178 monomer Substances 0.000 description 91
- 238000000034 method Methods 0.000 description 60
- 239000010410 layer Substances 0.000 description 55
- 238000004519 manufacturing process Methods 0.000 description 49
- 230000001681 protective effect Effects 0.000 description 43
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 41
- 229920000459 Nitrile rubber Polymers 0.000 description 40
- 239000002245 particle Substances 0.000 description 32
- 230000009477 glass transition Effects 0.000 description 28
- 239000011734 sodium Substances 0.000 description 28
- 239000000463 material Substances 0.000 description 26
- 238000005259 measurement Methods 0.000 description 25
- 229910052708 sodium Inorganic materials 0.000 description 25
- 238000012360 testing method Methods 0.000 description 25
- 239000000758 substrate Substances 0.000 description 24
- 239000000126 substance Substances 0.000 description 23
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 22
- 230000000694 effects Effects 0.000 description 22
- 238000006116 polymerization reaction Methods 0.000 description 22
- 239000007787 solid Substances 0.000 description 22
- 239000002585 base Substances 0.000 description 20
- 229910052751 metal Inorganic materials 0.000 description 20
- 239000002184 metal Substances 0.000 description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 19
- 239000002253 acid Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 18
- 229920001577 copolymer Polymers 0.000 description 17
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- 229920003169 water-soluble polymer Polymers 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 230000035882 stress Effects 0.000 description 15
- 239000004094 surface-active agent Substances 0.000 description 15
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 14
- 125000005396 acrylic acid ester group Chemical group 0.000 description 14
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 13
- 239000000701 coagulant Substances 0.000 description 13
- 238000002156 mixing Methods 0.000 description 13
- 229910052717 sulfur Inorganic materials 0.000 description 13
- 239000011593 sulfur Substances 0.000 description 13
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 10
- 239000004925 Acrylic resin Substances 0.000 description 10
- 229920000178 Acrylic resin Polymers 0.000 description 10
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 10
- 238000007720 emulsion polymerization reaction Methods 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 9
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- 229920005989 resin Polymers 0.000 description 9
- 239000005060 rubber Substances 0.000 description 9
- 239000000835 fiber Substances 0.000 description 8
- 229920001519 homopolymer Polymers 0.000 description 8
- 229910052700 potassium Inorganic materials 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- 125000000542 sulfonic acid group Chemical group 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000003431 cross linking reagent Substances 0.000 description 7
- 150000002825 nitriles Chemical class 0.000 description 7
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 7
- 239000003505 polymerization initiator Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 6
- 125000002843 carboxylic acid group Chemical group 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 6
- 239000004926 polymethyl methacrylate Substances 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 238000005187 foaming Methods 0.000 description 5
- 229920003049 isoprene rubber Polymers 0.000 description 5
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 5
- 230000000379 polymerizing effect Effects 0.000 description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 5
- 230000003746 surface roughness Effects 0.000 description 5
- 229920003051 synthetic elastomer Polymers 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 229920005549 butyl rubber Polymers 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 210000003811 finger Anatomy 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000149 argon plasma sintering Methods 0.000 description 3
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- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
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- 150000001768 cations Chemical class 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
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- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
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- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- 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 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
- IZFHMLDRUVYBGK-UHFFFAOYSA-N 2-methylene-3-methylsuccinic acid Chemical compound OC(=O)C(C)C(=C)C(O)=O IZFHMLDRUVYBGK-UHFFFAOYSA-N 0.000 description 2
- GIUBHMDTOCBOPA-UHFFFAOYSA-N 3h-1,3-benzothiazole-2-thione;zinc Chemical compound [Zn].C1=CC=C2SC(S)=NC2=C1 GIUBHMDTOCBOPA-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
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- 241000894006 Bacteria Species 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- 150000008064 anhydrides Chemical class 0.000 description 2
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- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
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- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 2
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 2
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
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- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
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- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 229940033623 potassium lauryl phosphate Drugs 0.000 description 1
- ONQDVAFWWYYXHM-UHFFFAOYSA-M potassium lauryl sulfate Chemical compound [K+].CCCCCCCCCCCCOS([O-])(=O)=O ONQDVAFWWYYXHM-UHFFFAOYSA-M 0.000 description 1
- 229940116985 potassium lauryl sulfate Drugs 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- HSJXWMZKBLUOLQ-UHFFFAOYSA-M potassium;2-dodecylbenzenesulfonate Chemical compound [K+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HSJXWMZKBLUOLQ-UHFFFAOYSA-M 0.000 description 1
- JTXIPOLAHSBNJM-UHFFFAOYSA-M potassium;decyl sulfate Chemical compound [K+].CCCCCCCCCCOS([O-])(=O)=O JTXIPOLAHSBNJM-UHFFFAOYSA-M 0.000 description 1
- GBEYVKHMIPVAHD-UHFFFAOYSA-M potassium;hexadecyl sulfate Chemical compound [K+].CCCCCCCCCCCCCCCCOS([O-])(=O)=O GBEYVKHMIPVAHD-UHFFFAOYSA-M 0.000 description 1
- FTCOOXFANFQPEC-UHFFFAOYSA-M potassium;octyl sulfate Chemical compound [K+].CCCCCCCCOS([O-])(=O)=O FTCOOXFANFQPEC-UHFFFAOYSA-M 0.000 description 1
- PYJBVGYZXWPIKK-UHFFFAOYSA-M potassium;tetradecanoate Chemical compound [K+].CCCCCCCCCCCCCC([O-])=O PYJBVGYZXWPIKK-UHFFFAOYSA-M 0.000 description 1
- WIBVOBURKHLIQM-UHFFFAOYSA-N potassium;tetradecyl benzenesulfonate Chemical compound [K].CCCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 WIBVOBURKHLIQM-UHFFFAOYSA-N 0.000 description 1
- DQFWABVCOIFBPO-UHFFFAOYSA-M potassium;tetradecyl sulfate Chemical compound [K+].CCCCCCCCCCCCCCOS([O-])(=O)=O DQFWABVCOIFBPO-UHFFFAOYSA-M 0.000 description 1
- OVMORFVFEKUOLJ-UHFFFAOYSA-N potassium;tridecyl benzenesulfonate Chemical compound [K].CCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 OVMORFVFEKUOLJ-UHFFFAOYSA-N 0.000 description 1
- BFHVMBPOAYYQFV-UHFFFAOYSA-N potassium;undecyl benzenesulfonate Chemical compound [K].CCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 BFHVMBPOAYYQFV-UHFFFAOYSA-N 0.000 description 1
- YKOOAYMDPZMOJG-UHFFFAOYSA-M potassium;undecyl sulfate Chemical compound [K+].CCCCCCCCCCCOS([O-])(=O)=O YKOOAYMDPZMOJG-UHFFFAOYSA-M 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- RAJUSMULYYBNSJ-UHFFFAOYSA-N prop-1-ene-1-sulfonic acid Chemical compound CC=CS(O)(=O)=O RAJUSMULYYBNSJ-UHFFFAOYSA-N 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- ZIWRUEGECALFST-UHFFFAOYSA-M sodium 4-(4-dodecoxysulfonylphenoxy)benzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCOS(=O)(=O)c1ccc(Oc2ccc(cc2)S([O-])(=O)=O)cc1 ZIWRUEGECALFST-UHFFFAOYSA-M 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- 229940067741 sodium octyl sulfate Drugs 0.000 description 1
- 229940045870 sodium palmitate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 229960000776 sodium tetradecyl sulfate Drugs 0.000 description 1
- UNZSHUCNBUBSGW-IFNWOZJISA-M sodium;(9z,12z,15z)-octadeca-9,12,15-trienoate Chemical compound [Na+].CC\C=C/C\C=C/C\C=C/CCCCCCCC([O-])=O UNZSHUCNBUBSGW-IFNWOZJISA-M 0.000 description 1
- HLWRUJAIJJEZDL-UHFFFAOYSA-M sodium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound [Na+].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC([O-])=O HLWRUJAIJJEZDL-UHFFFAOYSA-M 0.000 description 1
- RLJSXMVTLMHXJS-UHFFFAOYSA-M sodium;4-decylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 RLJSXMVTLMHXJS-UHFFFAOYSA-M 0.000 description 1
- XZTJQQLJJCXOLP-UHFFFAOYSA-M sodium;decyl sulfate Chemical compound [Na+].CCCCCCCCCCOS([O-])(=O)=O XZTJQQLJJCXOLP-UHFFFAOYSA-M 0.000 description 1
- GGXKEBACDBNFAF-UHFFFAOYSA-M sodium;hexadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCC([O-])=O GGXKEBACDBNFAF-UHFFFAOYSA-M 0.000 description 1
- GGHPAKFFUZUEKL-UHFFFAOYSA-M sodium;hexadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCOS([O-])(=O)=O GGHPAKFFUZUEKL-UHFFFAOYSA-M 0.000 description 1
- WFRKJMRGXGWHBM-UHFFFAOYSA-M sodium;octyl sulfate Chemical compound [Na+].CCCCCCCCOS([O-])(=O)=O WFRKJMRGXGWHBM-UHFFFAOYSA-M 0.000 description 1
- ORLPWCUCEDVJNN-UHFFFAOYSA-N sodium;tetradecyl benzenesulfonate Chemical compound [Na].CCCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 ORLPWCUCEDVJNN-UHFFFAOYSA-N 0.000 description 1
- UPUIQOIQVMNQAP-UHFFFAOYSA-M sodium;tetradecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCOS([O-])(=O)=O UPUIQOIQVMNQAP-UHFFFAOYSA-M 0.000 description 1
- NZRSEGYTVSNMCK-UHFFFAOYSA-N sodium;undecyl benzenesulfonate Chemical compound [Na].CCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 NZRSEGYTVSNMCK-UHFFFAOYSA-N 0.000 description 1
- UOWRKHDWHDWJHK-UHFFFAOYSA-M sodium;undecyl sulfate Chemical compound [Na+].CCCCCCCCCCCOS([O-])(=O)=O UOWRKHDWHDWJHK-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 1
- 229940052367 sulfur,colloidal Drugs 0.000 description 1
- 239000002335 surface treatment layer Substances 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- NEUOBESLMIKJSB-UHFFFAOYSA-J tetrasodium;tetraacetate Chemical compound [Na+].[Na+].[Na+].[Na+].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O NEUOBESLMIKJSB-UHFFFAOYSA-J 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 210000000707 wrist Anatomy 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- RKQOSDAEEGPRER-UHFFFAOYSA-L zinc diethyldithiocarbamate Chemical compound [Zn+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S RKQOSDAEEGPRER-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D19/00—Gloves
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D19/00—Gloves
- A41D19/015—Protective gloves
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
- C08L21/02—Latex
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
- C08L9/04—Latex
Definitions
- the present invention relates to a latex composition for dip molding, and more particularly, a latex composition for dip molding that is capable of providing a dip-molded article having excellent chemical permeation resistance and well-balanced wet grip and flexibility. Regarding.
- protective gloves are required to have excellent mechanical strength and durability, such as abrasion resistance, as well as excellent flexibility.
- protective gloves are often used in a state where they are wet with chemical solutions such as oil, they are also required to have excellent wet grip properties when the chemical solution is attached and resistance to chemical solution permeation.
- Patent Document 1 describes 50 to 80% by weight of 1,3-butadiene, 15 to 50% by weight of acrylonitrile, 0 to 10% by weight of an ethylenically unsaturated carboxylic acid monomer, and ethylene copolymerizable therewith.
- a copolymer latex for dip molding is described which has a surface tension difference of 6 mN/m or more and a methyl ethyl ketone (MEK) insoluble content of 50% or more.
- MEK methyl ethyl ketone
- the present invention has been made in view of such circumstances, and a latex composition for dip molding that is capable of providing a dip-molded article having excellent resistance to permeation of chemical solutions and having a good balance between wet grip properties and flexibility.
- the purpose is to provide goods.
- Another object of the present invention is to provide a dip-molded article which has excellent chemical liquid permeation resistance and which has a good balance between wet grip properties and flexibility.
- a dip-forming latex composition containing a polymer latex and an anionic surfactant, wherein the anionic surfactant has one anionic group and an aromatic ring. and a compound (b1) having two or more anionic groups and a benzene ring, or a compound (b2) having one anionic group and no aromatic ring.
- a molding latex composition is provided.
- the compound (b1) is preferably a compound having two anionic groups and a benzene ring, more preferably an alkyldiphenylether disulfonate.
- the compound (b2) is preferably an alkyl sulfate.
- the compound (a) is a sulfonate or a sulfate ester salt, and at least one of the compound (b1) and the compound (b2) is a sulfonate or Sulfuric acid ester salts are preferred.
- the content of compound (a) is 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the polymer component contained in the latex composition for dip molding.
- the total content of the compound (b1) and the content of the compound (b2) is It is preferably 0.1 to 10.0 parts by weight.
- the weight ratio of the content of compound (a) to the total content of compound (b1) and compound (b2) [weight of compound (a): compound (b1) and The total weight of compound (b2)] is preferably from 5:95 to 95:5.
- the compound (a) is preferably an alkylbenzenesulfonate.
- the polymer latex is preferably a nitrile group-containing conjugated diene polymer latex.
- a dip-molded article using the dip-molding latex composition is provided.
- the dip molded article of the present invention is preferably a glove.
- the present invention it is possible to provide a latex composition for dip molding that has excellent chemical liquid permeation resistance and can give a dip molded article that has an excellent balance of wet grip properties and flexibility.
- a dip-molded article which has excellent resistance to chemical liquid permeation and which has a good balance between wet grip properties and flexibility.
- the dip-forming latex composition of the present invention is a dip-forming latex composition containing a polymer latex and an anionic surfactant, wherein the anionic surfactant has one anionic group.
- a compound (a) having an aromatic ring and a compound (b1) having two or more anionic groups and a benzene ring or a compound (b2) having one anionic group and no aromatic ring It is a latex composition for dip molding containing.
- the dip molding latex composition of the present invention contains a polymer latex.
- the polymer constituting the polymer latex is not particularly limited, but examples include nitrile rubber (NBR), natural rubber (NR), styrene-butadiene rubber (SBR), synthetic polyisoprene rubber (IR), polybutadiene rubber ( BR), styrene-isoprene copolymer rubber, styrene-isoprene-styrene copolymer rubber and other conjugated diene polymers, polybutyl acrylate, butyl rubber (IIR), and the like.
- NBR nitrile rubber
- NR natural rubber
- SBR styrene-butadiene rubber
- IR polyisoprene rubber
- BR polybutadiene rubber
- styrene-isoprene copolymer rubber styrene-isoprene-styrene copolymer rubber and other conjugated diene polymers
- IIR butyl rubber
- NBR nitrile rubber
- SBR styrene-butadiene rubber
- IR synthetic polyisoprene rubber
- polybutyl acrylate are more preferable.
- Conjugated diene polymers containing nitrile groups such as NBR (hereinafter referred to as "nitrile group-containing conjugated diene polymers” as appropriate) are more preferred.
- conjugated diene polymers may be conjugated diene polymers containing carboxyl groups (hereinafter referred to as "carboxyl group-containing conjugated diene polymers” as appropriate).
- the nitrile group-containing conjugated diene-based polymer is not particularly limited. A copolymer obtained by copolymerizing other ethylenically unsaturated acid monomers can be used.
- the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer is not particularly limited, but an ethylenically unsaturated compound having a nitrile group and preferably having 3 to 18 carbon atoms can be used.
- Such ⁇ , ⁇ -ethylenically unsaturated nitrile monomers include, for example, acrylonitrile, methacrylonitrile, halogen-substituted acrylonitrile, etc. Among these, acrylonitrile is particularly preferred.
- These ⁇ , ⁇ -ethylenically unsaturated nitrile monomers may be used singly or in combination of two or more.
- the content ratio of the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer units in the nitrile group-containing conjugated diene polymer is, from the viewpoint of the flexibility and solvent resistance of the resulting dip-molded product, relative to the total monomer units. , preferably 10 to 45% by weight, more preferably 15 to 40% by weight, still more preferably 20 to 40% by weight.
- conjugated diene monomer a conjugated diene monomer having 4 to 6 carbon atoms such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and chloroprene is preferable. , 1,3-butadiene and isoprene are more preferred, and 1,3-butadiene is particularly preferred.
- conjugated diene monomers may be used singly or in combination of two or more.
- the content of conjugated diene monomer units in the nitrile group-containing conjugated diene polymer is preferably 40 to 89.9% by weight based on the total monomer units from the viewpoint of the flexibility of the resulting dip molded product. , more preferably 50 to 84% by weight, still more preferably 52 to 78% by weight, and particularly preferably 55 to 75% by weight.
- the nitrile group-containing conjugated diene polymer can be copolymerized with a monomer forming an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit and a monomer forming a conjugated diene monomer unit. may be copolymerized with other ethylenically unsaturated acid monomers.
- Such other copolymerizable ethylenically unsaturated acid monomers are not particularly limited, but examples include vinyl aromatic monomers such as styrene, alkylstyrene, and vinylnaphthalene, monomers, monocarboxylic acid ester group-containing ethylenically unsaturated monomers, dicarboxylic acid diester group-containing ethylenically unsaturated monomers, sulfonic acid group-containing ethylenically unsaturated monomers, phosphoric acid group-containing ethylenically unsaturated monomers Among them, the nitrile group-containing conjugated diene polymer can be one containing a carboxyl group, and as a result, the resulting dip-molded article has excellent mechanical properties.
- vinyl aromatic monomers such as styrene, alkylstyrene, and vinylnaphthalene
- monomers monocarboxylic acid ester group-containing ethylenically uns
- a carboxyl group-containing ethylenically unsaturated monomer is preferable from the viewpoint that it can be
- Polymers constituting the polymer latex include, for example, ⁇ , ⁇ -ethylenically unsaturated nitrile monomer units, conjugated diene monomer units in nitrile group-containing conjugated diene polymers, and carboxyl group-containing ethylenically unsaturated It may be a polymer consisting of only monomers.
- the carboxyl group-containing ethylenically unsaturated monomer is not particularly limited, but ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid; fumaric acid, maleic acid, itaconic acid, maleic anhydride, anhydride ethylenically unsaturated polycarboxylic acids such as itaconic acid and anhydrides thereof; partially esterified products of ethylenically unsaturated polycarboxylic acids such as methyl maleate and methyl itaconate; and the like.
- monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid
- partially esterified products of ethylenically unsaturated polycarboxylic acids such as
- the content ratio of the unit of the carboxyl group-containing ethylenically unsaturated monomer is the total monomer unit , preferably 0.1 to 15 wt%, more preferably 1 to 10 wt%, still more preferably 2 to 8 wt%.
- the monocarboxylic acid ester group-containing ethylenically unsaturated monomer is not particularly limited, but acrylic acid esters such as methyl acrylate, ethyl acrylate and n-butyl acrylate; methyl methacrylate, ethyl methacrylate, methacrylic acid; methacrylic acid esters such as n-butyl; crotonic acid esters such as methyl crotonate; and the like. Among them, acrylic acid esters and methacrylic acid esters are preferred, and methyl acrylate and methyl methacrylate are more preferred.
- dicarboxylic acid diester group-containing ethylenically unsaturated monomer examples include, but are not limited to, maleic acid diesters such as dimethyl maleate; itaconic acid diesters such as methyl itaconate; and the like.
- the sulfonic acid group-containing ethylenically unsaturated monomer is not particularly limited, but vinylsulfonic acid, methylvinylsulfonic acid, styrenesulfonic acid, (meth)allylsulfonic acid, ethyl (meth)acrylic acid-2-sulfonate. , 2-acrylamido-2-hydroxypropanesulfonic acid and the like.
- phosphate group-containing ethylenically unsaturated monomer examples include, but are not limited to, propyl (meth)acrylate-3-chloro-2-phosphate, ethyl (meth)acrylate-2-phosphate, 3-allyloxy -2-hydroxypropane phosphate and the like.
- copolymerizable ethylenically unsaturated acid monomers may be used as alkali metal salts or ammonium salts, and may be used singly or in combination of two or more. good.
- carboxyl group-containing ethylenically unsaturated monomers are preferred, ethylenically unsaturated monocarboxylic acids are more preferred, and acrylic acid and methacrylic acid are preferred. More preferred, methacrylic acid is particularly preferred.
- the ratio is preferably 0.1 to 45% by weight with respect to the total monomer units, and more It is preferably 1 to 40% by weight, more preferably 2 to 38% by weight.
- the polymer latex can be obtained, for example, by emulsion polymerization of a monomer mixture containing the above monomers.
- auxiliary materials for polymerization such as emulsifiers, polymerization initiators, and molecular weight modifiers can be used.
- the emulsifier used for emulsion polymerization is not particularly limited, and examples thereof include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. preferable.
- anionic surfactant used in emulsion polymerization examples include a compound (a) having one anionic group and an aromatic ring, and a compound (b1) having two or more anionic groups and a benzene ring, which will be described later. ), a compound (b2) having one anionic group and no aromatic ring, and the like.
- a compound (a) having one anionic group and an aromatic ring and a compound (b1) having two or more anionic groups and a benzene ring, which will be described later.
- a compound (b2) having one anionic group and no aromatic ring and the like.
- the amount of emulsifier used in emulsion polymerization is preferably 0.5 to 10 parts by weight, more preferably 1 to 8 parts by weight, based on 100 parts by weight of all the monomers used.
- radical initiators include, but are not limited to, inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, and hydrogen peroxide; t-butyl peroxide, cumene hydroperoxide, p-menthane hydroperoxide, di-t-butyl peroxide, t-butyl cumyl peroxide, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, dibenzoyl peroxide, 3,5,5-trimethylhexanoyl organic peroxides such as peroxides and t-butyl peroxyisobutyrate; azo compounds such as azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and methyl
- polymerization initiators may be used singly or in combination of two or more.
- the amount of polymerization initiator to be used is preferably 0.01 to 2 parts by weight, more preferably 0.05 to 1.5 parts by weight, per 100 parts by weight of all the monomers used.
- molecular weight modifiers include, but are not limited to, ⁇ -methylstyrene dimer; mercaptans such as t-dodecylmercaptan, n-dodecylmercaptan and octylmercaptan; halogenated compounds such as carbon tetrachloride, methylene chloride and methylene bromide; hydrocarbons; sulfur-containing compounds such as tetraethylthiuram disulfide, dipentamethylenethiuram disulfide, and diisopropyl xanthogen disulfide; These molecular weight modifiers may be used singly or in combination of two or more.
- the amount of the molecular weight modifier used varies depending on its type, but is preferably 0.1 to 1.5 parts by weight, more preferably 0.2 to 1.0 parts by weight, based on 100 parts by weight of the total monomers used. Department.
- Emulsion polymerization is usually carried out in water.
- the amount of water used is preferably 80 to 500 parts by weight, more preferably 100 to 200 parts by weight, per 100 parts by weight of all the monomers used.
- secondary polymerization materials other than the above may be used as necessary.
- auxiliary materials for polymerization include chelating agents, dispersants, pH adjusters, oxygen scavengers, particle size adjusters, and the like, and the types and amounts used are not particularly limited.
- Methods of adding the monomers include, for example, a method of collectively adding the monomers used in the reaction vessel, a method of continuously or intermittently adding the monomers as the polymerization progresses, and a method of partially adding the monomers. reaction to a specific conversion rate, and then the remaining monomers are added continuously or intermittently for polymerization, and any method may be employed.
- the composition of the mixture can be constant or varied.
- each monomer may be added to the reaction vessel after previously mixing various monomers to be used, or may be added to the reaction vessel separately.
- the polymerization temperature during emulsion polymerization is not particularly limited, but is usually 0 to 95°C, preferably 5 to 70°C.
- the polymerization time is not particularly limited, but is usually about 5 to 40 hours.
- unreacted monomers may be removed and the solid content concentration and pH may be adjusted.
- the glass transition temperature of the polymer constituting the latex of the polymer is preferably 10° C. or less, more preferably ⁇ 55° C. to 5° C., still more preferably, from the viewpoint that the effect of the present invention becomes more remarkable. is -45 to 0°C, particularly preferably -40 to -10°C.
- a method for adjusting the glass transition temperature of the polymer to the above range is not particularly limited, but includes, for example, a method for adjusting the content ratio of each monomer unit constituting the polymer to the above range.
- the volume average particle diameter of the polymer particles constituting the polymer latex is preferably 30 to 1000 nm, more preferably 50 to 500 nm, still more preferably 70, from the viewpoint that the effect of the present invention becomes more remarkable. ⁇ 200 nm.
- the volume-average particle size of the polymer particles constituting the polymer latex can be measured using, for example, a light scattering diffraction particle measuring device.
- the surface tension of the polymer latex at 25° C. is preferably 20 to 70 mN/m, more preferably 25 to 60 mN/m, still more preferably 30 to 50 mN/m, from the viewpoint that the effect of the present invention becomes more pronounced. is.
- the difference between the surface tension of the polymer latex at 25°C and the surface tension of the anionic surfactant at 25°C is preferably -10 to 15 mN/m, more than It is preferably -5 to 10 mN/m, more preferably 0 to 8 mN/m.
- the surface tension of the polymer latex at 25°C and the difference between the surface tension of the polymer latex at 25°C and the surface tension of the anionic surfactant at 25°C are described in Examples. method.
- the dip molding latex composition of the present invention contains an anionic surfactant in addition to the polymer latex.
- the anionic surfactants used in the present invention include a compound (a) having one anionic group and an aromatic ring, and a compound (b1) having two or more anionic groups and a benzene ring and/or an anion. and a compound (b2) having one functional group and no aromatic ring.
- Compound (a) having one anionic group and having an aromatic ring is a compound having only one anionic group and having an aromatic ring is.
- Examples of the anionic group possessed by the compound (a) include a carboxylic acid group (--COOH), a carboxylic acid group (--COOX), a sulfonic acid group (--SO 3 H), a sulfonic acid group (--SO 3 X), and a sulfate ester.
- X is an atom or molecule that constitutes a cation.
- Examples of X include metal atoms such as lithium, sodium, potassium, calcium, magnesium and aluminum, ammonium and the like, with sodium, potassium and ammonium being preferred, and sodium being more preferred.
- the anionic group possessed by the compound (a) is preferably a sulfonate group or a sulfate ester group, more preferably a sulfonate group, and still more preferably a sodium sulfonate group (--SO 3 Na). That is, compound (a) is preferably a sulfonate or a sulfate, more preferably a sulfonate, and even more preferably a sodium sulfonate.
- the aromatic ring of the compound (a) is not particularly limited as long as it is a ring having aromaticity, but non-condensed aromatic rings such as benzene ring, condensed aromatic rings such as naphthalene ring, and the like can be mentioned.
- the compound (a) preferably has a non-condensed aromatic ring, and although the number of non-condensed aromatic rings in the compound (a) is not particularly limited, one is preferred.
- the non-condensed aromatic ring of the compound (a) is preferably a benzene ring, and although the number of benzene rings in the compound (a) is not particularly limited, one is preferred.
- the compound (a) preferably has an alkyl group.
- the alkyl group in compound (a) preferably has 8 to 16 carbon atoms, more preferably 10 to 14 carbon atoms.
- Examples of the compound (a) include sodium decylbenzenesulfonate, potassium decylbenzenesulfonate, sodium undecylbenzenesulfonate, potassium undecylbenzenesulfonate, sodium dodecylbenzenesulfonate, potassium dodecylbenzenesulfonate, and tridecylbenzenesulfonic acid.
- Alkylbenzenesulfonates such as sodium, potassium tridecylbenzenesulfonate, sodium tetradecylbenzenesulfonate, and potassium tetradecylbenzenesulfonate can be mentioned.
- Acid salts are preferred, sodium alkylbenzenesulfonate is preferred, sodium dodecylbenzenesulfonate is preferred.
- Compound (a) may be used alone or in combination of two or more.
- the molecular weight of compound (a) is preferably from 100 to 600, more preferably from 200 to 500, even more preferably from 300 to 400, from the viewpoint that the effects of the present invention become more pronounced.
- the latex composition for dip molding of the present invention comprises, in addition to the compound (a), a compound (b1) having two or more anionic groups and a benzene ring and/or an aromatic ring having one anionic group. It contains the compound (b2) that does not have That is, the latex composition used in the present invention contains at least one of the compound (b1) and the compound (b2) in addition to the compound (a), and in addition to the compound (a), the compound (b1) and compound (b2).
- the latex composition for dip molding of the present invention more preferably contains at least the compound (b1) in addition to the compound (a) from the viewpoint that the effects of the present invention become more remarkable.
- the number of anionic groups may be two or more, particularly although not limited, the number is preferably two.
- Examples of the anionic group possessed by the compound (b1) include a carboxylic acid group (--COOH), a carboxylic acid group (--COOX), a sulfonic acid group (--SO 3 H), a sulfonic acid group (--SO 3 X), and a sulfate ester.
- X is an atom or molecule that constitutes a cation.
- Examples of X include metal atoms such as lithium, sodium, potassium, calcium, magnesium and aluminum, ammonium and the like, with sodium, potassium and ammonium being preferred, and sodium being more preferred.
- the anionic group possessed by the compound (b1) is preferably a sulfonate group or a sulfate ester group, more preferably a sulfonate group, and still more preferably a sodium sulfonate group (--SO 3 Na). That is, compound (b1) is preferably a sulfonate or a sulfate ester salt, more preferably a sulfonate, and even more preferably a sodium sulfonate.
- the two or more anionic groups possessed by compound (b1) may be the same or different, but are preferably the same.
- the compound (b1) has a benzene ring.
- the number of benzene rings in the compound (b1) is not particularly limited, it is preferably two or more, more preferably two.
- Compound (b1) may have an aromatic ring other than the benzene ring.
- aromatic rings other than benzene rings include heteroatom-containing non-condensed aromatic rings and condensed aromatic rings such as naphthalene rings.
- the number of aromatic rings other than the benzene ring in the compound (b1) is preferably 2 or less, more preferably 1 or less, and still more preferably 0. That is, compound (b1) preferably does not have an aromatic ring other than a benzene ring.
- the compound (b1) preferably has an ether bond, and more preferably has a diphenyl ether structure.
- the compound (b1) preferably has an alkyl group.
- the alkyl group in compound (b1) preferably has 8 to 16 carbon atoms, more preferably 10 to 14 carbon atoms.
- Examples of the compound (b1) include alkyldiphenylether disulfonates such as disodium alkyldiphenyletherdisulfonate, dipotassium alkyldiphenyletherdisulfonate, and diammonium alkyldiphenyletherdisulfonate. Among them, the effect of the present invention becomes more remarkable. From this point of view, disodium alkyldiphenyl ether disulfonate is preferable, disodium alkyldiphenylether disulfonate having an alkyl group having 8 to 16 carbon atoms is more preferable, and disodium alkyldiphenylether disulfonate having an alkyl group having 10 to 14 carbon atoms is preferable. Sodium is more preferred. Compound (b1) may be used alone or in combination of two or more.
- the molecular weight of compound (b1) is preferably from 100 to 1000, more preferably from 200 to 850, even more preferably from 300 to 750, and particularly preferably from 400 to 650, from the viewpoint that the effects of the present invention become more pronounced.
- a compound (b2) having one anionic group and no aromatic ring (hereinafter referred to as "compound (b2)" as appropriate) has only one anionic group and an aromatic ring It is a compound that does not have
- Examples of the anionic group possessed by the compound (b2) include a carboxylic acid group (--COOH), a carboxylic acid group (--COOX), a sulfonic acid group (--SO 3 H), a sulfonic acid group (--SO 3 X), and a sulfate ester.
- X is an atom or molecule that constitutes a cation.
- Examples of X include metal atoms such as lithium, sodium, potassium, calcium, magnesium and aluminum, ammonium and the like, with sodium, potassium and ammonium being preferred, and sodium being more preferred.
- the anionic group possessed by the compound (b2) is preferably a sulfonate group or a sulfate group, more preferably a sulfate group, and even more preferably a sodium sulfate group (--OSO 3 Na). That is, the compound (b2) is preferably a sulfonate or a sulfate, more preferably a sulfate, and even more preferably a sodium sulfate.
- the compound (b2) preferably has an alkyl group.
- the number of carbon atoms in the alkyl group in compound (b2) is preferably 8-16, more preferably 10-14.
- Compound (b2) includes fatty acid salts such as sodium laurate, potassium myristate, sodium palmitate, potassium oleate, sodium linolenate, sodium rosinate; di(2-ethylhexyl)sodium sulfosuccinate, di(2-ethylhexyl) ) Alkyl sulfosuccinates such as potassium sulfosuccinate and sodium dioctyl sulfosuccinate; sodium octyl sulfate, potassium octyl sulfate, sodium decyl sulfate, potassium decyl sulfate, sodium undecyl sulfate, potassium undecyl sulfate, sodium dodecyl sulfate (sodium lauryl sulfate), dodecyl Alkyl sulfate ester salts such as potassium sulfate (potassium lauryl s
- the molecular weight of compound (b2) is preferably from 100 to 600, more preferably from 200 to 450, even more preferably from 250 to 350, from the viewpoint that the effects of the present invention become more pronounced.
- the compound (a) is a sulfonate or a sulfate ester salt
- the compound (b1) or the compound (b2) ) is preferably a sulfonate or a sulfate.
- the content of the compound (a) in the latex composition for dip molding of the present invention is 100 parts by weight of the polymer component contained in the latex composition for dip molding, from the viewpoint that the effect of the present invention becomes more pronounced.
- 0.1 to 5.0 parts by weight is preferable, 0.5 to 3.0 parts by weight is more preferable, 0.8 to 2.4 parts by weight is more preferable, 1.0 to 2.0 parts by weight Part is particularly preferred.
- the effect of the present invention becomes more remarkable as the content of the compound (b1) in the latex composition for dip molding of the present invention.
- 0 to 5.0 parts by weight is more preferred, and 1.2 to 4.5 parts by weight is particularly preferred.
- the effect of the present invention becomes more remarkable as the content of the compound (b2) in the latex composition for dip molding of the present invention.
- 0 to 5.0 parts by weight is more preferred, and 1.2 to 4.5 parts by weight is particularly preferred.
- the total content of the compound (b1) and the content of the compound (b2) is the latex composition for dip molding from the viewpoint that the effect of the present invention becomes more remarkable.
- 100 parts by weight of the polymer component contained therein 0.1 to 10.0 parts by weight is preferable, 0.5 to 7.0 parts by weight is more preferable, and 1.0 to 5.0 parts by weight is further 1.2 to 4.5 parts by weight is particularly preferred.
- the weight ratio of the content of compound (a) to the total content of compound (b1) and compound (b2) is preferably from 5:95 to 95:5, more preferably from 10:90 to 90:10, from the viewpoint that the effect of the present invention becomes more pronounced. , 15:85 to 80:20, and particularly preferably 20:80 to 70:30.
- the latex composition for dip molding of the present invention preferably contains a latex of the polymer (A) having a glass transition temperature of 10° C. or lower, and a latex of the polymer (A) having a glass transition temperature of 10° C. or lower. In addition, it is more preferable to contain a latex of polymer (B) having a glass transition temperature of more than 10°C.
- Polymer (A) having a glass transition temperature of 10°C or lower (hereinafter referred to as “polymer (A) latex”) having a glass transition temperature of 10°C or lower ( A) (hereinafter referred to as “polymer (A)” as appropriate) is not particularly limited, but examples include nitrile rubber (NBR), natural rubber (NR), styrene-butadiene rubber (SBR), synthetic poly Examples include conjugated diene polymers such as isoprene rubber (IR), polybutadiene rubber (BR), styrene-isoprene copolymer rubber, styrene-isoprene-styrene copolymer rubber, polybutyl acrylate, butyl rubber (IIR), and the like.
- NBR nitrile rubber
- NR natural rubber
- SBR styrene-butadiene rubber
- synthetic poly Examples include conjugated diene polymers such as isoprene rubber (IR
- nitrile rubber NBR
- SBR styrene-butadiene rubber
- IR synthetic polyisoprene rubber
- polybutyl acrylate Preferred are nitrile group-containing conjugated diene polymers. These conjugated diene-based polymers may be carboxyl group-containing conjugated diene-based polymers.
- the polymer (A) having a glass transition temperature of 10° C. or lower those having a glass transition temperature of 10° C. or lower among those mentioned above as polymers constituting the latex of the polymer used in the present invention are suitable.
- the polymer (A) having a glass transition temperature of 10° C. or lower those mentioned above as the nitrile group-containing conjugated diene polymer capable of forming the latex of the polymer used in the present invention are suitable.
- the volume-average particle diameter of the polymer particles constituting the polymer (A) latex is preferably 30 to 1000 nm, more preferably 50 to 500 nm, and even more preferably 70 to 200 nm.
- the polymer (B) can be finely dispersed more favorably in the polymer (A) in the obtained dip molded article. As a result, the effects of the present invention become more pronounced, and the mechanical properties of the resulting dip-molded article can be enhanced.
- a polymer (B) (hereinafter referred to as “polymer (B)” as appropriate) is not particularly limited, but examples thereof include acrylic resins, PTFE resins, acrylonitrile-styrene (AS) resins, polyurethanes, vinyl chloride resins, and polystyrene resins. etc., and among these, acrylic resins are preferred. These polymers may be used individually by 1 type, and may be used in combination of 2 or more type.
- Acrylic resins include, for example, acrylic acid esters, methacrylic acid esters, acrylic acid, homopolymers of methacrylic acid, copolymers of acrylic acid esters and acrylic acid, copolymers of acrylic acid esters and methacrylic acid, methacrylic acid Copolymer of acid ester and acrylic acid, copolymer of methacrylic acid ester and methacrylic acid, copolymer of acrylic acid ester, methacrylic acid ester and acrylic acid, acrylic acid ester, methacrylic acid ester and methacrylic acid and copolymers of acrylic acid ester, methacrylic acid ester, acrylic acid and methacrylic acid.
- a homopolymer of acrylic acid ester, methacrylic acid ester, acrylic acid, or methacrylic acid and a homopolymer of methacrylic acid ester is used.
- the homopolymer of acrylic acid ester includes not only homopolymers of the same acrylic acid ester, but also copolymers of two or more acrylic acid esters (for example, ethyl acrylate and butyl acrylate).
- homopolymers of methacrylic acid esters include not only homopolymers of the same methacrylic acid esters, but also copolymers of two or more methacrylic acid esters.
- the total content of acrylic acid ester, methacrylic acid ester, acrylic acid, and methacrylic acid units in the acrylic resin is preferably 40 to 100% by weight, more preferably 70%, based on the total monomer units. ⁇ 100% by weight.
- Acrylic esters used to form acrylic resins include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec- Butyl, tert-butyl acrylate, n-pentyl acrylate, sec-pentyl acrylate, isopentyl acrylate, neopentyl acrylate, n-hexyl acrylate, isohexyl acrylate, neohexyl acrylate, sec-hexyl acrylate, and acrylic acid tert-hexyl and the like, among which methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, and n-butyl acrylate are preferred, and methyl acrylate is more preferred.
- Methacrylate esters used to form acrylic resins include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec- Butyl, tert-butyl methacrylate, n-pentyl methacrylate, sec-pentyl methacrylate, isopentyl methacrylate, neopentyl methacrylate, n-hexyl methacrylate, isohexyl methacrylate, neohexyl methacrylate, sec-hexyl methacrylate, and methacryl acid tert-hexyl and the like, among which methyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, and n-butyl methacrylate are preferred, and methyl methacrylate
- the acrylic resin may be obtained by copolymerizing an acrylic acid ester monomer, a methacrylic acid ester monomer, an acrylic acid monomer, or other monomers copolymerizable with a methacrylic acid monomer.
- copolymerizable monomers include ⁇ -olefin monomers such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene; styrene, ⁇ -methylstyrene , aromatic monomers such as vinylpyridine; ⁇ , ⁇ -ethylenically unsaturated polycarboxylic acids such as maleic acid, fumaric acid and itaconic acid; ⁇ , such as monomethyl maleate, monoethyl maleate and monoethyl itaconate, ⁇ -ethylenically unsaturated polycarboxylic acid monoesters; ⁇ , ⁇ -ethylenically unsaturated polycarboxylic acids such as dimethyl maleate, di-n-butyl fumarate, dimethyl itaconate, and di-2-ethylhexyl itaconate Polyvalent esters; vinyl ester monomers such as vinyl acetate and vinyl propionate; ⁇ , ⁇ -
- the method for producing the acrylic resin latex as the polymer (B) is not particularly limited as long as it is a method capable of polymerizing the above monomers. A method by turbidity polymerization and the like can be mentioned.
- the polymer (B) is preferably obtained by using a persulfate such as sodium persulfate, potassium persulfate and ammonium persulfate as a polymerization initiator.
- a persulfate such as sodium persulfate, potassium persulfate and ammonium persulfate
- the polymer (B) can be made to have a sulfuric acid group at the polymer chain end as a residue of the polymerization initiator, whereby the latex of the polymer (B) can be chemically Better stability can be achieved.
- the weight average molecular weight (Mw) of the acrylic resin as the polymer (B) is not particularly limited, but is preferably 10,000 to 10,000,000, more preferably 10,000 to 5,000,000. be.
- the glass transition temperature of the polymer (B) is higher than 10°C, and from the viewpoint that the effects of the present invention become more pronounced, it is preferably 30°C or higher, more preferably 70°C or higher, and even more preferably It is 95° C. or higher, particularly preferably 105° C. or higher.
- the upper limit of the glass transition temperature of the polymer (B) is not particularly limited, it is preferably 200°C or lower, more preferably 150°C or lower.
- a method for adjusting the glass transition temperature of the polymer (B) to the above range is not particularly limited, but includes a method of adjusting the content ratio of each monomer unit constituting the polymer.
- the latex composition for dip molding of the present invention comprises a latex of polymer (A) having a glass transition temperature of 10°C or lower and a latex of polymer (A) having a glass transition temperature of higher than 10°C. It is preferably a latex composition for dip molding obtained by mixing a latex of a certain polymer (B) in a latex state.
- the particles of the polymer (A) and the polymer (B) can be uniformly finely dispersed. Then, when a dip-molded article is formed by dip molding, the polymer (B) is finely dispersed in the matrix of the polymer (A) in the resulting dip-molded article, and the polymer (B) is co-precipitated. can be done. Therefore, the action of the finely dispersed polymer (B) makes it possible to make the resulting dip-molded article even more excellent in wet grip properties.
- the volume average particle diameter of the particles of the polymer (B) constituting the latex of the polymer (B) is is preferably smaller than the volume average particle diameter of the particles of the polymer (A) constituting the
- the volume average particle diameter of the particles of the polymer (B) constituting the latex of the polymer (B) is preferably 1 to 200 nm, more preferably 5 to 160 nm, even more preferably 5 to 120 nm, still more preferably 10 to 100 nm. 100 nm, particularly preferably 20 to 80 nm.
- the polymer (B) can be finely dispersed more favorably in the polymer (A) in the obtained dip molded article. As a result, the effects of the present invention become more pronounced, and the mechanical properties of the resulting dip-molded article can be enhanced.
- the amount and the content of the polymer (B) are not particularly limited, but the content of the polymer (A) in 100% by weight of the polymer component contained in the latex composition for dip molding is 75 to 100% by weight. %, more preferably 80 to 99% by weight, even more preferably 85 to 95% by weight.
- the content of the polymer (B) is preferably 0 to 25% by weight, more preferably 1 to 20% by weight, based on 100% by weight of the polymer component contained in the latex composition for dip molding.
- the weight ratio of the polymer (A) to the polymer (B) is The ratio is preferably 75:25 to 100:0, more preferably 80:20 to 99:1, still more preferably 85:15 to 95:5, since the effect of the invention becomes more pronounced.
- the latex composition for dip molding of the present invention preferably further contains a sulfur-based cross-linking agent in addition to the polymer latex and the anionic surfactant described above.
- the sulfur-based cross-linking agent is not particularly limited, but sulfur such as powdered sulfur, sulfur flowers, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur; sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, dibenzothia Sulfur-containing compounds such as dil disulfide, caprolactam disulfide, phosphorus-containing polysulfide, and polymeric polysulfides; sulfur-donating compounds such as tetramethylthiuram disulfide, selenium dimethyldithiocarbamate, and 2-(4′-morpholinodithio)benzothiazole; is mentioned.
- sulfur-based cross-linking agents may be used singly or in combination of two or more.
- the content of the sulfur-based cross-linking agent is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, with respect to 100 parts by weight of the polymer component contained in the latex composition for dip molding. It is preferably 0.1 to 2 parts by weight.
- the latex composition for dip molding of the present invention preferably further contains a cross-linking accelerator (vulcanization accelerator) and zinc oxide in addition to the sulfur-based cross-linking agent.
- a cross-linking accelerator vulcanization accelerator
- zinc oxide in addition to the sulfur-based cross-linking agent.
- cross-linking accelerator examples include, but are not limited to, dithiocarbamines such as diethyldithiocarbamate, dibutyldithiocarbamate, di-2-ethylhexyldithiocarbamate, dicyclohexyldithiocarbamate, diphenyldithiocarbamate, and dibenzyldithiocarbamate.
- dithiocarbamines such as diethyldithiocarbamate, dibutyldithiocarbamate, di-2-ethylhexyldithiocarbamate, dicyclohexyldithiocarbamate, diphenyldithiocarbamate, and dibenzyldithiocarbamate.
- the content of the cross-linking accelerator is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the polymer component contained in the latex composition for dip molding.
- the content of zinc oxide is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, with respect to 100 parts by weight of the polymer component contained in the latex composition for dip molding. .
- the latex composition for dip molding of the present invention may further contain a water-soluble polymer.
- water-soluble polymers examples include vinyl compounds such as polyvinyl alcohol and polyvinylpyrrolidone; cellulose derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose and carboxymethyl cellulose and salts thereof; polycarboxylic acid compounds such as polyacrylic acid and sodium salts thereof. ; polyoxyethylene derivatives such as polyethylene glycol ether; and the like.
- cellulose derivatives and salts thereof are preferred, and carboxymethylcellulose and sodium salts thereof are more preferred.
- the content of the water-soluble polymer is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the polymer component contained in the latex composition for dip molding.
- the viscosity of a 4% by weight aqueous solution of the water-soluble polymer is not particularly limited, but is preferably 1 mPa s or more, more preferably 10 mPa s or more, preferably 20,000 mPa s or less, and 10,000 mPa s. The following are more preferred.
- the viscosity of a 1% by weight aqueous solution of the water-soluble polymer is not particularly limited, but is preferably 1 mPa s or more, more preferably 10 mPa s or more, preferably 20,000 mPa s or less, and 10,000 mPa s. The following are more preferred.
- the viscosity of the water-soluble polymer aqueous solution can be measured, for example, using a Brookfield viscometer under the conditions of 25° C. and 6 rpm.
- the water-soluble polymer is not particularly limited as long as it is soluble in water, and the solubility of the water-soluble polymer in water is not particularly limited, but is preferably 1 g or more, more preferably 1 g or more, with respect to 100 g of water at a temperature of 25 ° C. It is 7 g or more, particularly preferably 10 g or more.
- the upper limit of the water solubility of the water-soluble polymer is not particularly limited, but is usually 1,000,000 g or less.
- the weight average molecular weight (Mw) of the water-soluble polymer is not particularly limited, but is preferably 100 or more, more preferably 1,000 or more, preferably 5,000,000 or less, and more preferably 3,000,000 or less.
- the amount of the water-soluble polymer is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the polymer component contained in the latex composition for dip molding of the present invention. and more preferably 0.15 to 4.5 parts by weight.
- the blending amount of the water-soluble polymer is within the above range, the resulting dip-molded article has even better wet grip properties.
- the latex composition for dip molding of the present invention includes carbon black, silica, calcium carbonate, aluminum silicate, magnesium silicate, calcium silicate, magnesium oxide, zinc (meth)acrylate, magnesium (meth)acrylate and titanium oxide.
- the amount of the filler compounded is preferably 0.5 to 30 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the polymer component contained in the latex composition for dip molding of the present invention. More preferably 2 to 5 parts by weight. When the blending amount of the filler is within the above range, the resulting dip-molded article has even better wet grip properties.
- the latex composition for dip molding of the present invention may optionally contain additives other than the above water-soluble salts and fillers, such as anti-aging agents, antioxidants, preservatives, antibacterial agents, wetting agents, Various additives such as dispersants, pigments, dyes, reinforcing agents, and pH adjusters can also be added in predetermined amounts.
- the volume average particle size of the polymer particles in the latex composition for dip molding of the present invention is preferably 30 to 250 nm, more preferably 30 to 200 nm, still more preferably 50 to 180 nm.
- the obtained latex composition for dip molding can be made excellent in storage stability, and the obtained The dip molded article can be made more excellent in wet grip properties.
- the volume average particle size of the polymer particles in the latex composition for dip molding of the present invention can be measured using, for example, a light scattering diffraction particle measuring device.
- the solid content concentration of the latex composition for dip molding of the present invention is preferably 20 to 65% by weight, more preferably 30 to 60% by weight, still more preferably 35 to 55% by weight.
- Methods for adjusting the solid content concentration of the latex composition for dip molding of the present invention within the range described above include, for example, a method of adjusting the solid content concentration of each component such as a polymer latex, and a concentration treatment or dilution treatment described later.
- the pH of the latex composition for dip molding of the present invention is preferably 5-13, more preferably 7-10, still more preferably 7.5-9.
- a latex composition for dip molding containing polymer latex, compound (a), compound (b1) and/or compound (b2) is obtained. It is not particularly limited as long as it is a manufacturing method that can be used.
- a method for producing the latex composition for dip molding of the present invention a method of preparing two or more types of polymer latex and mixing them in a latex state is preferable.
- a method for producing the latex composition for dip molding of the present invention a method of preparing two or more types of polymer latex and mixing them in a latex state will be exemplified below.
- the latex composition for dip molding of the present invention includes, for example, a latex (A 1 -a) containing a first polymer (A 1 ) having a glass transition temperature of 10° C. or lower and a compound ( a ), and a glass A production method in which a latex (A 2 -b) containing a second polymer (A 2 ) having a transition temperature of 10° C. or less and a compound (b1) and/or a compound (b2) is mixed in a latex state, Obtainable.
- the abbreviations "polymer (A 1 )", “latex (A 1 -a)", “polymer (A 2 )” and “latex (A 2 -b)” are used as appropriate.
- the latex composition for dip molding of the present invention As a method for producing the latex composition for dip molding of the present invention, a method of mixing latex (A 1 -a) and latex (A 2 -b) in a latex state is preferable, and the dip of the present invention obtained by this method is preferable.
- the latex composition for molding can further improve the balance between flexibility and wet grip while realizing excellent chemical liquid permeation resistance of the obtained dip-molded article. The reason for this is not clear, but by mixing the latex (A 1 -a) and the latex (A 2 -b) in the latex state, aggregates of appropriate size are generated, and the resulting dip-molded product It is presumed that this is due to the formation of an appropriate uneven structure on the surface.
- the composition of polymer (A 1 ) and the composition of polymer (A 2 ) may be the same or different.
- the polymer (A 1 ) is a nitrile group-containing conjugated diene polymer
- the polymer (A 2 ) is a nitrile group-containing conjugated diene polymer having the same or different composition as the polymer (A 1 ).
- it may be a polymer other than the nitrile group-containing conjugated diene polymer (for example, polybutyl acrylate).
- the polymer (A 2 ) is a nitrile group-containing conjugated diene polymer
- the polymer (A 1 ) is a nitrile group-containing conjugated diene polymer having the same or different composition as the polymer (A 2 ).
- it may be a polymer other than the nitrile group-containing conjugated diene polymer (for example, polybutyl acrylate).
- the difference between the glass transition temperature of the polymer (A 1 ) and the glass transition temperature of the polymer (A 2 ) is preferably 30° C. or less, more preferably 20° C. or less, and 15° C. or less. It is more preferably 10°C or lower, particularly preferably 10°C or lower, and most preferably 5°C or lower.
- the latex composition for dip molding of the present invention includes, for example, a latex (Aa) containing a polymer (A) having a glass transition temperature of 10° C. or less and a compound (a), and a latex (Aa) having a glass transition temperature of A latex (Bb) containing the polymer (B) having a temperature higher than 10° C. and the compound (b1) and/or the compound (b2) may be obtained by a production method of mixing in a latex state.
- abbreviations such as “latex (Aa)” and “latex (Bb)” are used as appropriate.
- the latex composition for dip molding of the present invention is, for example, a latex (Ab ), and a latex (Ba) containing a polymer (B) having a glass transition temperature of more than 10° C. and a compound (a), may be obtained by a production method of mixing in a latex state.
- a latex (Ab) a latex (Ab )
- a latex (Ab) latex (Ba) containing a polymer (B) having a glass transition temperature of more than 10° C. and a
- a latex
- the abbreviations “latex (Ab)” and “latex (Ba)” are used as appropriate.
- the compound (a) is contained in the latex containing the polymer and the compound (a) (latex (A 1 -a), latex (Aa), latex (Ba))
- the method of causing is not particularly limited, for example, a method of obtaining a latex containing a polymer and a compound (a) by performing polymerization in the presence of the compound (a), a method of preparing a latex containing a polymer, A method of adding the compound (a) can be mentioned. Among them, the method of polymerizing in the presence of the compound (a) is preferable.
- the latex containing the polymer and the compound (a) may further contain the compound (b1) and/or the compound (b2).
- the method for containing the compound (b1) and/or the compound (b2) is not particularly limited, and for example, the polymer is polymerized in the presence of the compound (b1) and/or the compound (b2). and a method of obtaining a latex containing compound (b1) and/or compound (b2), and a method of adding compound (b1) and/or compound (b2) after preparing a latex containing a polymer.
- the method of polymerizing in the presence of the compound (b1) and/or the compound (b2) is preferred.
- a latex containing a polymer and compound (b1) and/or compound (b2) (latex (A 2 -b), latex (Bb), latex (Ab))
- the method for containing the compound (b1) and/or the compound (b2) is not particularly limited. Examples include a method of obtaining a latex containing (b1) and/or compound (b2), and a method of adding compound (b1) and/or compound (b2) after preparing a latex containing a polymer. Among them, the method of polymerizing in the presence of the compound (b1) and/or the compound (b2) is preferred.
- the latex containing the polymer and compound (b1) and/or compound (b2) may further contain compound (a).
- the method of incorporating the compound (a) is not particularly limited, for example, a method of obtaining a latex containing the polymer and the compound (a) by performing polymerization in the presence of the compound (a), A method of adding the compound (a) after preparing a latex containing a polymer can be mentioned. Among them, the method of polymerizing in the presence of the compound (a) is preferable.
- latexes may be mixed in a latex state by appropriately combining the methods of mixing two types of latexes as described above.
- latex (A 1 -a), latex (A 2 -b), and latex (Ba) and/or latex (Bb) may be mixed in a latex state.
- the latex composition for dip molding of the present invention may be obtained through concentration treatment or dilution treatment.
- the latex composition for dip molding of the present invention is preferably obtained through a concentration treatment.
- the concentration treatment method is not particularly limited, and examples thereof include vacuum distillation, normal pressure distillation, centrifugation, membrane concentration, and the like. Among these, the concentration method accompanied by heating is preferable, and the vacuum distillation accompanied by heating is more preferable. By adopting a concentration method that involves heating, it is possible to reduce the number of odor-causing bacteria, or to suppress the growth of odor-causing bacteria. can be assumed.
- the heating temperature is preferably 50°C to 100°C.
- the pressure is preferably 20 kPa to 90 kPa.
- the concentration treatment may be applied to a mixture containing some of the components to be compounded in the latex composition for dip molding, or to a mixture containing all of the components to be compounded in the latex composition for dip molding. good too.
- Each component that is blended as necessary into the composition containing the polymer latex, the compound (a), and the compound (b1) and/or the compound (b2) obtained by the above production method. may be added.
- the dip-molded article of the present invention is a molded article obtained using the dip-molding latex composition of the present invention described above, and is usually dip-molded using the dip-molding latex composition of the present invention described above. obtained by Since the dip-molded article of the present invention is obtained using the above-described dip-molding latex composition of the present invention, it has excellent resistance to chemical permeation and excellent wet grip and flexibility in a well-balanced manner.
- the dip-molded article of the present invention contains the two or more polymers, and each polymer in the dip-molded article is usually the same as the content of each polymer in the latex composition for dip molding.
- the dip-molded product of the present invention is preferably a laminate having a substrate and a polymer layer formed on the substrate using the dip-molding latex composition of the present invention.
- the laminate may be, for example, a laminate of a substrate obtained by immersing the substrate in the dip molding latex composition of the present invention and a polymer layer composed of the dip molding latex composition. good.
- the dip molded article of the present invention may be a film molded article made of the latex composition for dip molding, which is obtained by immersing a dip mold in the latex composition for dip molding of the present invention. .
- the dip-molded article of the present invention is a laminate of a substrate and a polymer layer comprising the latex composition for dip molding of the present invention will be described as an example. It is not limited to this embodiment.
- the base material is not particularly limited, a fiber base material can be suitably used when the dip molded article of the present invention is used as a protective glove.
- the fiber base material is not particularly limited, for example, it is possible to use twisted monofilament yarns as fibers and to form a glove shape by weaving the twisted yarns.
- the average thickness of the fiber base material is preferably 50-3,000 ⁇ m, more preferably 100-2,000 ⁇ m.
- the dip-molded article of the present invention can be produced, for example, by immersing a substrate in the dip-molding latex composition to form a polymer layer composed of the dip-molding latex composition on the substrate. can be done. In this case, it is preferable to immerse the substrate in the latex composition for dip molding in a state in which the substrate is previously covered with a molding die having a desired shape.
- the molding die for covering the substrate is not particularly limited, but various materials such as porcelain, glass, metal, and plastic can be used.
- the shape of the molding die may be a desired shape according to the shape of the final product.
- various types of glove molds such as a mold having a shape from the wrist to the fingertips are used as the mold for covering the substrate. is preferred.
- the base material is previously immersed in the coagulant solution so that the coagulant solution adheres to the base material before the base material is immersed in the latex composition for dip molding.
- the drying temperature at this time is not particularly limited and may be selected according to the solvent used, but is preferably 10 to 80°C, more preferably 15 to 70°C. Although the drying time is not particularly limited, it is preferably 600 to 1 second, more preferably 300 to 5 seconds.
- the substrate to which the coagulant solution has been adhered is immersed in the latex composition for dip molding while being covered with a molding die having a desired shape, thereby solidifying the latex composition for dip molding.
- a polymer layer comprising a dip molding latex composition is deposited on the substrate.
- the drying temperature at this time is not particularly limited, but is preferably 10 to 80°C, more preferably 15 to 80°C. Although the drying time is not particularly limited, it is preferably 120 minutes to 5 seconds, more preferably 60 minutes to 10 seconds.
- the latex composition for dip molding may be previously aged (also referred to as pre-vulcanization). .
- the temperature conditions for aging are not particularly limited, but are preferably 20 to 50°C.
- the time for aging is preferably 4 hours or more and 120 hours or less, more preferably 24 hours, from the viewpoint of preventing separation between the substrate and the polymer layer and improving the mechanical properties of the polymer layer. 72 hours or less.
- the heating temperature for cross-linking is preferably 60 to 160°C, more preferably 80 to 150°C. By setting the heating temperature within the above range, the time required for the cross-linking reaction can be shortened and the productivity of the dip-molded product can be improved. It is possible to improve the physical properties of the dip-molded product.
- the heating time for cross-linking may be appropriately selected according to the heating temperature, but is usually 5 to 120 minutes.
- the polymer layer formed on the base material is immersed in warm water of 20 to 80° C. for about 0.5 to 60 minutes to obtain a heavy weight. It is preferable to remove water-soluble impurities (emulsifiers, water-soluble polymers, coagulants, etc.) from the combined layer.
- water-soluble impurities emulsifiers, water-soluble polymers, coagulants, etc.
- drying temperature and drying time at this time are not particularly limited, but may be the same as the drying temperature and drying time in the drying step after immersion in the latex composition for dip molding described above.
- the dip-molded article is obtained by detaching (or demolding) from the molding die.
- detaching or demolding
- the dip molded body Before or after detaching the dip molded body from the molding die, it may be further heat-treated at a temperature of 60 to 120°C for 10 to 120 minutes (post-crosslinking step). After the dip-molded body is removed from the molding die, a surface treatment layer may be formed on the inner and/or outer surfaces of the dip-molded body by chlorination treatment, coating treatment, or the like.
- a method for foaming a dip-molding latex composition other than the dip-molding latex composition of the present invention and performing dip molding can be considered.
- the arithmetic mean roughness Ra of the surface of the polymer layer of the dip-molded article to be obtained tends to be too small, which may lead to poor wet grip and poor flexibility.
- a water-soluble metal salt is attached to the surface of the dip layer. After drying, cross-linking, etc., if necessary, the water-soluble metal salt adhering to the surface is washed away.
- the maximum height roughness Rz and the arithmetic mean roughness Ra of the surface of the polymer layer of the resulting dip-molded product tend to be too large, resulting in poor flexibility and resistance to chemical permeation. There is a risk of being inferior in quality.
- a water-soluble metal salt-derived component for example, a metal component
- these methods require a foaming step, a step of adhering a water-soluble metal salt, and a step of washing off the water-soluble metal salt, which may reduce the production efficiency of the dip molded body.
- the latex composition for dip molding of the present invention By using the latex composition for dip molding of the present invention, excellent chemical liquid permeation resistance can be obtained without going through a foaming step, a step of adhering a water-soluble metal salt, and a step of washing off the water-soluble metal salt. It is possible to obtain the dip-molded article of the present invention which is excellent in wet grip and flexibility in a well-balanced manner. Therefore, by using the latex composition for dip molding of the present invention, it is possible to perform dip molding with high production efficiency while reducing the water-soluble metal salt-derived component (for example, metal component) on the surface of the dip molded article of the present invention. It is also possible to manufacture bodies.
- the water-soluble metal salt-derived component for example, metal component
- the thickness of the polymer layer composed of the latex composition for dip molding of the present invention is preferably 0.05 to 1.0 mm, more preferably 0.06 to 0.8 mm, and still more preferably. is 0.07 to 0.7 mm.
- the thickness of the laminate containing the base material and the polymer layer is preferably 0.1 to 10 mm, more preferably 0. .4 to 2.0 mm, more preferably 0.5 to 1.1 mm.
- the 100% tensile stress of the polymer layer composed of the latex composition for dip molding of the present invention in the dip-molded article of the present invention is preferably 1.1 MPa or less, more preferably 0.1 to 0.9 MPa. , more preferably 0.2 to 0.75 MPa, particularly preferably 0.3 to 0.7 MPa.
- the 100% tensile stress of the polymer layer is within the above range, and the dip has excellent wet grip properties and flexibility in a well-balanced manner, as well as excellent chemical liquid permeation resistance. A molded article can be obtained easily.
- the 100% tensile stress of the polymer layer may be controlled, for example, by adjusting the type of polymer latex used and the type and amount of surfactant such as an anionic surfactant used.
- the 100% tensile stress of the polymer layer can be controlled by adjusting the type and ratio of each polymer latex.
- the 100% tensile stress of the polymer layer composed of the latex composition for dip molding of the present invention in the dip-molded article of the present invention is measured by the following method.
- the latex of the polymer constituting the latex composition for dip molding, the compound (a), the compound (b1) and/or the compound (b2) are mixed in the same proportions as those in the latex composition for dip molding.
- Prepare a latex for measurement containing A film molding is obtained by coating the prepared latex for measurement on a glass substrate and drying it.
- the 100% tensile stress of the obtained film molding is measured, and the obtained value is defined as the 100% tensile stress value of the polymer layer.
- the latex composition for dip molding is a latex mixture containing a polymer latex, a compound (a), and a compound (b1) and/or a compound (b2). If it is obtained by adding additives such as system cross-linking agents, cross-linking accelerators, zinc oxide, water-soluble polymers, fillers, etc., the latex mixture (latex mixture before adding additives) , used as latex for measurement. Specifically, the 100% tensile stress of the polymer layer is measured by the method described in Examples.
- the maximum height roughness Rz of the surface of the polymer layer composed of the latex composition for dip molding of the present invention is preferably 135 to 350 ⁇ m, more preferably 155 to 320 ⁇ m, It is more preferably 180-310 ⁇ m, particularly preferably 230-300 ⁇ m, and most preferably 260-295 ⁇ m.
- the surface arithmetic mean roughness Ra of the polymer layer composed of the latex composition for dip molding of the present invention is preferably 20 to 72 ⁇ m, more preferably 25 to 65 ⁇ m, and further It is preferably 30-60 ⁇ m, particularly preferably 35-55 ⁇ m.
- the surface of the polymer layer comprising the latex composition for dip molding of the present invention has a load area ratio at 50% height of preferably 20 to 80%, more preferably 30 to 30%. 70%, more preferably 35 to 60%, particularly preferably 40 to 52%.
- the 50% height is the average height of the maximum height (100% height) and the minimum height (0% height) in the measurement area
- the load area ratio at 50% height is the measurement It is the projected area ratio of the portion where the height is higher than 50% in the area.
- the surface roughness of the polymer layer (maximum height roughness Rz, arithmetic mean roughness Ra, load area ratio at 50% height) is the height data of the surface of the polymer layer obtained using a laser microscope. Ask from Maximum height roughness Rz and arithmetic mean roughness Ra are obtained according to JIS B 0601:2013.
- the load area ratio at 50% height is obtained from the obtained height data, 50% height (average height of maximum height (100% height) and minimum height (0% height)) After calculating , it is obtained by calculating the projected area ratio of the portion whose height is higher than 50% in the measurement area. Specifically, it is determined by the method described in Examples.
- the dip-molded article of the present invention has excellent resistance to chemical liquid permeation, and is excellent in well-balanced wet grip properties and flexibility. For example, it can be suitably used for gloves, particularly for protective gloves. .
- the dip-molded product of the present invention is a laminate of a substrate and a polymer layer made of the latex composition for dip molding of the present invention has been exemplified and explained.
- the present invention is not limited to such an embodiment, and is a film molded article made of a latex composition for dip molding, which is obtained by immersing a dip mold in the latex composition for dip molding. Of course, it is also possible.
- a glove that is a laminate of a base material and a polymer layer made of a latex composition for dip molding tends to have a large thickness (thickness of the entire laminate of the base material and the polymer layer).
- grip performance tends to be insufficient.
- volume-average particle size of the polymer particles constituting the polymer latex was measured using a light scattering diffraction particle measuring device (manufactured by Coulter, trade name "LS-230").
- ⁇ Surface tension of polymer latex> A surface tension meter (DY-300, manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the surface tension of the polymer latex. Measured values are expressed in units of mN/m. Measurements were performed at 25°C.
- ⁇ Difference between surface tension of polymer latex and surface tension of anionic surfactant> The surface tension of the polymer latex was measured by the method described above.
- a 5.0% by weight aqueous solution of the anionic surfactant (compound (a), compound (b1), compound (b2)) used in each production example was prepared, and a surface tensiometer (DY-300, Kyowa interface (manufactured by Kagaku Co., Ltd.) was used to measure the surface tension (the surface tension of the surfactant). Measurements were performed at 25°C.
- ⁇ Content of surfactant in latex composition for dip molding The content of the surfactant in the latex composition for dip molding was calculated from the amount of surfactant used in each production example, the polymerization conversion rate in each production example, and the compounding ratio in each example.
- Tensilon universal testing machine (trade name "RTG-1210", manufactured by Orientec) was used to measure the 100% tensile stress of the test piece at a tensile speed of 500 mm / min. 100% tensile stress (100% tensile stress of the polymer layer).
- the surface roughness of the polymer layer of the protective glove (maximum height roughness Rz, arithmetic mean roughness Ra, load area ratio at 50% height) is measured using a laser microscope (Keyence VK-X100) as follows. conditions were used to obtain height data for the surface of the polymer layer of the protective glove. Then, using analysis software ("surface roughness" measurement function of VK shape analysis application VK-H1XJ manufactured by Keyence Corporation), from the obtained height data, according to JIS B 0601: 2013, the maximum height roughness Rz and arithmetic mean roughness Ra were obtained.
- the oil permeation amount of protective gloves was measured by the following procedure. (1) A finger-shaped test piece was obtained by cutting out the index finger portion of the protective glove (laminate). (2) Put test oil IRM903 into an aluminum cup. (3) A filter paper (weight: W 1 ) was placed inside the test piece, and the inner surface of the portion of the test piece corresponding to the pad of the finger (the portion with an area of about 2 to 5 cm 2 ) was brought into close contact with the filter paper. .
- protective glove A A dip molded product (laminate) having a base material and a polymer layer, which was obtained without a step of foaming the polymer layer or a surface treatment step after molding the dip layer. It is.
- the protective glove A has excellent flexibility, but does not have wet grip properties at all.
- Protective glove B A dip molded article (laminate) having a base material and a polymer layer, obtained through a surface treatment step after molding the dip layer.
- the protective glove B has relatively high wet grip properties.
- ⁇ Production Example 1> (Production of latex of polybutyl acrylate (A-1)) Into a 5 MPa pressure vessel equipped with a stirrer, 100 parts of n-butyl acrylate as an ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid ester monomer and sodium alkyldiphenyl ether disulfonate (sodium dodecyldiphenyl ether disulfonate as a main component) were added as a compound (b1).
- ⁇ Production Example 2> (Production of latex of carboxyl group-containing nitrile rubber (A-2)) A polymerization reactor was charged with 67.5 parts of 1,3-butadiene as a conjugated diene monomer, 27 parts of acrylonitrile as an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer, and methacryl as an ethylenically unsaturated monocarboxylic acid monomer.
- a latex of group-containing nitrile rubber (A-2) was obtained.
- the carboxyl group-containing nitrile rubber (A-2) contained in the obtained carboxyl group-containing nitrile rubber (A-2) latex had a glass transition temperature (Tg) of -24°C.
- Tg glass transition temperature
- the monomer composition of A-2) was almost the same as the charging ratio. Measurements were carried out in the same manner as in Production Example 1 using the carboxyl group-containing nitrile rubber (A-2) latex. Table 1 shows the results.
- ⁇ Production Example 3> (Production of Latex of Carboxyl Group-Containing Nitrile Rubber (A-3) Containing Methyl Methacrylate Units) 1,3-Butadiene was changed to 47.3 parts, acrylonitrile to 18.8 parts, methacrylic acid to 3.9 parts, and, together with these monomers, ⁇ , ⁇ -ethylenically unsaturated A carboxyl group containing a methyl methacrylate unit having a solid content concentration of 40% by weight and a pH of 8 was prepared in the same manner as in Production Example 2, except that 30 parts of methyl methacrylate was charged to the polymerization reactor as a monocarboxylic acid ester monomer.
- a latex containing nitrile rubber (A-3) was obtained.
- the glass transition temperature (Tg) of the carboxyl group-containing nitrile rubber (A-3) containing methyl methacrylate units contained in the obtained latex of the carboxyl group-containing nitrile rubber (A-3) containing methyl methacrylate units is The temperature was ⁇ 14° C., and the monomer composition of the carboxyl group-containing nitrile rubber (A-3) containing methyl methacrylate units was substantially the same as the charging ratio. Measurements were performed in the same manner as in Production Example 1 using a latex of carboxyl group-containing nitrile rubber (A-3) containing methyl methacrylate units. Table 1 shows the results.
- Examples 1 to 8 and Comparative Example 1> Preparation of aqueous dispersion of colloidal sulfur
- Colloidal sulfur manufactured by Hosoi Chemical Industry Co., Ltd.
- dispersant manufactured by Kao Corporation, trade name "Demoll N"
- potassium hydroxide aqueous solution manufactured by Wako Pure Chemical Industries
- 0015 parts and 1.0 part of water were pulverized and stirred in a ball mill for 48 hours to prepare an aqueous dispersion of colloidal sulfur having a solid concentration of 50% by weight.
- carboxymethyl cellulose manufactured by Daicel Corporation, trade name "Daicel 2200", weight average molecular weight: 550,000
- a latex composition for dip molding having a solid concentration of 40% by weight was obtained.
- the content of the surfactant in the latex composition for dip molding was determined. Table 2 shows the results.
- a coagulant solution was prepared by dissolving 2.0% by weight of calcium nitrate as a coagulant in methanol.
- the latex composition for dip molding obtained above was aged (also referred to as prevulcanization) at a temperature of 30° C. for 48 hours.
- a ceramic glove mold covered with a glove-shaped fiber base material material: nylon, linear density: 300 denier, gauge number: 13 gauge, thickness: 0.8 mm
- the ceramic glove mold is immersed in the aged dip molding latex composition for 5 seconds, pulled out from the aged dip molding latex composition, and dried at a temperature of 25° C. for 20 minutes.
- a dip layer was formed on the fiber substrate.
- the ceramic glove mold with the dip layer formed thereon was subjected to heat treatment at a temperature of 110° C. for 30 minutes to crosslink the polymer in the dip layer, thereby forming a polymer layer.
- the fiber base material on which the polymer layer was formed was peeled off from the ceramic glove mold to obtain a protective glove (dip molding).
- the thickness of the polymer layer was 0.15 mm
- the thickness of the protective glove thickness of the protective glove (thickness of the entire laminate including the substrate and the polymer layer) was 1.0 mm.
- the surface roughness of the polymer layer (maximum height roughness Rz, arithmetic mean roughness Ra, load area ratio at 50% height), wet grip properties of protective gloves, protective gloves
- Table 2 shows the results.
- the foaming step of the latex composition and the surface processing step after forming the dip layer water-soluble metal salt is attached to the surface of the dip layer and dried if necessary).
- cross-linking, etc., followed by washing away water-soluble metal salts attached to the surface) excellent chemical permeation resistance, excellent wet grip and flexibility in a well-balanced dip molding. I was able to get a body
- a latex composition for dip molding containing a polymer latex and an anionic surfactant, wherein the anionic surfactant has one anionic group and an aromatic ring. and a compound (b1) having two or more anionic groups and a benzene ring or a compound (b2) having one anionic group and no aromatic ring.
- the obtained dip-molded articles had excellent resistance to chemical liquid permeation, and were excellent in well-balanced wet grip and flexibility (Examples 1 to 8).
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Abstract
L'invention fournit une composition de latex pour moulage par immersion qui permet de procurer un corps moulé par immersion présentant une excellente résistance à la perméation de liquide chimique, et doté d'un excellent équilibre entre adhérence sur surface mouillée et souplesse. Plus précisément, l'invention fournit une composition de latex pour moulage par immersion qui comprend un latex de polymère et un agent tensio-actif anionique. Ledit agent tensio-actif anionique comprend un composé (a) possédant un groupe anionique et possédant un cycle aromatique, un composé (b1) possédant au moins deux groupes anioniques et possédant un cycle benzène ou un composé (b2) possédant un groupe anionique mais ne possédant pas de cycle aromatique.
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JPH107706A (ja) * | 1996-06-26 | 1998-01-13 | Sumika A B S Latex Kk | 共重合体ラテックスの製造方法 |
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US20110229646A1 (en) * | 2008-09-26 | 2011-09-22 | Lg Chem, Ltd. | Latex resin composition for rubber gloves without sulfur and vulcanization acceleator and method of manufacturing dip-formed article using the composition |
US20120149859A1 (en) * | 2009-06-12 | 2012-06-14 | Lg Chem, Ltd | Latex for dip molding, composition for dip molding, preparation method of dip molded product, and dip molded product prepared thereby |
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2022
- 2022-07-26 JP JP2023542295A patent/JPWO2023021946A1/ja active Pending
- 2022-07-26 WO PCT/JP2022/028816 patent/WO2023021946A1/fr active Application Filing
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