WO2013015043A1 - Polychloroprene latex composition and dip-molded article - Google Patents
Polychloroprene latex composition and dip-molded article Download PDFInfo
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- WO2013015043A1 WO2013015043A1 PCT/JP2012/065705 JP2012065705W WO2013015043A1 WO 2013015043 A1 WO2013015043 A1 WO 2013015043A1 JP 2012065705 W JP2012065705 W JP 2012065705W WO 2013015043 A1 WO2013015043 A1 WO 2013015043A1
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- mass
- polychloroprene latex
- parts
- latex composition
- zinc white
- Prior art date
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- 239000004816 latex Substances 0.000 title claims abstract description 119
- 229920000126 latex Polymers 0.000 title claims abstract description 119
- 229920001084 poly(chloroprene) Polymers 0.000 title claims abstract description 112
- 239000000203 mixture Substances 0.000 title claims abstract description 70
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 95
- 239000011787 zinc oxide Substances 0.000 claims abstract description 85
- 239000002131 composite material Substances 0.000 claims abstract description 75
- 239000007787 solid Substances 0.000 claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 28
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011575 calcium Substances 0.000 claims abstract description 9
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 9
- 239000011777 magnesium Substances 0.000 claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 239000011701 zinc Substances 0.000 claims abstract description 8
- 235000014692 zinc oxide Nutrition 0.000 claims description 83
- 238000007654 immersion Methods 0.000 claims description 35
- 239000000178 monomer Substances 0.000 claims description 16
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 claims description 11
- 239000004094 surface-active agent Substances 0.000 claims description 11
- LIFLRQVHKGGNSG-UHFFFAOYSA-N 2,3-dichlorobuta-1,3-diene Chemical compound ClC(=C)C(Cl)=C LIFLRQVHKGGNSG-UHFFFAOYSA-N 0.000 claims description 10
- 239000003963 antioxidant agent Substances 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 238000002441 X-ray diffraction Methods 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 239000001095 magnesium carbonate Substances 0.000 claims description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 239000002344 surface layer Substances 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 abstract description 4
- 238000004876 x-ray fluorescence Methods 0.000 abstract description 3
- -1 2-hydroxypropyl Chemical group 0.000 description 29
- 238000004073 vulcanization Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- 239000003995 emulsifying agent Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 10
- 239000002270 dispersing agent Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000001804 emulsifying effect Effects 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- OKJPEAGHQZHRQV-UHFFFAOYSA-N iodoform Chemical compound IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- PCPYTNCQOSFKGG-ONEGZZNKSA-N (1e)-1-chlorobuta-1,3-diene Chemical compound Cl\C=C\C=C PCPYTNCQOSFKGG-ONEGZZNKSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- 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 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 1
- FVIGODVHAVLZOO-UHFFFAOYSA-N Dixanthogen Chemical compound CCOC(=S)SSC(=S)OCC FVIGODVHAVLZOO-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 1
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
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- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
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- 150000002019 disulfides Chemical class 0.000 description 1
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- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
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- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
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- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
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- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- YWXYYJSYQOXTPL-SLPGGIOYSA-N isosorbide mononitrate Chemical compound [O-][N+](=O)O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 YWXYYJSYQOXTPL-SLPGGIOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KEZPMZSDLBJCHH-UHFFFAOYSA-N n-(4-anilinophenyl)-4-methylbenzenesulfonamide Chemical compound C1=CC(C)=CC=C1S(=O)(=O)NC(C=C1)=CC=C1NC1=CC=CC=C1 KEZPMZSDLBJCHH-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- ZWWQICJTBOCQLA-UHFFFAOYSA-N o-propan-2-yl (propan-2-yloxycarbothioyldisulfanyl)methanethioate Chemical compound CC(C)OC(=S)SSC(=S)OC(C)C ZWWQICJTBOCQLA-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
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- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
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- 239000011574 phosphorus Substances 0.000 description 1
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- 239000004014 plasticizer Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010092 rubber production Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- CBXWGGFGZDVPNV-UHFFFAOYSA-N so4-so4 Chemical class OS(O)(=O)=O.OS(O)(=O)=O CBXWGGFGZDVPNV-UHFFFAOYSA-N 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/105—Compounds containing metals of Groups 1 to 3 or of Groups 11 to 13 of the Periodic Table
Definitions
- the polychloroprene latex composition of the present embodiment contains at least 100 parts by mass of a solid content of polychloroprene latex and 0.01 to 10 parts by mass of composite zinc white containing an inorganic salt and zinc oxide.
- Polychloroprene latex is obtained by polymerizing a raw material monomer containing 30% by mass or less of 2,3-dichloro-1,3-butadiene in order to improve crystal resistance and improve properties such as flexibility. It is preferred that When the amount of 2,3-dichloro-1,3-butadiene exceeds 30% by mass, the polychloroprene latex may be excessively crystallized and the flexibility may be lowered. When 2,3-dichloro-1,3-butadiene and a monomer copolymerizable with these monomers are used, the amount of the monomer is changed to 2,3-dichloro-1,3-butadiene. And 30% by mass or less of 100% by mass of all monomers.
- the chain transfer agent is not particularly limited, and a chain transfer agent used for usual emulsion polymerization of chloroprene can be used.
- a chain transfer agent used for usual emulsion polymerization of chloroprene can be used.
- long chain alkyl mercaptans such as n-dodecyl mercaptan and tert-dodecyl mercaptan
- dialkylxanthogen disulfides such as diisopropylxanthogen disulfide and diethylxanthogen disulfide
- known chain transfer agents such as iodoform
- the polychloroprene latex composition of the present embodiment is blended with a composite zinc white containing an inorganic salt and zinc oxide for the purpose of improving the film forming property of the polychloroprene latex and improving the tensile strength of the resulting polychloroprene latex film. Has been.
- the particle size of the composite zinc white contained in the polychloroprene latex composition of the present embodiment is 0.01 to 1.0 ⁇ m. If the particle size of the composite zinc white is less than 0.01 ⁇ m, the composite zinc white aggregates and the reaction efficiency with the polychloroprene latex decreases. On the other hand, when a composite zinc white having a composite zinc white particle size exceeding 1.0 ⁇ m is used, the surface area of the composite zinc white per unit volume is reduced and the reaction efficiency with the polychloroprene latex is lowered.
- the structure of the composite zinc white contained in the polychloroprene latex composition of the present embodiment is not particularly limited, but a composite structure in which an inorganic salt is used as a nucleus and zinc oxide is laminated and coated as a surface layer is preferable.
- a composite structure in which an inorganic salt is used as a nucleus and zinc oxide is laminated and coated as a surface layer is preferable.
- the composite structure of composite zinc white can be analyzed by observing with a scanning electron microscope (Scanning Electron Microscope, SEM) or an energy dispersive X-ray analyzer (Energy Dispersive X-ray Spectrometer, EDS). .
- the polychloroprene latex composition described above can be used as it is as a material for an immersion molded product, but various additives can also be added. Specific examples of the various additives include metal oxides, sulfur, antioxidants, and surfactants.
- the metal oxide is not particularly limited, and for example, zinc oxide, lead oxide, trilead tetraoxide, and the like can be blended. These may be used alone or in combination of two or more as required.
- Antioxidant 0.1 to 5 parts by mass with respect to 100 parts by mass of solid content of polychloroprene latex
- the antioxidant is blended in order to improve the heat resistance and ozone resistance of the obtained molded product.
- Antioxidants for the purpose of imparting heat resistance are not only heat resistant but also less stain resistant (displacement such as discoloration), so octylated diphenylamine, p- (p-toluene-sulfonylamido) diphenylamine and 4,4 Diphenylamine systems such as' -bis ( ⁇ , ⁇ -dimethylbenzyl) diphenylamine are preferred.
- the surfactant is blended for colloidal stabilization of the polychloroprene latex.
- the surfactant sodium alkyl sulfate, sodium alkylbenzene sulfonate, sodium salt of naphthalene sulfonate formaldehyde condensate, rosin acid soap, fatty acid soap and the like can be used.
- the amount of these surfactants to be added is not particularly limited.
- a vulcanization accelerator a pH adjuster, a filler, a plasticizer, a pigment, a colorant, a wetting agent, Various additives such as an antifoaming agent can be blended.
- An immersion film was produced from the polychloroprene latex composition using a primary flocculant and a secondary flocculant described in Table 1 below.
- the primary flocculant promotes the solidification of the formed immersion molding liquid.
- the immersion film was produced by the following method. A test tube having an outer diameter of 40 mm and a length of 320 mm is immersed in a primary flocculant for 10 seconds to a depth of 150 mm with the mouth facing up, taken out from the primary flocculant and air-dried for 3 minutes, and then a polychloroprene latex composition An immersion film was produced on the surface of the test tube by immersing the product in the object for 1 minute.
- the obtained immersion film was leached (leached) with running water for 1 minute to remove water-soluble components. Subsequently, after being immersed in the secondary flocculant for 1 minute, the secondary flocculant on the surface of the immersion film was removed with running water. Furthermore, it dried at 70 degreeC for 2 hours, and produced the unvulcanized film.
- the particle size of the composite zinc white was measured with an SEM observation apparatus (FE-SEM SU6600: Hitachi High-Technologies Corporation), and the number average particle size of the composite zinc white was calculated from the obtained value.
- the number average particle size and particle size of zinc white were measured by diluting the composite zinc white with water, ultrasonically dispersing it, and then naturally drying it to obtain a powder.
- the specific surface area of the composite zinc white was quantified with a specific surface area measuring device (Monosorb: Yuasa Aonics Co., Ltd.). The specific surface area of the composite zinc white was measured by diluting the composite zinc white with water, ultrasonically dispersing it, and then drying it naturally to form a powder.
- Example 2 Polychloroprene latex LM-61 (manufactured by Denki Kagaku Kogyo Co., Ltd., solid content 60 mass%) 166.67 parts by mass (100 mass parts by solid content) and vulcanization accelerator A (Noxeller TP: Ouchi Shinsei Chemical Co., Ltd.) Manufactured, 50% by weight aqueous solution) 2 parts by weight (1 part by weight in solids) and 20 parts by weight of aqueous dispersion (wet) are mixed, and water is added to adjust the solids concentration of the entire formulation to 50%. Thus, a polychloroprene latex composition was prepared.
- aqueous dispersion 2 parts by mass of an anti-aging agent (NOCRACK 200: manufactured by Ouchi Shinsei Chemical Co., Ltd., powder) and vulcanization accelerator B (Noxeller TET: manufactured by Ouchi Shinsei Chemical Co., Ltd., powder) 1 part by mass, surfactant A (Darvan SMO: manufactured by RT Verderbilt Company, 33.3% by mass aqueous solution) 9 parts by mass (3 parts by mass in solid content), surfactant B (Darvan WAQ: R.D. 4 parts by mass (1 mass part in solid content) of T.
- NOCRACK 200 manufactured by Ouchi Shinsei Chemical Co., Ltd., powder
- vulcanization accelerator B Noxeller TET: manufactured by Ouchi Shinsei Chemical Co., Ltd., powder
- surfactant A Darvan SMO: manufactured by RT Verderbilt Company, 33.3% by mass aqueous solution
- surfactant B Darvan WAQ: R.D. 4 parts by mass (1
- Example 2 In Example 2, the same procedure as in Example 2 was performed except that the composite zinc white B was changed to 5 parts by mass of zinc white C (AZO-B: manufactured by Shodo Chemical Industry Co., Ltd., powder). A chloroprene latex composition and a film sample were prepared and evaluated and analyzed in the same manner as in Example 2.
- Example 3 (Comparative Example 3) In Example 2, except that the composite zinc white B was changed to 5 parts by mass of zinc white D (2 types of zinc white: manufactured by Sakai Chemical Industry Co., Ltd., powder), the same procedure as in Example 2 was followed. A chloroprene latex composition and a film sample were prepared and evaluated and analyzed in the same manner as in Example 2.
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Abstract
Provided are a polychloroprene latex composition, whereby a dip-molded article having excellent mechanical strength can be obtained, and a dip-molded article using same. A polychloroprene latex composition containing at least 100 mass parts, by solid content, of polychloroprene latex and 0.01 to 10 mass parts of a composite zinc oxide comprising an inorganic salt and zinc oxide, the composite zinc oxide having a number-average particle size of 0.05 to 0.35 μm, a particle size of 0.01 to 1.0 μm, and specific surface area of 10 to 35 m2/g, the quantitative values by X-ray fluorescence analysis being 20 to 98 mass% zinc, 1 to 30 mass% calcium, and 0.01 to 30 mass% magnesium; also, a dip-molded article obtained therefrom.
Description
本発明は、ポリクロロプレンラテックス組成物及び浸漬成形品に関する。より詳しくは、例えば手袋、風船、糸ゴム、長靴などの浸漬成形品、特に使い捨て手袋に好適に使用されるポリクロロプレンラテックス組成物及びこれらを用いた浸漬成形品に関する。
The present invention relates to a polychloroprene latex composition and an immersion molded product. More specifically, the present invention relates to an immersion molded product such as a glove, a balloon, a rubber thread, and a boot, and more particularly to a polychloroprene latex composition suitably used for a disposable glove and an immersion molded product using these.
ポリクロロプレンラテックス組成物は、機械的強度、耐候性、耐熱性及び耐薬品性などの特性が良好であるため、手袋などの浸漬成形品、繊維処理剤、紙加工剤、粘着剤、接着剤、弾性アスファルト(改質アスファルト)及び弾性セメントなどの分野で利用されている。特に、浸漬成形品では、家庭用、産業用、検査用、健康診断用及び手術用などの各種手袋の主原料のひとつとしてポリクロロプレンラテックス組成物が用いられている。
Since the polychloroprene latex composition has good properties such as mechanical strength, weather resistance, heat resistance and chemical resistance, it is a dip molding product such as gloves, a fiber treatment agent, a paper processing agent, an adhesive, an adhesive, It is used in fields such as elastic asphalt (modified asphalt) and elastic cement. In particular, in the dip-molded article, a polychloroprene latex composition is used as one of main raw materials for various gloves for household use, industrial use, inspection use, health check use, and surgical use.
従来、手袋用のポリクロロプレンラテックス組成物としては、柔軟性の経時安定性と引張り強度、引張り伸びとのバランスを良好にするため、単量体組成に加えて、重合体中のテトラハイドロフラン不溶分量及び結晶化速度を特定の範囲に調整した手袋用ポリクロロプレンラテックス組成物(特許文献1参照)や、クロロプレンポリマーの1質量%トルエン不溶分量を特定の範囲に調整した加硫ゴム製造用クロロプレン重合体ラテックス(特許文献2参照)などが提案されている。一方、ジエン系ゴムについては、各種亜鉛華を添加して、強度を向上させることが提案されている(特許文献3~6参照)。
Conventionally, as a polychloroprene latex composition for gloves, in order to improve the balance between the stability of flexibility over time, tensile strength, and tensile elongation, in addition to the monomer composition, insoluble in tetrahydrofuran. Polychloroprene latex composition for gloves (see Patent Document 1) in which the amount and crystallization rate are adjusted to a specific range, and chloroprene weight for vulcanized rubber production in which the 1% by mass toluene insoluble content of chloroprene polymer is adjusted to a specific range A combined latex (see Patent Document 2) has been proposed. On the other hand, for diene rubbers, it has been proposed to improve the strength by adding various zinc oxides (see Patent Documents 3 to 6).
しかしながら、従来のポリクロロプレンラテックス組成物では、特許文献1、2に記載されているように、ポリマーの共重合組成を最適化することのみでは浸漬成形した際の引張り強度等の機械的強度はまだ十分であるとは言えなかった。また、特許文献1には、ポリクロロプレンラテックスの固形分100質量部に対して、金属酸化物を1~10質量部配合する時に、他の金属酸化物や加硫促進剤等を更に添加する方法が記載されているが、この方法では、製造コストの増加や、浸漬成形品中に添加物が均一に分散されにくいといった問題がある。この点からも、従来のポリクロロプレンラテックス組成物は、浸漬成形した際の引張り強度等の機械的強度がまだ十分であるとは言えなかった。
However, in the conventional polychloroprene latex composition, as described in Patent Documents 1 and 2, mechanical strength such as tensile strength at the time of dip molding is not yet achieved only by optimizing the copolymer composition of the polymer. It was not enough. Patent Document 1 discloses a method of further adding another metal oxide, a vulcanization accelerator or the like when 1 to 10 parts by mass of a metal oxide is blended with 100 parts by mass of a solid content of polychloroprene latex. However, this method has problems such as an increase in manufacturing cost and difficulty in uniformly dispersing the additive in the dip-molded product. Also from this point, it could not be said that the conventional polychloroprene latex composition has sufficient mechanical strength such as tensile strength at the time of immersion molding.
そこで、本発明は、機械的強度に優れる浸漬成形品を得ることが出来るポリクロロプレンラテックス組成物及びこれを用いた浸漬成形品を提供することを主目的とする。
Therefore, the main object of the present invention is to provide a polychloroprene latex composition capable of obtaining an immersion molded article having excellent mechanical strength and an immersion molded article using the same.
本発明に係るポリクロロプレンラテックス組成物は、ポリクロロプレンラテックスの固形分100質量部と、無機塩及び酸化亜鉛を含む複合亜鉛華0.01~10質量部と、を少なくとも含有し、前記複合亜鉛華は、個数平均粒径が0.05~0.35μmであり、粒径が0.01~1.0μmであり、比表面積が10~35m2/gであり、蛍光X線分析による定量値で亜鉛20~98質量%、カルシウム1~30質量%およびマグネシウム0.01~30質量%である。
前記複合亜鉛華は、前記無機塩を核として、前記酸化亜鉛を表層に被覆させた複合構造であってもよい。
また、前記無機塩は、例えば、炭酸カルシウム、次亜塩素酸カルシウム、炭酸マグネシウム、酸化マグネシウム及び水酸化マグネシウムのうちから選ばれる少なくとも一種の化合物である。
前記ポリクロロプレンラテックスは、例えば、2,3-ジクロロ-1,3-ブタジエンを30質量%以下含有する原料単量体を25℃以上で重合して得られる。 The polychloroprene latex composition according to the present invention contains at least 100 parts by mass of a solid content of polychloroprene latex and 0.01 to 10 parts by mass of composite zinc white containing an inorganic salt and zinc oxide, and the composite zinc white Has a number average particle size of 0.05 to 0.35 μm, a particle size of 0.01 to 1.0 μm, a specific surface area of 10 to 35 m 2 / g, and a quantitative value by fluorescent X-ray analysis. Zinc is 20 to 98% by mass, calcium is 1 to 30% by mass and magnesium is 0.01 to 30% by mass.
The composite zinc white may have a composite structure in which the zinc salt is coated on the surface layer using the inorganic salt as a nucleus.
The inorganic salt is, for example, at least one compound selected from calcium carbonate, calcium hypochlorite, magnesium carbonate, magnesium oxide, and magnesium hydroxide.
The polychloroprene latex is obtained, for example, by polymerizing a raw material monomer containing 30% by mass or less of 2,3-dichloro-1,3-butadiene at 25 ° C. or more.
前記複合亜鉛華は、前記無機塩を核として、前記酸化亜鉛を表層に被覆させた複合構造であってもよい。
また、前記無機塩は、例えば、炭酸カルシウム、次亜塩素酸カルシウム、炭酸マグネシウム、酸化マグネシウム及び水酸化マグネシウムのうちから選ばれる少なくとも一種の化合物である。
前記ポリクロロプレンラテックスは、例えば、2,3-ジクロロ-1,3-ブタジエンを30質量%以下含有する原料単量体を25℃以上で重合して得られる。 The polychloroprene latex composition according to the present invention contains at least 100 parts by mass of a solid content of polychloroprene latex and 0.01 to 10 parts by mass of composite zinc white containing an inorganic salt and zinc oxide, and the composite zinc white Has a number average particle size of 0.05 to 0.35 μm, a particle size of 0.01 to 1.0 μm, a specific surface area of 10 to 35 m 2 / g, and a quantitative value by fluorescent X-ray analysis. Zinc is 20 to 98% by mass, calcium is 1 to 30% by mass and magnesium is 0.01 to 30% by mass.
The composite zinc white may have a composite structure in which the zinc salt is coated on the surface layer using the inorganic salt as a nucleus.
The inorganic salt is, for example, at least one compound selected from calcium carbonate, calcium hypochlorite, magnesium carbonate, magnesium oxide, and magnesium hydroxide.
The polychloroprene latex is obtained, for example, by polymerizing a raw material monomer containing 30% by mass or less of 2,3-dichloro-1,3-butadiene at 25 ° C. or more.
本発明に係るポリクロロプレンラテックス組成物は、更に、前記ポリクロロプレンラテックスの固形分100質量部に対して、金属酸化物0.1~10質量部と、硫黄0.1~3質量部と、酸化防止剤0.1~5質量部と、界面活性剤0.1~10質量部とを含有していてもよい。このポリクロロプレンラテックス組成物は、例えば、浸漬成形品に用いられる。
The polychloroprene latex composition according to the present invention further comprises 0.1 to 10 parts by mass of metal oxide, 0.1 to 3 parts by mass of sulfur, and 100% by mass of solid content of the polychloroprene latex. It may contain 0.1 to 5 parts by mass of an inhibitor and 0.1 to 10 parts by mass of a surfactant. This polychloroprene latex composition is used for, for example, an immersion molded article.
本発明に係る浸漬成形品は、前述したポリクロロプレンラテックス組成物を用いて浸漬成形されており、例えば、手袋がある。
The immersion molded product according to the present invention is immersion molded using the polychloroprene latex composition described above, and includes, for example, a glove.
本発明によれば、特定の量の複合亜鉛華を有し、当該複合亜鉛華の個数平均粒径、粒径、比表面積を特定の範囲に規定し、蛍光X線分析により定量される元素が特定の範囲にあるため、機械的強度に優れた浸漬成形品を得ることができる。
According to the present invention, an element that has a specific amount of composite zinc white, defines the number average particle diameter, particle diameter, specific surface area of the composite zinc white in a specific range, and is quantified by fluorescent X-ray analysis. Since it exists in a specific range, the immersion molded product excellent in mechanical strength can be obtained.
以下、本発明を実施するための形態について、詳細に説明する。なお、本発明は、以下に説明する実施形態に限定されるものではない。
Hereinafter, embodiments for carrying out the present invention will be described in detail. Note that the present invention is not limited to the embodiments described below.
(第1の実施形態)
<ポリクロロプレンラテックス組成物>
まず、本発明の第1の実施形態のポリクロロプレンラテックス組成物について説明する。本実施形態のポリクロロプレンラテックス組成物は、ポリクロロプレンラテックスの固形分100質量部と、無機塩及び酸化亜鉛を含む複合亜鉛華0.01~10質量部と、を少なくとも含有する。また、本実施形態のポリクロロプレンラテックス組成物では、複合亜鉛華は、個数平均粒径が0.05~0.35μmであり、粒径が0.01~1.0μmであり、比表面積が10~35m2/gであり、蛍光X線分析により定量される元素が亜鉛20~98質量%、カルシウム1~30質量%およびマグネシウム0.01~30質量%である。 (First embodiment)
<Polychloroprene latex composition>
First, the polychloroprene latex composition according to the first embodiment of the present invention will be described. The polychloroprene latex composition of the present embodiment contains at least 100 parts by mass of a solid content of polychloroprene latex and 0.01 to 10 parts by mass of composite zinc white containing an inorganic salt and zinc oxide. In the polychloroprene latex composition of the present embodiment, the composite zinc white has a number average particle diameter of 0.05 to 0.35 μm, a particle diameter of 0.01 to 1.0 μm, and a specific surface area of 10 ~ a 35m 2 / g, an element zinc 20-98 wt% of calcium from 1 to 30% by weight and magnesium 0.01 to 30 wt%, which is determined by X-ray fluorescence analysis.
<ポリクロロプレンラテックス組成物>
まず、本発明の第1の実施形態のポリクロロプレンラテックス組成物について説明する。本実施形態のポリクロロプレンラテックス組成物は、ポリクロロプレンラテックスの固形分100質量部と、無機塩及び酸化亜鉛を含む複合亜鉛華0.01~10質量部と、を少なくとも含有する。また、本実施形態のポリクロロプレンラテックス組成物では、複合亜鉛華は、個数平均粒径が0.05~0.35μmであり、粒径が0.01~1.0μmであり、比表面積が10~35m2/gであり、蛍光X線分析により定量される元素が亜鉛20~98質量%、カルシウム1~30質量%およびマグネシウム0.01~30質量%である。 (First embodiment)
<Polychloroprene latex composition>
First, the polychloroprene latex composition according to the first embodiment of the present invention will be described. The polychloroprene latex composition of the present embodiment contains at least 100 parts by mass of a solid content of polychloroprene latex and 0.01 to 10 parts by mass of composite zinc white containing an inorganic salt and zinc oxide. In the polychloroprene latex composition of the present embodiment, the composite zinc white has a number average particle diameter of 0.05 to 0.35 μm, a particle diameter of 0.01 to 1.0 μm, and a specific surface area of 10 ~ a 35m 2 / g, an element zinc 20-98 wt% of calcium from 1 to 30% by weight and magnesium 0.01 to 30 wt%, which is determined by X-ray fluorescence analysis.
[ポリクロロプレンラテックス]
本実施形態のポリクロロプレンラテックス組成物に用いられるポリクロロプレンラテックスは、2-クロロ-1,3-ブタジエン(以下クロロプレンと記す)の単独重合体、クロロプレンと2,3-ジクロロ-1,3-ブタジエンとの共重合体、又はクロロプレンと、2,3-ジクロロ-1,3-ブタジエンと、これらの単量体と共重合可能な単量体との共重合体である。 [Polychloroprene latex]
The polychloroprene latex used in the polychloroprene latex composition of this embodiment is a homopolymer of 2-chloro-1,3-butadiene (hereinafter referred to as chloroprene), chloroprene and 2,3-dichloro-1,3-butadiene. Or a copolymer of chloroprene, 2,3-dichloro-1,3-butadiene, and a monomer copolymerizable with these monomers.
本実施形態のポリクロロプレンラテックス組成物に用いられるポリクロロプレンラテックスは、2-クロロ-1,3-ブタジエン(以下クロロプレンと記す)の単独重合体、クロロプレンと2,3-ジクロロ-1,3-ブタジエンとの共重合体、又はクロロプレンと、2,3-ジクロロ-1,3-ブタジエンと、これらの単量体と共重合可能な単量体との共重合体である。 [Polychloroprene latex]
The polychloroprene latex used in the polychloroprene latex composition of this embodiment is a homopolymer of 2-chloro-1,3-butadiene (hereinafter referred to as chloroprene), chloroprene and 2,3-dichloro-1,3-butadiene. Or a copolymer of chloroprene, 2,3-dichloro-1,3-butadiene, and a monomer copolymerizable with these monomers.
クロロプレン及び2,3-ジクロロ-1,3-ブタジエンと共重合可能な単量体としては、例えば、アクリル酸メチル、アクリル酸ブチル、アクリル酸-2-エチルヘキシル等のアクリル酸のエステル類やメタクリル酸メチル、メタクリル酸ブチル、メタクリル酸-2-エチルヘキシル等のメタクリル酸エステル類や、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシメチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート等のヒドロキシ(メタ)アクリレート類や、1-クロロブタジエン、ブタジエン、イソプレン、エチレン、スチレン、アクリロニトリル等が挙げられる。
Examples of monomers copolymerizable with chloroprene and 2,3-dichloro-1,3-butadiene include acrylic acid esters such as methyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, and methacrylic acid. Methacrylic esters such as methyl, butyl methacrylate, and 2-ethylhexyl methacrylate, and hydroxy (such as 2-hydroxyethyl (meth) acrylate, 2-hydroxymethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate) And (meth) acrylates, 1-chlorobutadiene, butadiene, isoprene, ethylene, styrene, acrylonitrile and the like.
ポリクロロプレンラテックスは、耐結晶性を改良し、柔軟性などの特性を向上させるため、2,3-ジクロロ-1,3-ブタジエンを30質量%以下含有する原料単量体を重合することにより得られることが好ましい。2,3-ジクロロ-1,3-ブタジエンが30質量%を超える場合には、ポリクロロプレンラテックスの結晶化が進みすぎて柔軟性が低下する場合がある。また、2,3-ジクロロ-1,3-ブタジエン及びこれらの単量体と共重合可能な単量体を用いる場合は、該単量体の量を2,3-ジクロロ-1,3-ブタジエンと合わせて、全単量体100質量%中30質量%以下とすることが好ましい。
Polychloroprene latex is obtained by polymerizing a raw material monomer containing 30% by mass or less of 2,3-dichloro-1,3-butadiene in order to improve crystal resistance and improve properties such as flexibility. It is preferred that When the amount of 2,3-dichloro-1,3-butadiene exceeds 30% by mass, the polychloroprene latex may be excessively crystallized and the flexibility may be lowered. When 2,3-dichloro-1,3-butadiene and a monomer copolymerizable with these monomers are used, the amount of the monomer is changed to 2,3-dichloro-1,3-butadiene. And 30% by mass or less of 100% by mass of all monomers.
(ポリクロロプレンラテックスの製造方法)
次に、ポリクロロプレンラテックスの製造方法について説明する。ポリクロロプレンラテックスは、2,3-ジクロロ-1,3-ブタジエンを30質量%以下含有する原料単量体を25℃以上で重合することにより得られる。 (Production method of polychloroprene latex)
Next, the manufacturing method of polychloroprene latex is demonstrated. The polychloroprene latex can be obtained by polymerizing a raw material monomer containing 30% by mass or less of 2,3-dichloro-1,3-butadiene at 25 ° C. or more.
次に、ポリクロロプレンラテックスの製造方法について説明する。ポリクロロプレンラテックスは、2,3-ジクロロ-1,3-ブタジエンを30質量%以下含有する原料単量体を25℃以上で重合することにより得られる。 (Production method of polychloroprene latex)
Next, the manufacturing method of polychloroprene latex is demonstrated. The polychloroprene latex can be obtained by polymerizing a raw material monomer containing 30% by mass or less of 2,3-dichloro-1,3-butadiene at 25 ° C. or more.
単量体の重合方法としては、乳化重合、溶液重合、懸濁重合及び塊状重合などを適用することができるが、ポリクロロプレンラテックスの製造には、特に乳化重合法が好適である。また、原料単量体を乳化重合する際の乳化・分散剤としては、通常のロジン酸のアルカリ金属塩を用いることができる。
Emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization and the like can be applied as the monomer polymerization method, and the emulsion polymerization method is particularly suitable for the production of polychloroprene latex. Further, as an emulsifying / dispersing agent for emulsion polymerization of the raw material monomer, a normal alkali metal salt of rosin acid can be used.
また、乳化・分散剤には、前述したロジン酸のアルカリ金属塩と、カルボン酸型、スルホン酸型、硫酸エステル型、リン酸エステル型の乳化・分散剤を併用してもよい。これら併用可能な乳化・分散剤のうち、カルボン酸型の乳化・分散剤としては、例えば、脂肪族モノカルボン酸塩、ポリオキシエチレンアルキルエーテルカルボン酸塩、n-アシルサルコシン塩、n-アシルグルタミン酸塩などが挙げられる。
Further, as the emulsifier / dispersant, the alkali metal salt of rosin acid described above and a carboxylic acid type, sulfonic acid type, sulfate ester type, or phosphate ester type emulsifier / dispersant may be used in combination. Among these emulsifying / dispersing agents that can be used in combination, carboxylic acid type emulsifying / dispersing agents include, for example, aliphatic monocarboxylates, polyoxyethylene alkyl ether carboxylates, n-acyl sarcosine salts, and n-acyl glutamic acids. Examples include salt.
スルホン酸型の乳化・分散剤としては、例えば、ジアルキルスルホコハク酸塩、アルカンスルホン酸塩、α-オレフィンスルホン酸塩、直鎖アルキルベンゼンスルホン酸塩、アルキル(分岐型)ベンゼンスルホン酸塩、ナフタレンスルホン酸塩ホルムアルデヒド縮合物、アルキルナフタレンスルホン酸塩、n-メチル-n-アシルタウリン塩などが挙げられる。硫酸エステル型の乳化・分散剤としては、例えば、アルキル硫酸エステル塩、アルコールエトキシサルフェート、油脂硫酸エステル塩などが挙げられる。リン酸エステル型の乳化・分散剤としては、例えば、アルキルリン酸塩、ポリオキシエチレンアルキルエーテルリン酸塩、ポリオキシエチレンアルキルフェニルエーテルリン酸塩などが挙げられる。
Examples of sulfonic acid type emulsifying and dispersing agents include dialkyl sulfosuccinates, alkane sulfonates, α-olefin sulfonates, linear alkyl benzene sulfonates, alkyl (branched) benzene sulfonates, and naphthalene sulfonic acids. Salt formaldehyde condensates, alkyl naphthalene sulfonates, n-methyl-n-acyl taurine salts and the like. Examples of the sulfuric ester type emulsifying / dispersing agent include alkyl sulfate ester salts, alcohol ethoxy sulfates, and oil sulfate sulfate salts. Examples of the phosphoric acid ester type emulsifying / dispersing agent include alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, and the like.
更に、その他使用可能な乳化・分散剤としては、アルキルアリルスルホン酸、ポリオキシエチレンフェニルエーテル、ポリオキシアルキレンアルキルエーテル、ポリオキシエチレンアルキレンアルキルエーテル、ポリオキシエチレンスチレン化フェニルエーテル、ポリオキシエチレンジスチレン化フェニルエーテル、ポリオキシエチレントリベンジルフェニルエーテル、ポリオキシエチレンポリオキシプロピレングリコール、ポリオキシアルキレンアルケニルエーテル、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステルなどが挙げられる。
Furthermore, other usable emulsifying / dispersing agents include alkyl allyl sulfonic acid, polyoxyethylene phenyl ether, polyoxyalkylene alkyl ether, polyoxyethylene alkylene alkyl ether, polyoxyethylene styrenated phenyl ether, polyoxyethylene distyrene. Phenyloxy ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and the like.
連鎖移動剤としては、特に限定されるものではなく、通常のクロロプレンの乳化重合に使用される連鎖移動剤を使用できる。具体的には、n-ドデシルメルカプタンやtert-ドデシルメルカプタンなどの長鎖アルキルメルカプタン類、ジイソプロピルキサントゲンジスルフィドやジエチルキサントゲンジスルフィドなどのジアルキルキサントゲンジスルフィド類、ヨードホルムなどの公知の連鎖移動剤を使用することができる。
The chain transfer agent is not particularly limited, and a chain transfer agent used for usual emulsion polymerization of chloroprene can be used. Specifically, long chain alkyl mercaptans such as n-dodecyl mercaptan and tert-dodecyl mercaptan, dialkylxanthogen disulfides such as diisopropylxanthogen disulfide and diethylxanthogen disulfide, and known chain transfer agents such as iodoform can be used. .
重合開始剤としては、例えば、過硫酸カリウム、過硫酸アンモニウム、過硫酸ナトリウム、過酸化水素又は過酸化ベンゾイルなどの有機過酸化物類を用いることができる。
As the polymerization initiator, for example, organic peroxides such as potassium persulfate, ammonium persulfate, sodium persulfate, hydrogen peroxide or benzoyl peroxide can be used.
ポリクロロプレンラテックスの重合体の柔軟性の経時的安定性を保持するため、25℃以上の温度範囲で重合を行うことが好ましく、25~55℃の温度範囲で重合を行うことがより好ましく、さらに好ましくは30~50℃の範囲である。重合温度を25℃以上に設定することによって、ポリクロロプレンラテックスの結晶化を抑え、ポリクロロプレンラテックスを用いた手袋等の浸漬成形品の柔軟性を向上させることができる。
In order to maintain the flexibility of the polychloroprene latex polymer over time, the polymerization is preferably performed in a temperature range of 25 ° C. or more, more preferably in the temperature range of 25 to 55 ° C. Preferably, it is in the range of 30 to 50 ° C. By setting the polymerization temperature to 25 ° C. or higher, the crystallization of the polychloroprene latex can be suppressed, and the flexibility of an immersion molded product such as a glove using the polychloroprene latex can be improved.
また、原料単量体の重合転化率は、80~95%であることが好ましく、より好ましくは85~95%である。この重合転化率が80%未満である場合は、重合体ラテックスの固形分が低下し、生産性が低下する場合がある。また、重合転化率が95%より大きい場合は、重合時間が長くなって生産性が低下したり、浸漬成形品とした際の機械的強度が低下したり、脆くなる場合がある。
The polymerization conversion rate of the raw material monomer is preferably 80 to 95%, more preferably 85 to 95%. When this polymerization conversion rate is less than 80%, the solid content of the polymer latex is lowered, and the productivity may be lowered. On the other hand, when the polymerization conversion rate is larger than 95%, the polymerization time may be prolonged to lower the productivity, the mechanical strength when the dip-molded product is made, or the brittleness may be caused.
原料単量体の重合転化率が100%に達する前に重合を停止する際に添加する重合停止剤は、例えば、チオジフェニルアミン、4-tert-ブチルカテコール、2,2-メチレンビス-4-メチル-6-tert-ブチルフェノール、ジエチルヒドロキシルアミンなどを用いることができる。
The polymerization terminator added when the polymerization is terminated before the polymerization conversion rate of the raw material monomer reaches 100% is, for example, thiodiphenylamine, 4-tert-butylcatechol, 2,2-methylenebis-4-methyl- 6-tert-butylphenol, diethylhydroxylamine and the like can be used.
[複合亜鉛華]
本実施形態のポリクロロプレンラテックス組成物には、ポリクロロプレンラテックスの製膜性を向上させるとともに、得られるポリクロロプレンラテックスフィルムの引張強度を向上させる目的で無機塩及び酸化亜鉛を含む複合亜鉛華が配合されている。 [Composite zinc white]
The polychloroprene latex composition of the present embodiment is blended with a composite zinc white containing an inorganic salt and zinc oxide for the purpose of improving the film forming property of the polychloroprene latex and improving the tensile strength of the resulting polychloroprene latex film. Has been.
本実施形態のポリクロロプレンラテックス組成物には、ポリクロロプレンラテックスの製膜性を向上させるとともに、得られるポリクロロプレンラテックスフィルムの引張強度を向上させる目的で無機塩及び酸化亜鉛を含む複合亜鉛華が配合されている。 [Composite zinc white]
The polychloroprene latex composition of the present embodiment is blended with a composite zinc white containing an inorganic salt and zinc oxide for the purpose of improving the film forming property of the polychloroprene latex and improving the tensile strength of the resulting polychloroprene latex film. Has been.
複合亜鉛華は、ポリクロロプレンラテックスの固形分100質量部に対して、0.01~10質量部配合する。ポリクロロプレンラテックス中、複合亜鉛華の配合量が0.01質量部未満であると、加硫速度が遅くなり、浸漬成形品の機械的強度が低下する。一方、ポリクロロプレンラテックス中、複合亜鉛華の配合量が10質量部を超えると、複合亜鉛華の粒子をラテックス中に均一分散させることが困難になる。
The composite zinc white is blended in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the solid content of the polychloroprene latex. If the blending amount of the composite zinc white is less than 0.01 parts by mass in the polychloroprene latex, the vulcanization rate becomes slow and the mechanical strength of the immersion molded product is lowered. On the other hand, when the compounding amount of the composite zinc white exceeds 10 parts by mass in the polychloroprene latex, it is difficult to uniformly disperse the composite zinc white particles in the latex.
本実施形態のポリクロロプレンラテックス組成物に含まれる複合亜鉛華の個数平均粒径は、0.05~0.35μmとする。複合亜鉛華の個数平均粒径が0.35μmを超えてしまうと、単位体積あたりの複合亜鉛華の表面積が小さくなり、ポリクロロプレンラテックスとの反応効率が低下するため、得られるフィルムの引張強度を向上させるという目的を達成できない。一方、複合亜鉛華の個数平均粒径が0.05μmに満たないと、工業的な生産性が低下するだけでなく、ポリクロロプレンラテックスに添加する際に、複合亜鉛華同士が凝集するなど、取り扱い性が低下する。なお、複合亜鉛華の個数平均粒径は、SEM観察によりJIS Z8901に準拠した方法で測定することができる。
The number average particle size of the composite zinc white contained in the polychloroprene latex composition of the present embodiment is 0.05 to 0.35 μm. If the number average particle diameter of the composite zinc white exceeds 0.35 μm, the surface area of the composite zinc white per unit volume decreases, and the reaction efficiency with the polychloroprene latex decreases, so the tensile strength of the resulting film is reduced. The goal of improving cannot be achieved. On the other hand, when the number average particle size of the composite zinc white is less than 0.05 μm, not only the industrial productivity is lowered but also the composite zinc white aggregates when added to the polychloroprene latex. Sex is reduced. In addition, the number average particle size of the composite zinc white can be measured by a method based on JIS Z8901 by SEM observation.
また、本実施形態のポリクロロプレンラテックス組成物に含まれる複合亜鉛華の粒径は、0.01~1.0μmとする。複合亜鉛華の粒径が0.01μmに満たないと複合亜鉛華同士が凝集し、ポリクロロプレンラテックスとの反応効率が低下する。一方、複合亜鉛華の粒径が1.0μmを越える複合亜鉛華を用いると単位体積あたりの複合亜鉛華の表面積が小さくなり、ポリクロロプレンラテックスとの反応効率が低下する。
The particle size of the composite zinc white contained in the polychloroprene latex composition of the present embodiment is 0.01 to 1.0 μm. If the particle size of the composite zinc white is less than 0.01 μm, the composite zinc white aggregates and the reaction efficiency with the polychloroprene latex decreases. On the other hand, when a composite zinc white having a composite zinc white particle size exceeding 1.0 μm is used, the surface area of the composite zinc white per unit volume is reduced and the reaction efficiency with the polychloroprene latex is lowered.
複合亜鉛華の比表面積は、10~35m2/gとする。複合亜鉛華の比表面積が10m2/gに満たないと、ポリクロロプレンラテックスとの反応効率が低下し、得られるフィルムの引張強度を向上させるという目的を達成できない。複合亜鉛華の比表面積が35m2/gを超えると、ポリクロロプレンラテックス組成物の工業的な生産性が低下したり、吸湿により品質が劣化したりする。なお、複合亜鉛華の比表面積は、JIS Z8830に準拠した方法で測定することができる。
The specific surface area of the composite zinc white is 10 to 35 m 2 / g. If the specific surface area of the composite zinc white is less than 10 m 2 / g, the reaction efficiency with the polychloroprene latex decreases, and the purpose of improving the tensile strength of the resulting film cannot be achieved. When the specific surface area of the composite zinc white exceeds 35 m 2 / g, the industrial productivity of the polychloroprene latex composition is lowered, or the quality is deteriorated due to moisture absorption. In addition, the specific surface area of a composite zinc white can be measured by the method based on JISZ8830.
また、本実施形態のポリクロロプレンラテックス組成物に含まれる複合亜鉛華には、亜鉛が20~98質量%、カルシウムが1~30質量%、マグネシウムが0.01~10質量%の元素が含まれている。複合亜鉛華中の元素として、亜鉛、カルシウム、及びマグネシウムは蛍光X線分析により定量する。複合亜鉛華中、亜鉛、カルシウム、及びマグネシウムの夫々が上記の範囲を外れると、加硫速度が遅くなるために機械的強度が低下したり、加硫速度が速過ぎるためにスコーチを起こしたりする。なお、蛍光X線分析は、例えば、JIS K 0119に記載された蛍光X線分析法に準拠して行うことができる。なお、複合亜鉛華には、ケイ素、硫黄、鉄、アルミニウム、ジルコニウム又はリンなどの元素が不純物として含まれていてもよい。
In addition, the composite zinc white contained in the polychloroprene latex composition of the present embodiment includes elements of 20 to 98% by mass of zinc, 1 to 30% by mass of calcium, and 0.01 to 10% by mass of magnesium. ing. As elements in the composite zinc white, zinc, calcium, and magnesium are quantified by fluorescent X-ray analysis. If each of zinc, calcium, and magnesium is out of the above range in the composite zinc white, the vulcanization speed becomes slow, so that the mechanical strength is lowered, or the vulcanization speed is too fast, and scorch is caused. The fluorescent X-ray analysis can be performed in accordance with, for example, the fluorescent X-ray analysis method described in JIS K 0119. The composite zinc white may contain elements such as silicon, sulfur, iron, aluminum, zirconium, or phosphorus as impurities.
本実施形態のポリクロロプレンラテックス組成物に含まれる複合亜鉛華の構造は、特に限定されないが、無機塩を核として、その表層として酸化亜鉛を積層、被覆させた複合構造であることが好ましい。複合亜鉛華を、このような複合構造にすることによって、複合亜鉛華粒子に含有される亜鉛分を効率よくポリクロロプレンラテックスと反応させることができる。なお、複合亜鉛華の複合構造については、走査型電子顕微鏡(Scanning Electron Microscope、SEM)又はエネルギー分散型X線分析装置(Energy Dispersive X-ray Spectrometer、EDS)で観察することにより分析することができる。
The structure of the composite zinc white contained in the polychloroprene latex composition of the present embodiment is not particularly limited, but a composite structure in which an inorganic salt is used as a nucleus and zinc oxide is laminated and coated as a surface layer is preferable. By making the composite zinc white into such a composite structure, the zinc content contained in the composite zinc white particles can be efficiently reacted with the polychloroprene latex. The composite structure of composite zinc white can be analyzed by observing with a scanning electron microscope (Scanning Electron Microscope, SEM) or an energy dispersive X-ray analyzer (Energy Dispersive X-ray Spectrometer, EDS). .
複合亜鉛華の核に用いる無機塩としては、炭酸カルシウム、次亜塩素酸カルシウム、炭酸マグネシウム、酸化マグネシウム及び水酸化マグネシウムのうちから選ばれる少なくとも一種の化合物を使用することができる。複合亜鉛華に、無機塩として、炭酸カルシウム、次亜塩素酸カルシウム、炭酸マグネシウム、酸化マグネシウム及び水酸化マグネシウムのうちから選ばれる少なくとも一種の化合物を含有させることによって、複合亜鉛華自身の比重を調製することができ、ポリクロロプレンラテックスに添加した際の複合亜鉛華の分散性を向上させることができる。
As the inorganic salt used for the core of the composite zinc white, at least one compound selected from calcium carbonate, calcium hypochlorite, magnesium carbonate, magnesium oxide and magnesium hydroxide can be used. Prepare the specific gravity of the composite zinc white by adding at least one compound selected from calcium carbonate, calcium hypochlorite, magnesium carbonate, magnesium oxide and magnesium hydroxide as an inorganic salt. It is possible to improve the dispersibility of the composite zinc white when added to the polychloroprene latex.
本実施形態のポリクロロプレンラテックス組成物は、乳化剤を使用して複合亜鉛華を水中に分散させ、複合亜鉛華をポリクロロプレンラテックスに添加することにより得られる。
The polychloroprene latex composition of this embodiment is obtained by dispersing the composite zinc white in water using an emulsifier and adding the composite zinc white to the polychloroprene latex.
複合亜鉛華を水中に分散させるための乳化剤としては、一般的なアニオン系乳化剤を用いればよく、例えば、R.T.Verderbilt Company製のDarvan No.1(商品名)などの市販品が挙げられる。
As an emulsifier for dispersing the composite zinc white in water, a general anionic emulsifier may be used. T.A. Vervanbilt Company's Darvan No. Commercial products such as 1 (trade name) are listed.
前述したポリクロロプレンラテックス組成物は、そのままでも浸漬成形品の材料をして用いることができるが、各種添加剤を添加することもできる。この各種添加剤としては、具体的には、金属酸化物、硫黄、酸化防止剤及び界面活性剤などが挙げられる。
The polychloroprene latex composition described above can be used as it is as a material for an immersion molded product, but various additives can also be added. Specific examples of the various additives include metal oxides, sulfur, antioxidants, and surfactants.
[金属酸化物:ポリクロロプレンラテックスの固形分100質量部に対して0.1~10質量部]
本実施形態のポリクロロプレンラテックス組成物では、金属酸化物は、特に限定されるものではなく、例えば酸化亜鉛、酸化鉛及び四酸化三鉛などを配合することができる。これらは単独で使用してもよいが、必要に応じて2種以上を組み合わせて用いることもできる。 [Metal oxide: 0.1 to 10 parts by mass with respect to 100 parts by mass of the solid content of polychloroprene latex]
In the polychloroprene latex composition of the present embodiment, the metal oxide is not particularly limited, and for example, zinc oxide, lead oxide, trilead tetraoxide, and the like can be blended. These may be used alone or in combination of two or more as required.
本実施形態のポリクロロプレンラテックス組成物では、金属酸化物は、特に限定されるものではなく、例えば酸化亜鉛、酸化鉛及び四酸化三鉛などを配合することができる。これらは単独で使用してもよいが、必要に応じて2種以上を組み合わせて用いることもできる。 [Metal oxide: 0.1 to 10 parts by mass with respect to 100 parts by mass of the solid content of polychloroprene latex]
In the polychloroprene latex composition of the present embodiment, the metal oxide is not particularly limited, and for example, zinc oxide, lead oxide, trilead tetraoxide, and the like can be blended. These may be used alone or in combination of two or more as required.
金属酸化物配合量は、特に限定するものではないが、ポリクロロプレンラテックスの固形分100質量部に対して0.1~10質量部の範囲にすることで、成形品の触感を維持しつつ、成形品の引張り強度及びモジュラスの基本特性をより向上させることができる。
The amount of the metal oxide blended is not particularly limited, but by maintaining the tactile feel of the molded product within the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the solid content of the polychloroprene latex, The basic properties of the tensile strength and modulus of the molded product can be further improved.
[硫黄:ポリクロロプレンラテックスの固形分100質量部に対して0.1~3質量部]
本実施形態のポリクロロプレンラテックス組成物では、硫黄は、ポリクロロプレンの加硫を促進させるために配合する。硫黄の配合量は、特に限定するものではないが、ポリクロロプレンラテックスの固形分100質量部に対して0.1~3質量部の範囲にすることで、加硫後の耐熱性の低下や製品表面へのブリードを防止しつつ加硫促進効果を得ることができる。 [Sulfur: 0.1 to 3 parts by mass with respect to 100 parts by mass of solid content of polychloroprene latex]
In the polychloroprene latex composition of this embodiment, sulfur is blended in order to promote vulcanization of polychloroprene. The amount of sulfur blended is not particularly limited, but the heat resistance after vulcanization can be reduced and the product can be reduced to 0.1-3 parts by weight with respect to 100 parts by weight of the solid content of the polychloroprene latex. The effect of promoting vulcanization can be obtained while preventing bleeding on the surface.
本実施形態のポリクロロプレンラテックス組成物では、硫黄は、ポリクロロプレンの加硫を促進させるために配合する。硫黄の配合量は、特に限定するものではないが、ポリクロロプレンラテックスの固形分100質量部に対して0.1~3質量部の範囲にすることで、加硫後の耐熱性の低下や製品表面へのブリードを防止しつつ加硫促進効果を得ることができる。 [Sulfur: 0.1 to 3 parts by mass with respect to 100 parts by mass of solid content of polychloroprene latex]
In the polychloroprene latex composition of this embodiment, sulfur is blended in order to promote vulcanization of polychloroprene. The amount of sulfur blended is not particularly limited, but the heat resistance after vulcanization can be reduced and the product can be reduced to 0.1-3 parts by weight with respect to 100 parts by weight of the solid content of the polychloroprene latex. The effect of promoting vulcanization can be obtained while preventing bleeding on the surface.
[酸化防止剤:ポリクロロプレンラテックスの固形分100質量部に対して0.1~5質量部]
本実施形態のポリクロロプレンラテックス組成物では、酸化防止剤は、得られる成形品の耐熱性や耐オゾン性を向上させるために配合する。耐熱性付与目的の酸化防止剤としては、耐熱性だけでなく、耐汚染性(変色などの移行)も少ないことから、オクチル化ジフェニルアミン、p-(p-トルエン-スルホニルアミド)ジフェニルアミンや4,4’-ビス(α,α-ジメチルベンジル)ジフェニルアミンなどのジフェニルアミン系が好適である。 [Antioxidant: 0.1 to 5 parts by mass with respect to 100 parts by mass of solid content of polychloroprene latex]
In the polychloroprene latex composition of the present embodiment, the antioxidant is blended in order to improve the heat resistance and ozone resistance of the obtained molded product. Antioxidants for the purpose of imparting heat resistance are not only heat resistant but also less stain resistant (displacement such as discoloration), so octylated diphenylamine, p- (p-toluene-sulfonylamido) diphenylamine and 4,4 Diphenylamine systems such as' -bis (α, α-dimethylbenzyl) diphenylamine are preferred.
本実施形態のポリクロロプレンラテックス組成物では、酸化防止剤は、得られる成形品の耐熱性や耐オゾン性を向上させるために配合する。耐熱性付与目的の酸化防止剤としては、耐熱性だけでなく、耐汚染性(変色などの移行)も少ないことから、オクチル化ジフェニルアミン、p-(p-トルエン-スルホニルアミド)ジフェニルアミンや4,4’-ビス(α,α-ジメチルベンジル)ジフェニルアミンなどのジフェニルアミン系が好適である。 [Antioxidant: 0.1 to 5 parts by mass with respect to 100 parts by mass of solid content of polychloroprene latex]
In the polychloroprene latex composition of the present embodiment, the antioxidant is blended in order to improve the heat resistance and ozone resistance of the obtained molded product. Antioxidants for the purpose of imparting heat resistance are not only heat resistant but also less stain resistant (displacement such as discoloration), so octylated diphenylamine, p- (p-toluene-sulfonylamido) diphenylamine and 4,4 Diphenylamine systems such as' -bis (α, α-dimethylbenzyl) diphenylamine are preferred.
また、耐オゾン性付与目的の酸化防止剤としては、N,N’-ジフェニル-p-フェニレジアミン(DPPD)やN-イソプロピル-N’-フェニル-p-フェニレンジアミン(IPPD)が好適である。ただし、通常、使い捨て手袋などのように、外観、特に色調や衛生性を重視される場合には、ヒンダードフェノール系酸化防止剤が好適である。これら耐熱性付与目的の酸化防止剤と耐オゾン性付与目的の酸化防止剤とは、併用することが好ましい。
Further, N, N′-diphenyl-p-phenylediamine (DPPD) and N-isopropyl-N′-phenyl-p-phenylenediamine (IPPD) are suitable as the antioxidant for imparting ozone resistance. . However, a hindered phenolic antioxidant is usually preferred when the appearance, particularly color tone and hygiene, are important, such as disposable gloves. These antioxidants for imparting heat resistance and antioxidants for imparting ozone resistance are preferably used in combination.
これら酸化防止剤の添加量は、特に限定するものではないが、ポリクロロプレンラテックスの固形分100質量部に対して、0.1~5質量部の範囲にすることで、ポリクロロプレンの加硫阻害や、色調の低下を防止しつつ、十分な酸化防止効果を得ることができる。
The amount of these antioxidants to be added is not particularly limited. However, when the amount is 0.1 to 5 parts by mass with respect to 100 parts by mass of the solid content of the polychloroprene latex, vulcanization inhibition of polychloroprene is inhibited. In addition, a sufficient antioxidant effect can be obtained while preventing a decrease in color tone.
[界面活性剤:ポリクロロプレンラテックスの固形分100質量部に対して0.1~10質量部]
本実施形態のポリクロロプレンラテックス組成物では、界面活性剤は、ポリクロロプレンラテックスのコロイド安定化のために配合する。界面活性剤としては、アルキル硫酸ナトリウム、アルキルベンゼンスルホン酸ナトリウム、ナフタレンスルホン酸ホルムアルデヒド縮合物のナトリウム塩やロジン酸石鹸、脂肪酸石鹸などを使用することができる。これら界面活性剤の添加量は、特に限定するものではないが、ポリクロロプレンラテックスの固形分100質量部に対して0.1~10質量部の範囲にすることで、成形品の発泡やピンホールなどの欠陥が発生することを防止しつつ、十分なコロイドの安定化を行うことができる。 [Surfactant: 0.1 to 10 parts by mass with respect to 100 parts by mass of solid content of polychloroprene latex]
In the polychloroprene latex composition of this embodiment, the surfactant is blended for colloidal stabilization of the polychloroprene latex. As the surfactant, sodium alkyl sulfate, sodium alkylbenzene sulfonate, sodium salt of naphthalene sulfonate formaldehyde condensate, rosin acid soap, fatty acid soap and the like can be used. The amount of these surfactants to be added is not particularly limited. By setting the amount in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the polychloroprene latex, foaming of a molded product or pinhole It is possible to sufficiently stabilize the colloid while preventing the occurrence of such defects.
本実施形態のポリクロロプレンラテックス組成物では、界面活性剤は、ポリクロロプレンラテックスのコロイド安定化のために配合する。界面活性剤としては、アルキル硫酸ナトリウム、アルキルベンゼンスルホン酸ナトリウム、ナフタレンスルホン酸ホルムアルデヒド縮合物のナトリウム塩やロジン酸石鹸、脂肪酸石鹸などを使用することができる。これら界面活性剤の添加量は、特に限定するものではないが、ポリクロロプレンラテックスの固形分100質量部に対して0.1~10質量部の範囲にすることで、成形品の発泡やピンホールなどの欠陥が発生することを防止しつつ、十分なコロイドの安定化を行うことができる。 [Surfactant: 0.1 to 10 parts by mass with respect to 100 parts by mass of solid content of polychloroprene latex]
In the polychloroprene latex composition of this embodiment, the surfactant is blended for colloidal stabilization of the polychloroprene latex. As the surfactant, sodium alkyl sulfate, sodium alkylbenzene sulfonate, sodium salt of naphthalene sulfonate formaldehyde condensate, rosin acid soap, fatty acid soap and the like can be used. The amount of these surfactants to be added is not particularly limited. By setting the amount in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the polychloroprene latex, foaming of a molded product or pinhole It is possible to sufficiently stabilize the colloid while preventing the occurrence of such defects.
なお、前述した各成分のうち、水に不溶であったり、ポリクロロプレンラテックスのコロイド状態を不安定化させたりする成分は、予め水系分散体を調製してからポリクロロプレンラテックスに添加することが好ましい。
Of the components described above, components that are insoluble in water or destabilize the colloidal state of the polychloroprene latex are preferably added to the polychloroprene latex after preparing an aqueous dispersion in advance. .
更に、本実施形態のポリクロロプレンラテックス組成物には、必要に応じて、前述した各成分に加えて、加硫促進剤、pH調整剤、充填剤、可塑剤、顔料、着色剤、湿潤剤及び消泡剤などの各種添加剤を配合することができる。
Further, in the polychloroprene latex composition of the present embodiment, a vulcanization accelerator, a pH adjuster, a filler, a plasticizer, a pigment, a colorant, a wetting agent, Various additives such as an antifoaming agent can be blended.
以上詳述したように、本実施形態のポリクロロプレンラテックス組成物は、特定量の複合亜鉛華を含有し、当該複合亜鉛華の個数平均粒径、粒径及び比表面積を特定の範囲に規定し、蛍光X線分析により定量される元素が特定の範囲にあるため、ポリクロロプレンラテックスが本来有する基本特性を維持しつつ、浸漬成形した際の引張り強度や柔軟性等の機械的強度を向上することができる。これにより、ポリクロロプレンラテックス組成物を用いてフィルムを成形した際に、フィルム厚を薄くすることができる。更にポリクロロプレンラテックス組成物は、手袋などの浸漬成形品に使用することができる。
As described above in detail, the polychloroprene latex composition of the present embodiment contains a specific amount of composite zinc white, and defines the number average particle diameter, particle size, and specific surface area of the composite zinc white within a specific range. Since the elements quantified by X-ray fluorescence analysis are in a specific range, the mechanical properties such as tensile strength and flexibility when dip-molding are improved while maintaining the basic properties inherent in polychloroprene latex. Can do. Thereby, when shape | molding a film using a polychloroprene latex composition, film thickness can be made thin. Furthermore, the polychloroprene latex composition can be used for immersion molded articles such as gloves.
(第2の実施形態)
次に、本発明の第2の実施形態の浸漬成形品について説明する。本実施形態の浸漬成形品は、前述した第1の実施形態のポリクロロプレンラテックス組成物を浸漬成形して得られ、例えば手袋である。 (Second Embodiment)
Next, the immersion molded product of the second embodiment of the present invention will be described. The immersion molded product of the present embodiment is obtained by immersion molding of the polychloroprene latex composition of the first embodiment described above, and is, for example, a glove.
次に、本発明の第2の実施形態の浸漬成形品について説明する。本実施形態の浸漬成形品は、前述した第1の実施形態のポリクロロプレンラテックス組成物を浸漬成形して得られ、例えば手袋である。 (Second Embodiment)
Next, the immersion molded product of the second embodiment of the present invention will be described. The immersion molded product of the present embodiment is obtained by immersion molding of the polychloroprene latex composition of the first embodiment described above, and is, for example, a glove.
本実施形態の浸漬成形品の製造方法は、特に限定されるものではなく、通常の方法で浸漬成形し、加硫すればよい。具体的には、凝集剤をコーティングした成形型を、ポリクロロプレンラテックス組成物に浸漬し、その表面にポリクロロプレンラテックス組成物を凝固させて未加硫のゴム皮膜を作製する。そして、浸出により水溶性不純物を除去し、乾燥させた後、加硫して、得られたゴム皮膜を離型する。これにより、フィルム状の浸漬成形品が得られる。
The manufacturing method of the immersion molded product of the present embodiment is not particularly limited, and may be immersion molded and vulcanized by a normal method. Specifically, a mold coated with a flocculant is immersed in a polychloroprene latex composition, and the polychloroprene latex composition is coagulated on the surface to produce an unvulcanized rubber film. Then, water-soluble impurities are removed by leaching, and after drying, vulcanization is performed to release the obtained rubber film. Thereby, a film-like immersion molded product is obtained.
本実施形態の浸漬成形品の厚さは、ポリクロロプレンラテックス組成物に、成形型を浸漬する時間、又は、ポリクロロプレンラテックス組成物の固形分濃度によって調整することができる。即ち、浸漬成形品の厚さを薄くしたい場合は、浸漬時間を短縮したり、ポリクロロプレンラテックス組成物の固形分濃度を低く調整すればよい。
The thickness of the immersion molded product of the present embodiment can be adjusted by the time during which the mold is immersed in the polychloroprene latex composition or the solid content concentration of the polychloroprene latex composition. That is, when it is desired to reduce the thickness of the immersion molded product, the immersion time may be shortened or the solid content concentration of the polychloroprene latex composition may be adjusted low.
以上詳述したように、本実施形態の浸漬成形品は、前述した第1の実施形態のポリクロロプレンラテックス組成物を使用しているため、機械的強度が改良され、薄肉成形性に優れる。
As described above in detail, since the immersion molded product of this embodiment uses the polychloroprene latex composition of the first embodiment described above, the mechanical strength is improved and the thin-wall moldability is excellent.
以下に、実施例及び比較例を挙げて本発明を説明するが、本発明はこれらの実施例に限定されるものではない。
Hereinafter, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited to these examples.
(実施例1)
<ポリクロロプレンラテックス組成物>
ポリクロロプレンラテックスLM-61(電気化学工業株式会社製、固形分60質量%)166.67質量部(固形分で100質量部)と、複合亜鉛華A(META-Z Latex(井上石灰工業株式会社製、固形分50質量%)10質量部(固形分で5質量部)と、加硫促進剤A(ノクセラーTP:大内新興化学株式会社製、50質量%水溶液)2質量部(固形分で1質量部)と、水分散液20質量部とを混合し、水を加えて配合物全体の固形分濃度を50%に調節して、ポリクロロプレンラテックス組成物を作製した。水分散液については、老化防止剤(ノクラック200:大内新興化学株式会社製、粉体)2質量部、加硫促進剤B(ノクセラーTET:大内新興化学株式会社製、粉体)1質量部、界面活性剤A(Darvan SMO:R.T.Verderbilt Company製、33.3質量%水溶液)9質量部(固形分で3質量部)、界面活性剤B(Darvan WAQ:R.T.Verderbilt Company製、25質量%水溶液)4質量部(固形分で1質量部)、水4質量部を、陶器製ボールミルを用いて、20℃で16時間混合し、調製した。 Example 1
<Polychloroprene latex composition>
Polychloroprene latex LM-61 (manufactured by Denki Kagaku Kogyo Co., Ltd., solid content 60 mass%) 166.67 parts by mass (100 mass parts by solid content) and composite zinc white A (META-Z Latex (Inoue Lime Industry Co., Ltd.) Made, 50 mass% solid content) 10 mass parts (5 mass parts in solid content) and vulcanization accelerator A (Noxeller TP: manufactured by Ouchi Shinsei Chemical Co., Ltd., 50 mass% aqueous solution) 2 mass parts (in solid content) 1 part by mass) and 20 parts by mass of an aqueous dispersion were mixed, and water was added to adjust the solid content concentration of the entire formulation to 50% to prepare a polychloroprene latex composition. , Anti-aging agent (NOCRACK 200: manufactured by Ouchi Shinsei Chemical Co., Ltd., powder) 2 parts by mass, Vulcanization accelerator B (Noxeller TET: manufactured by Ouchi Shinsei Chemical Co., Ltd., powder) 1 part by mass, surfactant A (Darvan SMO 9 parts by mass (3 mass parts by solid, 33.3 mass% aqueous solution) manufactured by RT Verderbilt Company, 4 parts by mass of surfactant B (Darvan WAQ: manufactured by RT Verderbilt Company, 25 mass% aqueous solution) Parts (1 part by mass in terms of solid content) and 4 parts by mass of water were prepared by mixing at 20 ° C. for 16 hours using a ceramic ball mill.
<ポリクロロプレンラテックス組成物>
ポリクロロプレンラテックスLM-61(電気化学工業株式会社製、固形分60質量%)166.67質量部(固形分で100質量部)と、複合亜鉛華A(META-Z Latex(井上石灰工業株式会社製、固形分50質量%)10質量部(固形分で5質量部)と、加硫促進剤A(ノクセラーTP:大内新興化学株式会社製、50質量%水溶液)2質量部(固形分で1質量部)と、水分散液20質量部とを混合し、水を加えて配合物全体の固形分濃度を50%に調節して、ポリクロロプレンラテックス組成物を作製した。水分散液については、老化防止剤(ノクラック200:大内新興化学株式会社製、粉体)2質量部、加硫促進剤B(ノクセラーTET:大内新興化学株式会社製、粉体)1質量部、界面活性剤A(Darvan SMO:R.T.Verderbilt Company製、33.3質量%水溶液)9質量部(固形分で3質量部)、界面活性剤B(Darvan WAQ:R.T.Verderbilt Company製、25質量%水溶液)4質量部(固形分で1質量部)、水4質量部を、陶器製ボールミルを用いて、20℃で16時間混合し、調製した。 Example 1
<Polychloroprene latex composition>
Polychloroprene latex LM-61 (manufactured by Denki Kagaku Kogyo Co., Ltd., solid content 60 mass%) 166.67 parts by mass (100 mass parts by solid content) and composite zinc white A (META-Z Latex (Inoue Lime Industry Co., Ltd.) Made, 50 mass% solid content) 10 mass parts (5 mass parts in solid content) and vulcanization accelerator A (Noxeller TP: manufactured by Ouchi Shinsei Chemical Co., Ltd., 50 mass% aqueous solution) 2 mass parts (in solid content) 1 part by mass) and 20 parts by mass of an aqueous dispersion were mixed, and water was added to adjust the solid content concentration of the entire formulation to 50% to prepare a polychloroprene latex composition. , Anti-aging agent (NOCRACK 200: manufactured by Ouchi Shinsei Chemical Co., Ltd., powder) 2 parts by mass, Vulcanization accelerator B (Noxeller TET: manufactured by Ouchi Shinsei Chemical Co., Ltd., powder) 1 part by mass, surfactant A (Darvan SMO 9 parts by mass (3 mass parts by solid, 33.3 mass% aqueous solution) manufactured by RT Verderbilt Company, 4 parts by mass of surfactant B (Darvan WAQ: manufactured by RT Verderbilt Company, 25 mass% aqueous solution) Parts (1 part by mass in terms of solid content) and 4 parts by mass of water were prepared by mixing at 20 ° C. for 16 hours using a ceramic ball mill.
(未加硫フィルム)
ポリクロロプレンラテックス組成物を、下記表1に記載の一次凝集剤及び二次凝集剤を用いて浸漬フィルムを作製した。なお、一次凝集剤は、成膜した浸漬成形液の凝固を促進させる。その際、浸漬フィルムは次に示す方法で作製した。外径40mm、長さ320mmの試験管を、口部が上になるようにして深さ150mmまで一次凝集剤に10秒間浸漬し、一次凝集剤から取り出して3分間風乾した後、ポリクロロプレンラテックス組成物に1分間浸漬させて、試験管の表面に浸漬フィルムを作製した。得られた浸漬フィルムを流水で1分間リーチング(浸出)して水溶性成分を除去した。次いで二次凝集剤に1分間浸漬した後、流水で浸漬フィルム表面の二次凝集剤を除去した。更に70℃、2時間乾燥して未加硫フィルムを作製した。 (Unvulcanized film)
An immersion film was produced from the polychloroprene latex composition using a primary flocculant and a secondary flocculant described in Table 1 below. The primary flocculant promotes the solidification of the formed immersion molding liquid. At that time, the immersion film was produced by the following method. A test tube having an outer diameter of 40 mm and a length of 320 mm is immersed in a primary flocculant for 10 seconds to a depth of 150 mm with the mouth facing up, taken out from the primary flocculant and air-dried for 3 minutes, and then a polychloroprene latex composition An immersion film was produced on the surface of the test tube by immersing the product in the object for 1 minute. The obtained immersion film was leached (leached) with running water for 1 minute to remove water-soluble components. Subsequently, after being immersed in the secondary flocculant for 1 minute, the secondary flocculant on the surface of the immersion film was removed with running water. Furthermore, it dried at 70 degreeC for 2 hours, and produced the unvulcanized film.
ポリクロロプレンラテックス組成物を、下記表1に記載の一次凝集剤及び二次凝集剤を用いて浸漬フィルムを作製した。なお、一次凝集剤は、成膜した浸漬成形液の凝固を促進させる。その際、浸漬フィルムは次に示す方法で作製した。外径40mm、長さ320mmの試験管を、口部が上になるようにして深さ150mmまで一次凝集剤に10秒間浸漬し、一次凝集剤から取り出して3分間風乾した後、ポリクロロプレンラテックス組成物に1分間浸漬させて、試験管の表面に浸漬フィルムを作製した。得られた浸漬フィルムを流水で1分間リーチング(浸出)して水溶性成分を除去した。次いで二次凝集剤に1分間浸漬した後、流水で浸漬フィルム表面の二次凝集剤を除去した。更に70℃、2時間乾燥して未加硫フィルムを作製した。 (Unvulcanized film)
An immersion film was produced from the polychloroprene latex composition using a primary flocculant and a secondary flocculant described in Table 1 below. The primary flocculant promotes the solidification of the formed immersion molding liquid. At that time, the immersion film was produced by the following method. A test tube having an outer diameter of 40 mm and a length of 320 mm is immersed in a primary flocculant for 10 seconds to a depth of 150 mm with the mouth facing up, taken out from the primary flocculant and air-dried for 3 minutes, and then a polychloroprene latex composition An immersion film was produced on the surface of the test tube by immersing the product in the object for 1 minute. The obtained immersion film was leached (leached) with running water for 1 minute to remove water-soluble components. Subsequently, after being immersed in the secondary flocculant for 1 minute, the secondary flocculant on the surface of the immersion film was removed with running water. Furthermore, it dried at 70 degreeC for 2 hours, and produced the unvulcanized film.
(加硫フィルム物性)
未加硫フィルムを110℃、25分あるいは141℃、30分で加硫して加硫フィルムとし、JIS-K6251に記載の方法でダンベル状3号形に打ち抜いて試験片とし、株式会社上島製作所製の引張り試験機(ユニコーンII)を用いて300%伸長時のモジュラス、破断伸び、及び破断破断強度の測定を行った。 (Physical properties of vulcanized film)
The unvulcanized film was vulcanized at 110 ° C. for 25 minutes or 141 ° C. for 30 minutes to obtain a vulcanized film, which was punched into a dumbbell shape No. 3 by the method described in JIS-K6251 to obtain a test piece. The modulus at 300% elongation, elongation at break, and strength at break were measured using a tensile tester (Unicorn II).
未加硫フィルムを110℃、25分あるいは141℃、30分で加硫して加硫フィルムとし、JIS-K6251に記載の方法でダンベル状3号形に打ち抜いて試験片とし、株式会社上島製作所製の引張り試験機(ユニコーンII)を用いて300%伸長時のモジュラス、破断伸び、及び破断破断強度の測定を行った。 (Physical properties of vulcanized film)
The unvulcanized film was vulcanized at 110 ° C. for 25 minutes or 141 ° C. for 30 minutes to obtain a vulcanized film, which was punched into a dumbbell shape No. 3 by the method described in JIS-K6251 to obtain a test piece. The modulus at 300% elongation, elongation at break, and strength at break were measured using a tensile tester (Unicorn II).
(複合亜鉛華の個数平均粒径及び粒径)
SEM観察装置(FE-SEM SU6600:株式会社日立ハイテクノロジーズ)にて複合亜鉛華の粒径を測定し、得られた値から複合亜鉛華の個数平均粒径を算出した。なお、亜鉛華の個数平均粒径及び粒径は、複合亜鉛華を水希釈し、超音波分散した後に自然乾燥し、粉末状にして測定した。 (Number average particle size and particle size of composite zinc white)
The particle size of the composite zinc white was measured with an SEM observation apparatus (FE-SEM SU6600: Hitachi High-Technologies Corporation), and the number average particle size of the composite zinc white was calculated from the obtained value. The number average particle size and particle size of zinc white were measured by diluting the composite zinc white with water, ultrasonically dispersing it, and then naturally drying it to obtain a powder.
SEM観察装置(FE-SEM SU6600:株式会社日立ハイテクノロジーズ)にて複合亜鉛華の粒径を測定し、得られた値から複合亜鉛華の個数平均粒径を算出した。なお、亜鉛華の個数平均粒径及び粒径は、複合亜鉛華を水希釈し、超音波分散した後に自然乾燥し、粉末状にして測定した。 (Number average particle size and particle size of composite zinc white)
The particle size of the composite zinc white was measured with an SEM observation apparatus (FE-SEM SU6600: Hitachi High-Technologies Corporation), and the number average particle size of the composite zinc white was calculated from the obtained value. The number average particle size and particle size of zinc white were measured by diluting the composite zinc white with water, ultrasonically dispersing it, and then naturally drying it to obtain a powder.
(複合亜鉛華の比表面積)
比表面積測定装置(モノソーブ:ユアサアオオニクス株式会社)にて複合亜鉛華の比表面積を定量した。なお、複合亜鉛華の比表面積は、複合亜鉛華を水希釈し、超音波分散した後に自然乾燥し、粉末状にして測定した。 (Specific surface area of composite zinc white)
The specific surface area of the composite zinc white was quantified with a specific surface area measuring device (Monosorb: Yuasa Aonics Co., Ltd.). The specific surface area of the composite zinc white was measured by diluting the composite zinc white with water, ultrasonically dispersing it, and then drying it naturally to form a powder.
比表面積測定装置(モノソーブ:ユアサアオオニクス株式会社)にて複合亜鉛華の比表面積を定量した。なお、複合亜鉛華の比表面積は、複合亜鉛華を水希釈し、超音波分散した後に自然乾燥し、粉末状にして測定した。 (Specific surface area of composite zinc white)
The specific surface area of the composite zinc white was quantified with a specific surface area measuring device (Monosorb: Yuasa Aonics Co., Ltd.). The specific surface area of the composite zinc white was measured by diluting the composite zinc white with water, ultrasonically dispersing it, and then drying it naturally to form a powder.
(複合亜鉛華の成分分析)
複合亜鉛華を乾燥機にて70℃で12時間乾燥させた試料を粉砕した後、複合亜鉛華の含有元素を蛍光X線分析装置(ZSX100e:株式会社リガク)にて定量した。 (Component analysis of composite zinc white)
A sample obtained by drying the composite zinc white for 12 hours at 70 ° C. with a dryer was pulverized, and then the elements contained in the composite zinc white were quantified with a fluorescent X-ray analyzer (ZSX100e: Rigaku Corporation).
複合亜鉛華を乾燥機にて70℃で12時間乾燥させた試料を粉砕した後、複合亜鉛華の含有元素を蛍光X線分析装置(ZSX100e:株式会社リガク)にて定量した。 (Component analysis of composite zinc white)
A sample obtained by drying the composite zinc white for 12 hours at 70 ° C. with a dryer was pulverized, and then the elements contained in the composite zinc white were quantified with a fluorescent X-ray analyzer (ZSX100e: Rigaku Corporation).
(複合亜鉛華の含有鉱物)
X線回折装置(RINT 2500V:株式会社リガク)にて複合亜鉛華の含有鉱物を同定した。 (Contained mineral of composite zinc white)
A complex zinc white-containing mineral was identified with an X-ray diffractometer (RINT 2500V: Rigaku Corporation).
X線回折装置(RINT 2500V:株式会社リガク)にて複合亜鉛華の含有鉱物を同定した。 (Contained mineral of composite zinc white)
A complex zinc white-containing mineral was identified with an X-ray diffractometer (RINT 2500V: Rigaku Corporation).
(実施例2)
ポリクロロプレンラテックスLM-61(電気化学工業株式会社製、固形分60質量%)166.67質量部(固形分で100質量部)と、加硫促進剤A(ノクセラーTP:大内新興化学株式会社製、50質量%水溶液)2質量部(固形分で1質量部)と、水分散液20質量部(wet)とを混合し、水を加えて配合物全体の固形分濃度を50%に調節して、ポリクロロプレンラテックス組成物を作製した。水分散液については、老化防止剤(ノクラック200:大内新興化学株式会社製、粉体)を2質量部、加硫促進剤B(ノクセラーTET:大内新興化学株式会社製、粉体)を1質量部、界面活性剤A(Darvan SMO:R.T.Verderbilt Company製、33.3質量%水溶液)を9質量部(固形分で3質量部)、界面活性剤B(Darvan WAQ:R.T.Verderbilt Company製、25質量%水溶液)を4質量部(固形分で1質量部)、複合亜鉛華B(META-Z 102(井上石灰工業株式会社製、粉体)5質量部、水13質量部を、陶器製ボールミルを用いて、20℃で16時間混合し、調製した。フィルムサンプル作製については実施例1と同様に行い、実施例1と同様に評価と分析を行った。 (Example 2)
Polychloroprene latex LM-61 (manufactured by Denki Kagaku Kogyo Co., Ltd., solid content 60 mass%) 166.67 parts by mass (100 mass parts by solid content) and vulcanization accelerator A (Noxeller TP: Ouchi Shinsei Chemical Co., Ltd.) Manufactured, 50% by weight aqueous solution) 2 parts by weight (1 part by weight in solids) and 20 parts by weight of aqueous dispersion (wet) are mixed, and water is added to adjust the solids concentration of the entire formulation to 50%. Thus, a polychloroprene latex composition was prepared. For the aqueous dispersion, 2 parts by mass of an anti-aging agent (NOCRACK 200: manufactured by Ouchi Shinsei Chemical Co., Ltd., powder) and vulcanization accelerator B (Noxeller TET: manufactured by Ouchi Shinsei Chemical Co., Ltd., powder) 1 part by mass, surfactant A (Darvan SMO: manufactured by RT Verderbilt Company, 33.3% by mass aqueous solution) 9 parts by mass (3 parts by mass in solid content), surfactant B (Darvan WAQ: R.D. 4 parts by mass (1 mass part in solid content) of T. Verderbilt Company, 25 mass% aqueous solution), 5 parts by mass of composite zinc white B (META-Z 102 (manufactured by Inoue Lime Industry Co., Ltd., powder)), water 13 A mass part was prepared by mixing for 16 hours at 20 ° C. using a ceramic ball mill, and film samples were prepared in the same manner as in Example 1 and evaluated and analyzed in the same manner as in Example 1. It was.
ポリクロロプレンラテックスLM-61(電気化学工業株式会社製、固形分60質量%)166.67質量部(固形分で100質量部)と、加硫促進剤A(ノクセラーTP:大内新興化学株式会社製、50質量%水溶液)2質量部(固形分で1質量部)と、水分散液20質量部(wet)とを混合し、水を加えて配合物全体の固形分濃度を50%に調節して、ポリクロロプレンラテックス組成物を作製した。水分散液については、老化防止剤(ノクラック200:大内新興化学株式会社製、粉体)を2質量部、加硫促進剤B(ノクセラーTET:大内新興化学株式会社製、粉体)を1質量部、界面活性剤A(Darvan SMO:R.T.Verderbilt Company製、33.3質量%水溶液)を9質量部(固形分で3質量部)、界面活性剤B(Darvan WAQ:R.T.Verderbilt Company製、25質量%水溶液)を4質量部(固形分で1質量部)、複合亜鉛華B(META-Z 102(井上石灰工業株式会社製、粉体)5質量部、水13質量部を、陶器製ボールミルを用いて、20℃で16時間混合し、調製した。フィルムサンプル作製については実施例1と同様に行い、実施例1と同様に評価と分析を行った。 (Example 2)
Polychloroprene latex LM-61 (manufactured by Denki Kagaku Kogyo Co., Ltd., solid content 60 mass%) 166.67 parts by mass (100 mass parts by solid content) and vulcanization accelerator A (Noxeller TP: Ouchi Shinsei Chemical Co., Ltd.) Manufactured, 50% by weight aqueous solution) 2 parts by weight (1 part by weight in solids) and 20 parts by weight of aqueous dispersion (wet) are mixed, and water is added to adjust the solids concentration of the entire formulation to 50%. Thus, a polychloroprene latex composition was prepared. For the aqueous dispersion, 2 parts by mass of an anti-aging agent (NOCRACK 200: manufactured by Ouchi Shinsei Chemical Co., Ltd., powder) and vulcanization accelerator B (Noxeller TET: manufactured by Ouchi Shinsei Chemical Co., Ltd., powder) 1 part by mass, surfactant A (Darvan SMO: manufactured by RT Verderbilt Company, 33.3% by mass aqueous solution) 9 parts by mass (3 parts by mass in solid content), surfactant B (Darvan WAQ: R.D. 4 parts by mass (1 mass part in solid content) of T. Verderbilt Company, 25 mass% aqueous solution), 5 parts by mass of composite zinc white B (META-Z 102 (manufactured by Inoue Lime Industry Co., Ltd., powder)), water 13 A mass part was prepared by mixing for 16 hours at 20 ° C. using a ceramic ball mill, and film samples were prepared in the same manner as in Example 1 and evaluated and analyzed in the same manner as in Example 1. It was.
(実施例3)
複合亜鉛華A(META-Z Latex(井上石灰工業株式会社製、固形分50質量%)の添加量を、20質量部(固形分で10質量部)に変更したこと以外は、すべて実施例1と同じ手順で、ポリクロロプレンラテックス組成物及びフィルムサンプルを作製し、実施例1と同様に評価と分析を行った。 (Example 3)
Example 1 except that the added amount of composite zinc white A (META-Z Latex (Inoue Lime Industry Co., Ltd., solid content 50 mass%) was changed to 20 mass parts (10 mass parts solid content). A polychloroprene latex composition and a film sample were prepared by the same procedure as in Example 1 and evaluated and analyzed in the same manner as in Example 1.
複合亜鉛華A(META-Z Latex(井上石灰工業株式会社製、固形分50質量%)の添加量を、20質量部(固形分で10質量部)に変更したこと以外は、すべて実施例1と同じ手順で、ポリクロロプレンラテックス組成物及びフィルムサンプルを作製し、実施例1と同様に評価と分析を行った。 (Example 3)
Example 1 except that the added amount of composite zinc white A (META-Z Latex (Inoue Lime Industry Co., Ltd., solid content 50 mass%) was changed to 20 mass parts (10 mass parts solid content). A polychloroprene latex composition and a film sample were prepared by the same procedure as in Example 1 and evaluated and analyzed in the same manner as in Example 1.
(比較例1)
複合亜鉛華A(META-Z Latex(井上石灰工業株式会社製、固形分50質量%))の添加量を、30質量部(固形分で15質量部)に変更したこと以外は、すべて実施例1と同じ手順で、ポリクロロプレンラテックス組成物およびフィルムサンプルを作製し、実施例1と同様に評価と分析を行った。 (Comparative Example 1)
Except for changing the amount of composite zinc white A (META-Z Latex (manufactured by Inoue Lime Industry Co., Ltd., solid content 50 mass%)) to 30 mass parts (solid content 15 mass parts), all examples In the same procedure as in Example 1, a polychloroprene latex composition and a film sample were prepared and evaluated and analyzed in the same manner as in Example 1.
複合亜鉛華A(META-Z Latex(井上石灰工業株式会社製、固形分50質量%))の添加量を、30質量部(固形分で15質量部)に変更したこと以外は、すべて実施例1と同じ手順で、ポリクロロプレンラテックス組成物およびフィルムサンプルを作製し、実施例1と同様に評価と分析を行った。 (Comparative Example 1)
Except for changing the amount of composite zinc white A (META-Z Latex (manufactured by Inoue Lime Industry Co., Ltd., solid content 50 mass%)) to 30 mass parts (solid content 15 mass parts), all examples In the same procedure as in Example 1, a polychloroprene latex composition and a film sample were prepared and evaluated and analyzed in the same manner as in Example 1.
(比較例2)
実施例2において、複合亜鉛華Bを、亜鉛華C(AZO-B:正同化学工業株式会社製、粉体)5質量部に変更したこと以外は、すべて実施例2と同じ手順で、ポリクロロプレンラテックス組成物及びフィルムサンプルを作製し、実施例2と同様に評価と分析を行った。 (Comparative Example 2)
In Example 2, the same procedure as in Example 2 was performed except that the composite zinc white B was changed to 5 parts by mass of zinc white C (AZO-B: manufactured by Shodo Chemical Industry Co., Ltd., powder). A chloroprene latex composition and a film sample were prepared and evaluated and analyzed in the same manner as in Example 2.
実施例2において、複合亜鉛華Bを、亜鉛華C(AZO-B:正同化学工業株式会社製、粉体)5質量部に変更したこと以外は、すべて実施例2と同じ手順で、ポリクロロプレンラテックス組成物及びフィルムサンプルを作製し、実施例2と同様に評価と分析を行った。 (Comparative Example 2)
In Example 2, the same procedure as in Example 2 was performed except that the composite zinc white B was changed to 5 parts by mass of zinc white C (AZO-B: manufactured by Shodo Chemical Industry Co., Ltd., powder). A chloroprene latex composition and a film sample were prepared and evaluated and analyzed in the same manner as in Example 2.
(比較例3)
実施例2において、複合亜鉛華Bを、亜鉛華D(亜鉛華2種:堺化学工業株式会社製、粉体)5質量部に変更したこと以外は、すべて実施例2と同じ手順で、ポリクロロプレンラテックス組成物及びフィルムサンプルを作製し、実施例2と同様に評価と分析を行った。 (Comparative Example 3)
In Example 2, except that the composite zinc white B was changed to 5 parts by mass of zinc white D (2 types of zinc white: manufactured by Sakai Chemical Industry Co., Ltd., powder), the same procedure as in Example 2 was followed. A chloroprene latex composition and a film sample were prepared and evaluated and analyzed in the same manner as in Example 2.
実施例2において、複合亜鉛華Bを、亜鉛華D(亜鉛華2種:堺化学工業株式会社製、粉体)5質量部に変更したこと以外は、すべて実施例2と同じ手順で、ポリクロロプレンラテックス組成物及びフィルムサンプルを作製し、実施例2と同様に評価と分析を行った。 (Comparative Example 3)
In Example 2, except that the composite zinc white B was changed to 5 parts by mass of zinc white D (2 types of zinc white: manufactured by Sakai Chemical Industry Co., Ltd., powder), the same procedure as in Example 2 was followed. A chloroprene latex composition and a film sample were prepared and evaluated and analyzed in the same manner as in Example 2.
以上の評価結果と測定結果を表2に示す。
Table 2 shows the above evaluation results and measurement results.
上記表2に示すように、比較例1のポリクロロプレンラテックス組成物は、複合亜鉛華の含有量が10質量部を超えており、複合亜鉛華粒子が凝集しやすくなり、フィルム中で微分散しなかったため、加硫フィルムの破断強度が低かった。比較例2のポリクロロプレンラテックス組成物は、亜鉛華に蛍光X線分析により定量された元素にカルシウム及びマグネシウムが含まれておらず、実施例1~3に比べて、加硫速度が遅かったため、加硫フィルムの破断強度が低かった。更に、比較例3のポリクロロプレンラテックス組成物も、亜鉛華に蛍光X線分析により定量された元素にカルシウム及びマグネシウムが含まれておらず、実施例1~3に比べて、加硫速度が遅かったため、加硫フィルムの破断強度が低かった。
As shown in Table 2 above, in the polychloroprene latex composition of Comparative Example 1, the content of composite zinc white exceeds 10 parts by mass, the composite zinc white particles tend to aggregate, and are finely dispersed in the film. As a result, the rupture strength of the vulcanized film was low. Since the polychloroprene latex composition of Comparative Example 2 does not contain calcium and magnesium in the elements determined by fluorescent X-ray analysis in zinc white, the vulcanization rate was slower than in Examples 1 to 3, The rupture strength of the vulcanized film was low. Furthermore, the polychloroprene latex composition of Comparative Example 3 does not contain calcium and magnesium in the elements determined by fluorescent X-ray analysis in zinc white, and the vulcanization rate is slower than in Examples 1 to 3. Therefore, the rupture strength of the vulcanized film was low.
これに対して、表2に示すように、本発明の範囲内で作製した実施例1~3のポリクロロプレンラテックス組成物は、いずれの項目においても優れた特性を示した。また、実施例1~3のポリクロロプレンラテックス組成物を用いて、常法の浸漬成形法により手袋を作成した。得られた手袋は、肌触りがよく、破断強度に優れていた。これらの結果より、本発明によれば、浸漬成形品を成形した際に機械的強度が優れるポリクロロプレンラテックス組成物を実現できることが確認された。
On the other hand, as shown in Table 2, the polychloroprene latex compositions of Examples 1 to 3 produced within the scope of the present invention exhibited excellent characteristics in all items. In addition, gloves were prepared by the conventional immersion molding method using the polychloroprene latex compositions of Examples 1 to 3. The obtained glove had a good touch and was excellent in breaking strength. From these results, according to the present invention, it was confirmed that a polychloroprene latex composition having excellent mechanical strength when an immersion molded article was formed can be realized.
On the other hand, as shown in Table 2, the polychloroprene latex compositions of Examples 1 to 3 produced within the scope of the present invention exhibited excellent characteristics in all items. In addition, gloves were prepared by the conventional immersion molding method using the polychloroprene latex compositions of Examples 1 to 3. The obtained glove had a good touch and was excellent in breaking strength. From these results, according to the present invention, it was confirmed that a polychloroprene latex composition having excellent mechanical strength when an immersion molded article was formed can be realized.
Claims (8)
- ポリクロロプレンラテックスの固形分100質量部と、
無機塩及び酸化亜鉛を含む複合亜鉛華0.01~10質量部と、を少なくとも含有し、
前記複合亜鉛華は、
個数平均粒径が0.05~0.35μmであり、
粒径が0.01~1.0μmであり、
比表面積が10~35m2/gであり、
蛍光X線分析による定量値で、亜鉛20~98質量%、カルシウム1~30質量%及びマグネシウム0.01~30質量%を含有する
ポリクロロプレンラテックス組成物。 100 parts by mass of solid content of polychloroprene latex;
0.01 to 10 parts by mass of composite zinc white containing an inorganic salt and zinc oxide,
The composite zinc white is
The number average particle size is 0.05 to 0.35 μm,
The particle size is 0.01 to 1.0 μm,
The specific surface area is 10 to 35 m 2 / g,
A polychloroprene latex composition containing 20 to 98% by weight of zinc, 1 to 30% by weight of calcium and 0.01 to 30% by weight of magnesium as determined by fluorescent X-ray analysis. - 前記複合亜鉛華は、前記無機塩を核として、前記酸化亜鉛を表層に被覆させた複合構造であることを特徴とする請求項1に記載のポリクロロプレンラテックス組成物。 2. The polychloroprene latex composition according to claim 1, wherein the composite zinc white has a composite structure in which the inorganic salt is used as a core and the zinc oxide is coated on a surface layer.
- 前記無機塩は、炭酸カルシウム、次亜塩素酸カルシウム、炭酸マグネシウム、酸化マグネシウム及び水酸化マグネシウムのうちから選ばれる少なくとも一種の化合物であることを特徴とする請求項1または請求項2に記載のポリクロロプレンラテックス組成物。 3. The poly according to claim 1, wherein the inorganic salt is at least one compound selected from calcium carbonate, calcium hypochlorite, magnesium carbonate, magnesium oxide, and magnesium hydroxide. Chloroprene latex composition.
- 前記ポリクロロプレンラテックスが、2,3-ジクロロ-1,3-ブタジエンを30質量%以下含有する原料単量体を25℃以上で重合したものであることを特徴とする請求項1~3のいずれか一項に記載のポリクロロプレンラテックス組成物。 4. The polychloroprene latex is obtained by polymerizing a raw material monomer containing 30% by mass or less of 2,3-dichloro-1,3-butadiene at 25 ° C. or more. The polychloroprene latex composition according to claim 1.
- 更に、前記ポリクロロプレンラテックスの固形分100質量部に対して、
金属酸化物0.1~10質量部と、
硫黄0.1~3質量部と、
酸化防止剤0.1~5質量部と、
界面活性剤0.1~10質量部と
を配合したことを特徴とする請求項1~4のいずれか一項に記載のポリクロロプレンラテックス組成物。 Furthermore, with respect to 100 parts by mass of the solid content of the polychloroprene latex,
0.1 to 10 parts by mass of metal oxide,
0.1 to 3 parts by mass of sulfur,
0.1 to 5 parts by mass of an antioxidant,
The polychloroprene latex composition according to any one of claims 1 to 4, wherein 0.1 to 10 parts by mass of a surfactant is blended. - 浸漬成形品用であることを特徴とする請求項1~5のいずれか一項に記載のポリクロロプレンラテックス組成物。 The polychloroprene latex composition according to any one of claims 1 to 5, which is used for a dip-molded product.
- 請求項1~5のいずれか一項に記載のポリクロロプレンラテックス組成物を用いて浸漬成形された浸漬成形品。 An immersion molded article formed by immersion molding using the polychloroprene latex composition according to any one of claims 1 to 5.
- 手袋であることを特徴とする請求項7に記載の浸漬成形品。
It is a glove, The immersion molded product of Claim 7 characterized by the above-mentioned.
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