WO2022209827A1 - Foam rubber latex composition and foam rubber - Google Patents
Foam rubber latex composition and foam rubber Download PDFInfo
- Publication number
- WO2022209827A1 WO2022209827A1 PCT/JP2022/011392 JP2022011392W WO2022209827A1 WO 2022209827 A1 WO2022209827 A1 WO 2022209827A1 JP 2022011392 W JP2022011392 W JP 2022011392W WO 2022209827 A1 WO2022209827 A1 WO 2022209827A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- foam rubber
- weight
- latex composition
- latex
- solid content
- Prior art date
Links
- 229920001821 foam rubber Polymers 0.000 title claims abstract description 142
- 239000000203 mixture Substances 0.000 title claims abstract description 85
- 229920000126 latex Polymers 0.000 claims abstract description 125
- 229920001577 copolymer Polymers 0.000 claims abstract description 82
- 239000000178 monomer Substances 0.000 claims abstract description 52
- 239000007787 solid Substances 0.000 claims abstract description 52
- -1 nitroxyl radical compound Chemical class 0.000 claims abstract description 46
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 21
- 150000001993 dienes Chemical class 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 14
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004816 latex Substances 0.000 claims description 63
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 claims description 19
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 12
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 claims description 11
- QYTDEUPAUMOIOP-UHFFFAOYSA-N TEMPO Chemical group CC1(C)CCCC(C)(C)N1[O] QYTDEUPAUMOIOP-UHFFFAOYSA-N 0.000 claims description 11
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 description 35
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 30
- 238000000034 method Methods 0.000 description 23
- 229920001971 elastomer Polymers 0.000 description 22
- 238000002845 discoloration Methods 0.000 description 18
- 239000003921 oil Substances 0.000 description 16
- 230000006866 deterioration Effects 0.000 description 14
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 238000004073 vulcanization Methods 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 238000007720 emulsion polymerization reaction Methods 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 7
- 239000002537 cosmetic Substances 0.000 description 7
- 239000003995 emulsifying agent Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000005187 foaming Methods 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 125000000962 organic group Chemical group 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical group CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 239000000701 coagulant Substances 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 230000035943 smell Effects 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
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- 239000011787 zinc oxide Substances 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229940096992 potassium oleate Drugs 0.000 description 3
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- WUXMSJQQHBZNIK-UHFFFAOYSA-N 9-hydroxy-9-azabicyclo[3.3.1]nonane Chemical group C1CCC2CCCC1N2O WUXMSJQQHBZNIK-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium 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
- 125000000129 anionic group Chemical group 0.000 description 2
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- 125000004432 carbon atom Chemical group C* 0.000 description 2
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- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000004663 dialkyl amino group Chemical group 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 238000010438 heat treatment Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
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- 229940123973 Oxygen scavenger Drugs 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- BYRRPYMBVHTVKO-UHFFFAOYSA-N [Na].[Ti] Chemical compound [Na].[Ti] BYRRPYMBVHTVKO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- YLFIGGHWWPSIEG-UHFFFAOYSA-N aminoxyl Chemical group [O]N YLFIGGHWWPSIEG-UHFFFAOYSA-N 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- XTKDAFGWCDAMPY-UHFFFAOYSA-N azaperone Chemical compound C1=CC(F)=CC=C1C(=O)CCCN1CCN(C=2N=CC=CC=2)CC1 XTKDAFGWCDAMPY-UHFFFAOYSA-N 0.000 description 1
- VJRITMATACIYAF-UHFFFAOYSA-N benzenesulfonohydrazide Chemical compound NNS(=O)(=O)C1=CC=CC=C1 VJRITMATACIYAF-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- DHNRXBZYEKSXIM-UHFFFAOYSA-N chloromethylisothiazolinone Chemical compound CN1SC(Cl)=CC1=O DHNRXBZYEKSXIM-UHFFFAOYSA-N 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- TXGQALXWGNPMKD-UHFFFAOYSA-L diazanium;zinc;disulfate;hexahydrate Chemical compound [NH4+].[NH4+].O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O TXGQALXWGNPMKD-UHFFFAOYSA-L 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 1
- JBSLOWBPDRZSMB-BQYQJAHWSA-N dibutyl (e)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C\C(=O)OCCCC JBSLOWBPDRZSMB-BQYQJAHWSA-N 0.000 description 1
- IEPRKVQEAMIZSS-AATRIKPKSA-N diethyl fumarate Chemical compound CCOC(=O)\C=C\C(=O)OCC IEPRKVQEAMIZSS-AATRIKPKSA-N 0.000 description 1
- KQJLZBJOEUYHIM-UHFFFAOYSA-N diethylaminomethyl prop-2-enoate Chemical compound CCN(CC)COC(=O)C=C KQJLZBJOEUYHIM-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- RBVLUTAXWVILBT-UHFFFAOYSA-N ethyl prop-2-eneperoxoate Chemical compound CCOOC(=O)C=C RBVLUTAXWVILBT-UHFFFAOYSA-N 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 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
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- BSDQITJYKQHXQR-UHFFFAOYSA-N methyl prop-2-eneperoxoate Chemical compound COOC(=O)C=C BSDQITJYKQHXQR-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 150000003109 potassium Chemical class 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
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- JTDPJYXDDYUJBS-UHFFFAOYSA-N quinoline-2-carbohydrazide Chemical compound C1=CC=CC2=NC(C(=O)NN)=CC=C21 JTDPJYXDDYUJBS-UHFFFAOYSA-N 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 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
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940052367 sulfur,colloidal Drugs 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 150000003751 zinc Chemical class 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/32—Compounds containing nitrogen bound to oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
- C08L9/04—Latex
Definitions
- the present invention relates to a latex composition for foam rubber and a foam rubber, and more particularly, it has excellent oil resistance, has a soft touch, and appropriately suppresses discoloration, deterioration, and odor generation during repeated use.
- the present invention relates to a foam rubber latex composition capable of providing foam rubber, and to a foam rubber obtained using such a foam rubber latex composition.
- Foam rubber manufactured using polymer rubber latex is used for various purposes such as mattresses, cosmetic sponges (puffs), rolls, and shock absorbers.
- foam rubber particularly as a puff, there is a demand for foam rubber that has good oil resistance to cosmetics and a soft feel.
- a material for forming a foam rubber suitable for a puff as a cosmetic sponge for example, in Patent Document 1, a cyano group-containing ethylenically unsaturated monomer 45-60% by weight, 15-52% by weight of 1,3-butadiene, 3-40% by weight of isoprene, and 0-30% by weight of other ethylenically unsaturated monomers copolymerizable therewith.
- a copolymer rubber latex for foam rubber has been proposed, which is a copolymer rubber latex obtained by emulsion polymerization of a mixture and characterized in that the gel content of the copolymer rubber is 65% by weight or less.
- Patent Document 1 Although a foam rubber having excellent oil resistance and a soft feel can be obtained, there are problems such as discoloration, deterioration, and odor when repeatedly used. .
- the present invention has been made in view of such circumstances, and provides a foam rubber that has excellent oil resistance, has a soft feel, and is appropriately suppressed in discoloration, deterioration, and odor generation during repeated use. It is an object of the present invention to provide a latex composition for foam rubber which can be prepared and a foam rubber obtained using such a latex composition for foam rubber.
- a copolymer rubber latex containing 30 to 60% by weight of cyano group-containing ethylenically unsaturated monomer units and 40 to 70% by weight of aliphatic conjugated diene monomer units,
- a latex composition for foam rubber containing a nitroxyl radical compound and a thiazoline compound and having a solid content concentration of 55 to 75% by weight is provided.
- the content of the nitroxyl radical compound is preferably 100 to 10,000 ppm by weight.
- the content of the thiazoline compound is preferably 10 to 1,000 ppm by weight.
- the nitroxyl radical compound is preferably 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO).
- the thiazoline compound is preferably 2-methyl-4-isothiazolin-3-one (MIT) or 1,2-benzisothiazolin-3-one (BIT).
- the foam rubber latex composition of the present invention preferably has a solid content concentration of 60 to 70% by weight.
- the foam rubber latex composition of the present invention preferably has a solid content concentration of 63 to 69% by weight.
- the foam rubber latex composition of the present invention preferably has a solid content concentration of 64.5 to 67.5% by weight.
- a foam rubber obtained by using the above latex composition for foam rubber.
- a latex composition for foam rubber which is excellent in oil resistance, has a soft feel, and is capable of providing a foam rubber in which discoloration, deterioration and generation of odor during repeated use are appropriately suppressed. And a foam rubber obtained using such a latex composition for foam rubber can be provided.
- the latex composition for foam rubber of the present invention is a copolymer rubber containing 30 to 60% by weight of cyano group-containing ethylenically unsaturated monomer units and 40 to 70% by weight of aliphatic conjugated diene monomer units. It contains latex, a nitroxyl radical compound and a thiazoline compound, and has a solid concentration of 55 to 75% by weight.
- the copolymer rubber latex used in the present invention is a copolymer rubber containing 30 to 60% by weight of cyano group-containing ethylenically unsaturated monomer units and 40 to 70% by weight of aliphatic conjugated diene monomer units. More specifically, it is a dispersion in which particles of copolymer rubber having such a monomer composition are dispersed in water.
- the copolymer rubber latex used in the present invention includes, for example, a cyano group-containing ethylenically unsaturated monomer, an aliphatic conjugated diene-based monomer, and, if necessary, other polymers copolymerizable therewith. It can be obtained by emulsion polymerization of a monomer mixture containing an ethylenically unsaturated monomer.
- cyano group-containing unsaturated monomers examples include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -cyanoethyl acrylate and the like. These can be used individually by 1 type or in combination of 2 or more types. Among these, acrylonitrile and methacrylonitrile are preferred, and acrylonitrile is more preferred.
- the content of the cyano group-containing unsaturated monomer units in the copolymer rubber constituting the copolymer rubber latex is 30 to 60% by weight, preferably 35 to 55% by weight, based on the total monomer units. %, more preferably 40 to 50% by weight.
- the obtained foam rubber will have insufficient oil resistance, while if it is too large, the resulting foam rubber will have a hard hand and a rough texture. become worse.
- aliphatic conjugated diene monomers examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and chloroprene. mentioned. These can be used individually by 1 type or in combination of 2 or more types. Among these, 1,3-butadiene and isoprene are preferred, and 1,3-butadiene is more preferred.
- the content of the aliphatic conjugated diene monomer units in the copolymer rubber constituting the copolymer rubber latex is 40 to 70% by weight, preferably 45 to 65% by weight, based on the total monomer units.
- % more preferably 50 to 60% by weight. If the content of the aliphatic conjugated diene-based monomer unit is too small, the resulting foam rubber will be hard, while if it is too large, the resulting foam rubber will have insufficient oil resistance.
- the aliphatic conjugated diene-based monomer two or more types can be used in combination.
- 1,3-butadiene and isoprene may be used in combination.
- the content of isoprene units is preferably 30% by weight or less, and 20% by weight or less, based on the total monomer units. more preferably 2 to 10% by weight.
- the content ratio of 1,3-butadiene units and isoprene units is preferably 70:30 to 95:5, more preferably 80:20 in terms of weight ratio of 1,3-butadiene units:isoprene units. ⁇ 92:8.
- copolymer rubber constituting the copolymer rubber latex used in the present invention may optionally contain cyano group-containing ethylenically unsaturated monomer units and aliphatic conjugated diene monomer units in addition to , may contain units of other ethylenically unsaturated monomers copolymerizable with these monomers.
- ethylenically unsaturated monomers that can be copolymerized include, for example, (meth)acrylic acid, (anhydride) maleic acid, fumaric acid, ethylenically unsaturated carboxylic acids such as itaconic acid; methyl (meth)acrylate; ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, mono- or dimethyl maleate, mono- or diethyl fumarate, mono- or di-n-butyl fumarate, itaconic acid mono- or di-alkyl esters of said ethylenically unsaturated carboxylic acids such as mono- or di-n-butyl; alkoxyalkyl esters of said ethylenically unsaturated carboxylic acids such as methoxyacrylate, ethoxyacrylate, methoxyethoxyethyl acryl
- the content of other ethylenically unsaturated monomer units in the copolymer rubber constituting the copolymer rubber latex is preferably 10% by weight or less, more preferably 5% by weight or less.
- the gel content of the copolymer rubber constituting the copolymer rubber latex used in the present invention is not particularly limited. 80% by weight, more preferably 10 to 75% by weight, and even more preferably 20 to 70% by weight.
- the gel content was obtained by obtaining a copolymer rubber film and immersing the film in methyl ethyl ketone for 48 hours in a constant temperature and humidity room at a temperature of 23° C. and a humidity of 50%. By measuring the weight of the insoluble component, the insoluble content of methyl ethyl ketone can be determined.
- the gel content of the copolymer rubber can be adjusted by appropriately adjusting the emulsion polymerization conditions.
- the copolymer rubber latex used in the present invention can be produced by a normal emulsion polymerization technique.
- Polymerization agents such as emulsifiers (surfactants), polymerization initiators, chelating agents, oxygen scavengers, and molecular weight modifiers used for emulsion polymerization can be conventionally known agents, and are not particularly limited.
- Anionic and/or nonionic emulsifiers are usually used as emulsifiers.
- anionic emulsifiers include fatty acid salts such as potassium tallow fatty acid, potassium partially hydrogenated tallow fatty acid, potassium oleate, and sodium oleate; potassium rosinate, sodium rosinate, hydrogenated potassium rosinate, hydrogenated sodium rosinate; Alkylbenzenesulfonates such as sodium dodecylbenzenesulfonate and the like.
- nonionic emulsifiers include polyethylene glycol ester type, polyethylene glycol ester type, and pluronic type emulsifiers such as block copolymers of ethylene oxide and propylene oxide. These can be used individually by 1 type or in combination of 2 or more types.
- the amount of emulsifier to be used is preferably 0.5 to 5 parts by weight per 100 parts by weight of all the monomers used for polymerization.
- polymerization initiators include thermal decomposition initiators such as persulfates such as potassium persulfate and ammonium persulfate; t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, octanoyl peroxide, Organic peroxides such as 3,5,5-trimethylhexanoyl peroxide; azo compounds such as azobisisobutyronitrile; and redox initiators comprising these and reducing agents such as divalent iron ions. be done. These can be used individually by 1 type or in combination of 2 or more types. Among these, redox initiators are preferred.
- the amount of polymerization initiator to be used is preferably 0.01 to 10 parts by weight per 100 parts by weight of all monomers used for polymerization.
- molecular weight modifiers include alkylmercaptans such as n-hexylmercaptan, n-octylmercaptan, t-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan and n-stearylmercaptan; xanthogen compounds such as sulfides; thiuram compounds such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, and tetramethylthiuram monosulfide; phenolic compounds such as 2,6-di-t-butyl-4-methylphenol and styrenated phenol; allyl compounds such as allyl alcohol; halogenated hydrocarbon compounds such as dichloromethane, dibromomethane, carbon tetrabromide; ⁇ -benzyloxystyrene, ⁇ -benzyloxyacrylon
- the amount of the molecular weight modifier used is preferably 0.1 to 3 parts by weight, more preferably 0.2 to 2 parts by weight, and particularly preferably 0.3 to 1 part by weight with respect to 100 parts by weight of the total monomers used for polymerization. .5 parts by weight.
- the emulsion polymerization reaction may be either continuous or batchwise, and the polymerization time is not particularly limited.
- the method of adding the monomer is not particularly limited, and for example, a batch addition method, a split addition method, or the like can be used, but the viewpoint is that the resulting foam rubber can have a better balance between oil resistance and flexibility. More preferably, a method of continuing the polymerization by adding a part of the aliphatic conjugated diene-based monomer used for the polymerization to the reactor after starting the polymerization reaction can be employed.
- the cyano group-containing ethylenically unsaturated monomer and part of the aliphatic conjugated diene monomer are added to the reactor to initiate the polymerization reaction, and the polymerization reaction rate in the reactor is 20. It is preferable to add the remainder of the aliphatic conjugated diene-based monomer in batches or in portions to the reactor and continue the polymerization reaction between 65% and 65%.
- the polymerization conversion rate when stopping polymerization is not particularly limited, but is preferably 70 to 95% by weight, more preferably 75 to 90% by weight. By setting the polymerization conversion rate within the above range, it is possible to improve the productivity while keeping the gel content within a suitable range.
- the polymerization temperature is not particularly limited, it is preferably 0 to 50°C, more preferably 3 to 40°C.
- a particle size enlarging treatment After polymerization, if necessary, after removing unreacted monomers, it is preferable to apply a particle size enlarging treatment by a known method. , can be increased to a range suitable for foam rubber.
- Examples of the particle size enlarging treatment include a method of stopping the reaction during polymerization and vigorously stirring; a method of adding an aliphatic conjugated diene monomer or toluene as a solvent after completion of polymerization and vigorously stirring; and a method of adding a particle size enlarging agent such as a contained polymer latex to a copolymer rubber latex and stirring.
- the solid content concentration is adjusted to the optimum range by the concentration operation.
- the solid content concentration of the copolymer rubber latex is preferably in the range of 55-75% by weight, more preferably in the range of 60-70% by weight.
- the viscosity of the copolymer rubber latex used in the present invention is preferably 1000 cps or less, more preferably 100 to 800 cps, still more preferably 200 to 500 cps.
- the viscosity of the copolymer rubber latex can be measured using a Brookfield viscometer under conditions of a temperature of 25° C. and a rotational speed of 60 rpm.
- the copolymer rubber latex of the present invention may have a viscosity at 25° C.
- the viscosity at 25° C. is preferably within the above range.
- concentration is performed by a method such as vacuum distillation, normal pressure distillation, centrifugation, membrane concentration, etc. to adjust the solid content concentration.
- the above viscosity measurement can be performed after adjusting the solid content concentration by adding water for dilution.
- the volume average particle size of the copolymer rubber contained in the copolymer rubber latex is not particularly limited, but is usually 300 to 3000 nm, preferably about 400 to 2000 nm.
- the volume average particle size can be measured using a laser diffraction particle size distribution analyzer.
- a laser diffraction particle size distribution analyzer there is a laser diffraction particle size distribution analyzer (model "LS-13320", manufactured by Beckman Coulter, Inc.).
- the latex composition for foam rubber of the present invention is obtained by blending a nitroxyl radical compound and a thiazoline compound with the copolymer rubber latex described above, and has a solid content concentration in the range of 55 to 75% by weight. It is what was done.
- the resulting foam rubber has excellent oil resistance and a soft feel.
- discoloration, deterioration and generation of odor during repeated use can be appropriately suppressed.
- the nitroxyl radical compound is a compound that acts as a stabilizer in the foam rubber latex composition of the present invention, and the nitroxyl radical compound is not particularly limited as long as it has a nitroxyl radical structure.
- TEMPO 2,2,6,6-tetramethylpiperidine-1-oxyl
- 2 - azaadamantane-N-oxyl (AZADO) 1-methyl-2-azaadamantane-N-oxyl (1-Me-AZADO) or 9-azabicyclo[3.3.1]nonane-N-oxyl (ABNO), etc.
- TEMPO 2,2,6,6-tetramethylpiperidine-1-oxyl
- 2 - azaadamantane-N-oxyl azaadamantane-N-
- TEMPO 2,2,6,6-tetramethylpiperidine-1-oxyl
- the content of the nitroxyl radical compound in the latex composition for foam rubber of the present invention is not particularly limited, but is preferably 100 to 10,000 ppm by weight, more preferably 300 to 7,000 ppm by weight, and more preferably 300 to 7,000 ppm by weight. It is preferably 500 to 5,000 ppm by weight, more preferably 500 to 2,500 ppm by weight, still more preferably 500 to 2,000 ppm by weight, and particularly preferably 700 to 1,300 ppm by weight.
- the thiazoline-based compound is not particularly limited as long as it is a compound having a thiazoline structure. compound and the like.
- R 1 represents a hydrogen atom or an optionally substituted organic group
- R 2 and R 3 each independently represent a hydrogen atom, a halogen atom, or a substituted Indicates an organic group which may have a group.
- R 1 , R 2 and R 3 are hydrocarbon groups, they may have a chain carbon skeleton such as a straight or branched chain, or may have a cyclic carbon skeleton, or It may have a substituent such as a halogen atom, an alkoxyl group, a dialkylamino group, an acyl group, or an alkoxycarbonyl group.
- the number of carbon atoms in the hydrocarbon group is preferably 1-12, more preferably 1-10, and particularly preferably 1-8.
- Specific examples of such hydrocarbon groups include methyl, ethyl, propyl, isopropyl, butyl, hexyl, cyclohexyl, octyl and 2-ethylhexyl groups.
- R 4 represents a hydrogen atom or an optionally substituted organic group
- R 5 each independently represents a hydrogen atom or a substituent indicates a good organic group.
- R 4 is a hydrocarbon group
- R 5 is an organic group
- the organic group includes an aliphatic group such as an alkyl group or a cycloalkyl group, or an aromatic group, and is preferably an aliphatic group.
- the number of carbon atoms in the alkyl group is preferably 1-12, more preferably 1-10, and particularly preferably 1-8.
- alkyl groups and cycloalkyl groups may have substituents such as halogen atoms, alkoxyl groups, dialkylamino groups, acyl groups and alkoxycarbonyl groups.
- substituents such as halogen atoms, alkoxyl groups, dialkylamino groups, acyl groups and alkoxycarbonyl groups.
- Specific examples of aliphatic groups include methyl, ethyl, propyl, isopropyl, butyl, hexyl, cyclohexyl, octyl and 2-ethylhexyl groups.
- n represents an integer of 0-4.
- isothiazolin-based compounds represented by the general formula (1) include 2-methyl-4-isothiazolin-3-one (MIT), 2-n-octyl-4-isothiazolin-3-one, 4- chloro-2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2-n-octyl-4-isothiazolin-3-one and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one and the like.
- MIT 2-methyl-4-isothiazolin-3-one
- 2-n-octyl-4-isothiazolin-3-one 4- chloro-2-n-octyl-4-isothiazolin-3-one
- 5-chloro-2-methyl-4-isothiazolin-3-one 5-chloro-2-n-octyl-4-isothiazolin-3
- benzisothiazoline compound represented by the general formula (2) examples include 1,2-benzisothiazolin-3-one (BIT) and Nn-butyl-1,2-benzisothiazoline-3 -on and the like.
- BIT 1,2-benzisothiazolin-3-one
- MIT 2-methyl-4-isothiazolin-3-one
- MIT 2-methyl-4-isothiazolin-3-one
- BIT 1,2-benzisothiazolin-3-one
- BIT 1,2-benzisothiazolin-3-one
- the content of the thiazoline-based compound in the foam rubber latex composition of the present invention is not particularly limited, but is preferably 10 to 1,000 ppm by weight, more preferably 10 to 500 ppm by weight, still more preferably 50 ppm by weight. ⁇ 450 ppm by weight, even more preferably 80 to 400 ppm by weight, even more preferably 100 to 400 ppm by weight, particularly preferably 100 to 250 ppm by weight, most preferably 100 to 150 ppm by weight.
- the contents of the nitroxyl radical compound and the thiazoline compound in the latex composition for foam rubber of the present invention may be within the above ranges, but the resulting foam rubber may be discolored, deteriorated, and odorous during repeated use. From the point of view that the inhibitory effect can be further enhanced, the content of these is preferably in the range of 1:1 to 30:1 in terms of the weight ratio of "nitroxyl radical compound: thiazoline compound", and 5: It is more preferably in the range of 1 to 20:1, more preferably in the range of 8:1 to 12:1.
- the foam rubber latex composition of the present invention may further contain a vulcanizing agent.
- a vulcanizing agent those commonly used in the production of foam rubber can be used, for example, sulfur such as powdered sulfur, sulfur flower, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur; Morpholine disulfide, alkylphenol disulfide, N,N'-dithio-bis(hexahydro-2H-azepinone-2), phosphorus-containing polysulfide, polymeric polysulfide, sulfur such as 2-(4'-morpholinodithio)benzothiazole containing compounds.
- sulfur can be preferably used.
- a vulcanizing agent can be used individually by 1 type or in combination of 2 or more types.
- the content of the vulcanizing agent in the latex composition for foam rubber of the present invention is not particularly limited, but is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the rubber component in the latex composition for foam rubber. parts, more preferably 0.2 to 3 parts by weight.
- the foam rubber latex composition of the present invention may further contain a vulcanization accelerator.
- vulcanization accelerators those commonly used in the production of foam rubber can be used. dithiocarbamic acids and zinc salts thereof; 2-mercaptobenzothiazole, 2-mercaptobenzothiazole zinc, 2-mercaptothiazoline, dibenzothiazyl disulfide, 2-(2,4-dinitrophenylthio)benzothiazole, (N,N-diethylthiocarbylthio)benzothiazole, 2-(2,6-dimethyl-4-morpholinothio)benzothiazole, 2-(4'-morpholinodithio)benzothiazole, 4-morphonylyl-2-benzothiazyl disulfide, 1,3-bis(2-benzothiazyl-mercaptomethyl)urea and the like.
- a vulcanization accelerator can be used individually by 1 type or in combination of 2 or more types.
- the content of the vulcanization accelerator in the latex composition for foam rubber of the present invention is not particularly limited, but is preferably 0.05 to 5 parts per 100 parts by weight of the rubber component in the latex composition for foam rubber. parts by weight, more preferably 0.1 to 2 parts by weight.
- the foam rubber latex composition of the present invention may further contain zinc oxide.
- the content of zinc oxide in the latex composition for foam rubber of the present invention is not particularly limited, but is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the rubber component in the latex composition for foam rubber. , more preferably 0.2 to 2 parts by weight.
- the method for preparing the latex composition for foam rubber of the present invention is not particularly limited. A method of mixing various compounding agents such as a sulfur accelerator and zinc oxide can be used.
- the nitroxyl radical compound acts as a stabilizer, it also acts as a polymerization terminator or a polymerization inhibitor for terminating the polymerization reaction. Some of them may be blended as a polymerization terminator for terminating the polymerization reaction when obtaining a copolymer rubber latex by emulsion polymerization.
- part of the nitroxyl radical compound may be present in a state of being bound to the termination side terminal of the copolymer rubber constituting the copolymer rubber latex.
- the copolymer rubber latex and the compounding agents other than the nitroxyl radical compound may be added in the form of an aqueous dispersion or aqueous solution containing them.
- the latex composition for foam rubber of the present invention includes, for example, an antioxidant; a coloring agent; a foam stabilizer; a dispersant such as NASF (naphthalenesulfonic acid formalin condensate sodium salt); , sodium alginate, polyvinyl alcohol and other thickeners; aliphatic alkaline soaps such as potassium oleate, surfactants as foaming agents such as sulfates of higher alcohols such as sodium dodecyl sulfate; good.
- NASF naphthalenesulfonic acid formalin condensate sodium salt
- aliphatic alkaline soaps such as potassium oleate
- surfactants as foaming agents such as sulfates of higher alcohols such as sodium dodecyl sulfate; good.
- the foam rubber latex composition of the present invention has a solid content concentration in the range of 55 to 75% by weight, preferably 60 to 70% by weight, more preferably 63 to 69% by weight, and still more preferably 64.5 to 67.5% by weight, particularly preferably 65 to 67% by weight. If the solid content concentration is too low, rough foam will occur when obtaining a foam rubber, resulting in a poor appearance of the resulting foam rubber. put away.
- the solid content concentration can be adjusted, for example, by adjusting the solid content concentration of the copolymer rubber latex used, the amount of compounding agents, and the like.
- the foam rubber of the present invention is obtained using the above-described latex composition for foam rubber of the present invention.
- the foam rubber of the present invention can be obtained by foaming the above latex composition for foam rubber of the present invention, coagulating it, and vulcanizing it if necessary.
- Air is usually used for foaming latex compositions for foam rubber, and carbonates such as ammonium carbonate and sodium bicarbonate; azo compounds such as azodicarboxylic acid amide and azobisisobutyronitrile; gas generating substances such as benzenesulfonylhydrazide. can also be used.
- carbonates such as ammonium carbonate and sodium bicarbonate
- azo compounds such as azodicarboxylic acid amide and azobisisobutyronitrile
- gas generating substances such as benzenesulfonylhydrazide.
- the copolymer rubber latex is agitated and foamed by entraining the air.
- an oak foaming machine, an ultrasonic foaming machine, or the like is used.
- the foamed latex composition is coagulated to fix the foamed state.
- the coagulation method is not particularly limited as long as it is a method capable of gelling and solidifying the foam rubber latex composition, and any conventionally known method can be used.
- a silicon fluoride compound such as sodium hexafluorosilicate, potassium hexafluorosilicate (sodium silicofluoride, potassium silicofluoride), titanium sodium silicofluoride, etc. is added to the foamed latex composition for foam rubber.
- Dunlop method normal temperature coagulation method
- heat-sensitive coagulation method in which a heat-sensitive coagulant such as organopolysiloxane, polyvinyl methyl ether, zinc ammonium sulfate complex is added to a foamed latex composition for foam rubber; be.
- the amount of the coagulant used is not particularly limited, but it is usually about 0.5 to 10 parts by weight with respect to 100 parts by weight of the foam rubber latex composition (solid content).
- the foam rubber can be obtained by transferring the foamed latex composition for foam rubber in a fluid state to which the coagulant has been added to a mold of a predetermined shape and solidifying it.
- heating may be performed for vulcanization.
- the conditions for vulcanization are preferably conditions for heat treatment at a temperature of 100 to 160° C. for preferably 15 to 120 minutes.
- the method of washing is not particularly limited, but for example, a method of washing with water of about 20 to 70° C. by stirring for about 5 to 15 minutes using a washing machine or the like can be mentioned. After washing, it is preferable to drain the water and dry at a temperature of about 30 to 90°C so as not to impair the texture of the foam rubber.
- the foam rubber thus obtained can be used as a puff (cosmetic sponge) or the like by, for example, slicing it into a predetermined thickness, cutting it into a predetermined shape, and polishing the side surface with a rotating grindstone or the like. can.
- the foam rubber of the present invention is obtained by using the above-described latex composition for foam rubber of the present invention, it has excellent oil resistance, has a soft feel, and discolors, deteriorates and smells during repeated use. generation is appropriately suppressed, and is suitable as a puff (cosmetic sponge). In addition to puffs (cosmetic sponges), it can also be suitably used for various applications such as mattresses, rolls, and shock absorbers.
- ⁇ Odor of Copolymer Rubber Latex 50 mL of the copolymer rubber latex was placed in a 100 mL container that can be sealed and left at 25° C. for 24 hours. Judgment was carried out according to the following criteria. A: No putrid smell is felt by any of the five persons. B: 1 to 4 out of 5 people felt putrid smell. C: All 5 out of 5 people feel putrid smell.
- a test piece is obtained by punching a disk-shaped foam rubber having a thickness of 0.8 cm into a circle having a diameter of about 38 mm, and the obtained test piece is immersed in toluene at 23 ° C. for 24 hours.
- ⁇ F type hardness of foam rubber The hardness of the foam rubber was measured using an Asker rubber hardness meter F type (manufactured by Kobunshi Keiki Co., Ltd.). It can be judged that the lower the value, the softer the foam rubber and the better the touch.
- a disc-shaped foam rubber having a thickness of 0.8 cm was punched into a circle having a diameter of about 38 mm to obtain a test piece, and the obtained test piece was repeatedly used.
- the repeated use operation first, the test piece was immersed in silicone oil (decamethylcyclopentasiloxane), washed with a neutral kitchen detergent, and air-dried at room temperature for 24 hours. This operation was first repeated 10 times, and then left at 25° C. for 10 days to obtain a test piece after repeated use. Discoloration, deterioration, and odor during repeated use were evaluated using the test piece after repeated use.
- each test piece was placed in a 100 mL container and left at room temperature for 24 hours.
- Example 1> (Preparation of copolymer rubber latex) 200 parts of ion-exchanged water, 1.5 parts of potassium oleate, 35 parts of acrylonitrile, 0.5 parts of t-dodecyl mercaptan, 0.03 parts of sodium formaldehyde sulfoxylate, and 0.003 parts of ferrous sulfate are placed in a pressure-resistant reaction vessel. 0.008 part of ethylenediaminetetraacetic acid/sodium was added, and after sufficient degassing, 45 parts of 1,3-butadiene was added.
- 0.05 parts of cumene hydroperoxide as a polymerization initiator and an appropriate amount of reducing agent were added to initiate emulsion polymerization at a reaction temperature of 5°C.
- the polymerization conversion reached 40%, 10 parts of 1,3-butadiene was added to continue the polymerization reaction.
- the polymerization conversion reached 60%, 10 parts of 1,3-butadiene was added to continue the polymerization reaction.
- TEMPO 2,2,6,6-tetramethylpiperidine-1-oxyl
- the amount of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) used was set to 2,000 ppm by weight in the final foam rubber latex composition. Then, after removing the unreacted monomer, 80 parts of 1,3-butadiene is added, the temperature in the system is set to 15° C., and the mixture is stirred for 5 hours at a rotation speed of 1,000 rpm using a paddle type stirring blade. Then, a grain size enlarging treatment was performed. Next, after removing 1,3-butadiene, concentration was carried out to obtain a copolymer rubber latex having a solid content concentration of 67% by weight.
- TEMPO 2,2,6,6-tetramethylpiperidine-1-oxyl
- the resulting copolymer rubber latex had a pH of 11.3 and a viscosity (B type viscosity) of 280 cps.
- the composition of the monomer units contained in the copolymer rubber constituting the copolymer rubber latex was almost the same as the charged amount (also in Examples 2 to 5 and Comparative Examples 1 to 5 described later). Similarly.).
- the copolymer latex composition for foam rubber obtained above is stirred using a stand mixer (ESM945 manufactured by Electrolux Co., Ltd.) and foamed so as to be about five times its volume, and then silicified.
- a foamed product was obtained by adding 1.5 parts of an aqueous soda dispersion (solid concentration: 20% by weight) and further stirring for 1 minute.
- the resulting foam was poured into a mold (7 cm in diameter, 8 cm in height), solidified, and vulcanized at 110° C. for 1 hour to obtain a foam rubber.
- the foam rubber removed from the mold was washed with hot water at 40°C for 10 minutes, dried in an oven at 60°C for 4 hours, and then cut into discs with a thickness of 0.8 cm.
- a foam rubber was obtained, and oil resistance, F-type hardness, and discoloration, deterioration and odor during repeated use were measured and evaluated according to the above methods. Table 1 shows the results.
- Example 2 The amount of acrylonitrile used was changed to 45 parts, the amount of 1,3-butadiene used at the start of polymerization was changed to 35 parts, and 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) A copolymer rubber having a solid content concentration of 65% by weight was prepared in the same manner as in Example 1, except that the amount used was adjusted to 1,000 ppm by weight in the final foam rubber latex composition. A latex was prepared. The pH and viscosity (B-type viscosity) of the obtained copolymer rubber latex were as shown in Table 1.
- Example 3 In the same manner as in Example 2, except that the amount of 1,3-butadiene used at the start of polymerization was changed to 30 parts, and 5 parts of isoprene was further blended at the start of polymerization, a copolymer having a solid content concentration of 67% by weight was prepared. A coalesced rubber latex was prepared. The pH and viscosity (B-type viscosity) of the obtained copolymer rubber latex were as shown in Table 1. Then, in the same manner as in Example 1, except that the copolymer rubber latex obtained above was used, a latex composition for foam rubber (67% by weight of solid content) was prepared and a foam rubber was produced. performed and evaluated in the same way. Table 1 shows the results.
- Example 4 Example except that the amount of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) used was 500 ppm by weight in the finally obtained foam rubber latex composition.
- a copolymer rubber latex having a solid concentration of 65% by weight was prepared in the same manner as in Example 2.
- the pH and viscosity (B-type viscosity) of the obtained copolymer rubber latex were as shown in Table 1.
- a latex composition for foam rubber (65% by weight of solid content) was prepared and a foam rubber was produced. performed and evaluated in the same way. Table 1 shows the results.
- Example 5 While using a copolymer rubber latex obtained in the same manner as in Example 2, instead of 1,2-benzisothiazolin-3-one (BIT), the same amount of 2-methyl-4-isothiazolin-3 A latex composition for foam rubber (solid concentration: 65% by weight) was prepared and foam rubber was produced in the same manner as in Example 2, except that MIT was used, and evaluated in the same manner. Table 1 shows the results.
- BIT 1,2-benzisothiazolin-3-one
- ⁇ Comparative Example 1> The amount of acrylonitrile used was changed to 47 parts, and the amount of 1,3-butadiene used at the start of polymerization was changed to 18 parts. ,6-Tetramethylpiperidine-1-oxyl (TEMPO) was replaced with an aqueous dispersion of diethylhydroxyamine (HAS) in the same manner as in Example 1, except that a solid content concentration of 65 wt. % copolymer rubber latex was prepared. The amount of diethylhydroxyamine (HAS) used was set to 2,000 ppm by weight in the finally obtained latex composition for foam rubber. The pH and viscosity (B-type viscosity) of the obtained copolymer rubber latex were as shown in Table 1.
- Example 2 In the same manner as in Example 2, except that an aqueous dispersion of diethylhydroxyamine (HAS) was used instead of the aqueous dispersion of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO). A copolymer rubber latex having a solids concentration of 65% by weight was prepared. The amount of diethylhydroxyamine (HAS) used was set to 2,000 ppm by weight in the finally obtained latex composition for foam rubber. The pH and viscosity (B-type viscosity) of the obtained copolymer rubber latex were as shown in Table 1.
- HAS diethylhydroxyamine
- TEMPO 2,2,6,6-tetramethylpiperidine-1-oxyl
- Example 3 A copolymer rubber latex having a solid concentration of 65% by weight was prepared in the same manner as in Example 2, except that 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) was not used. In Comparative Example 3, no polymerization terminator for emulsion polymerization was used. The pH and viscosity (B-type viscosity) of the obtained copolymer rubber latex were as shown in Table 1. Then, in the same manner as in Example 1 except that the copolymer rubber latex obtained above was used, a latex composition for foam rubber (66% by weight of solid content) was prepared and foam rubber was produced. performed and evaluated in the same way. Table 1 shows the results.
- TEMPO 2,2,6,6-tetramethylpiperidine-1-oxyl
- Example 4 In the same manner as in Example 2, except that the copolymer rubber latex obtained in the same manner as in Example 2 was used, and 1,2-benzisothiazolin-3-one (BIT) was not used, A latex composition for foam rubber (solid concentration: 65% by weight) was prepared, and foam rubber was produced and evaluated in the same manner. Table 1 shows the results.
- Example 5 A copolymer rubber having a solid content concentration of 65% by weight was prepared in the same manner as in Example 3, except that the amount of acrylonitrile used was changed to 20 parts and the amount of 1,3-butadiene used at the start of polymerization was changed to 55 parts. A latex was prepared. The pH and viscosity (B-type viscosity) of the obtained copolymer rubber latex were as shown in Table 1. Then, in the same manner as in Example 1, except that the copolymer rubber latex obtained above was used, a latex composition for foam rubber (65% by weight of solid content) was prepared and a foam rubber was produced. performed and evaluated in the same way. Table 1 shows the results.
- a foam rubber obtained by using a latex composition for foam rubber containing a xyl radical compound and a thiazoline-based compound and having a solid content concentration of 55 to 75% by weight has excellent oil resistance and a soft feel. Moreover, discoloration, deterioration and generation of odor during repeated use were appropriately suppressed (Examples 1 to 5).
- the resulting foam rubber will be inferior in oil resistance and will also have a low F-type hardness. A soft feel could not be obtained (Comparative Example 5).
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Abstract
Description
本発明は、このような実状に鑑みてなされたものであり、耐油性に優れ、やわらかい感触を有し、かつ、繰り返し使用時の変色、劣化および臭気の発生が適切に抑制されたフォームラバーを与えることのできるフォームラバー用ラテックス組成物、およびこのようなフォームラバー用ラテックス組成物を用いて得られるフォームラバーを提供することを目的とする。 According to the technique of Patent Document 1, although a foam rubber having excellent oil resistance and a soft feel can be obtained, there are problems such as discoloration, deterioration, and odor when repeatedly used. .
The present invention has been made in view of such circumstances, and provides a foam rubber that has excellent oil resistance, has a soft feel, and is appropriately suppressed in discoloration, deterioration, and odor generation during repeated use. It is an object of the present invention to provide a latex composition for foam rubber which can be prepared and a foam rubber obtained using such a latex composition for foam rubber.
本発明のフォームラバー用ラテックス組成物において、前記チアゾリン系化合物の含有量が10~1,000重量ppmであることが好ましい。
本発明のフォームラバー用ラテックス組成物において、前記ニトロキシルラジカル化合物が、2,2,6,6-テトラメチルピペリジン-1-オキシル(TEMPO)であることが好ましい。
本発明のフォームラバー用ラテックス組成物において、前記チアゾリン系化合物が、2-メチル-4-イソチアゾリン-3-オン(MIT)または1,2-ベンゾイソチアゾリン-3-オン(BIT)であることが好ましい。
本発明のフォームラバー用ラテックス組成物は、固形分濃度が60~70重量%であることが好ましい。
本発明のフォームラバー用ラテックス組成物は、固形分濃度が63~69重量%であることが好ましい。
本発明のフォームラバー用ラテックス組成物は、固形分濃度が64.5~67.5重量%であることが好ましい。 In the latex composition for foam rubber of the present invention, the content of the nitroxyl radical compound is preferably 100 to 10,000 ppm by weight.
In the foam rubber latex composition of the present invention, the content of the thiazoline compound is preferably 10 to 1,000 ppm by weight.
In the foam rubber latex composition of the present invention, the nitroxyl radical compound is preferably 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO).
In the foam rubber latex composition of the present invention, the thiazoline compound is preferably 2-methyl-4-isothiazolin-3-one (MIT) or 1,2-benzisothiazolin-3-one (BIT). .
The foam rubber latex composition of the present invention preferably has a solid content concentration of 60 to 70% by weight.
The foam rubber latex composition of the present invention preferably has a solid content concentration of 63 to 69% by weight.
The foam rubber latex composition of the present invention preferably has a solid content concentration of 64.5 to 67.5% by weight.
本発明で用いる共重合体ゴムラテックスは、シアノ基含有エチレン性不飽和単量体単位30~60重量%、および脂肪族共役ジエン系単量体単位40~70重量%を含有する共重合体ゴムのラテックスであり、より具体的には、このような単量体組成を有する共重合体ゴムの粒子が、水中に分散してなる分散液である。 <Copolymer rubber latex>
The copolymer rubber latex used in the present invention is a copolymer rubber containing 30 to 60% by weight of cyano group-containing ethylenically unsaturated monomer units and 40 to 70% by weight of aliphatic conjugated diene monomer units. More specifically, it is a dispersion in which particles of copolymer rubber having such a monomer composition are dispersed in water.
本発明のフォームラバー用ラテックス組成物は、上記した共重合体ゴムラテックスに、ニトロキシルラジカル化合物、およびチアゾリン系化合物を配合してなるものであり、固形分濃度が55~75重量%の範囲とされたものである。 <Latex composition for foam rubber>
The latex composition for foam rubber of the present invention is obtained by blending a nitroxyl radical compound and a thiazoline compound with the copolymer rubber latex described above, and has a solid content concentration in the range of 55 to 75% by weight. It is what was done.
に対して、好ましくは0.05~5重量部であり、より好ましくは0.1~2重量部である。加硫促進剤の配合量を上記範囲とすることにより、得られるフォームラバーの強度をより高めることができる。 The content of the vulcanization accelerator in the latex composition for foam rubber of the present invention is not particularly limited, but is preferably 0.05 to 5 parts per 100 parts by weight of the rubber component in the latex composition for foam rubber. parts by weight, more preferably 0.1 to 2 parts by weight. By setting the amount of the vulcanization accelerator within the above range, the strength of the obtained foam rubber can be further increased.
本発明のフォームラバーは、上記した本発明のフォームラバー用ラテックス組成物を用いて得られるものである。
具体的には、本発明のフォームラバーは、上記した本発明のフォームラバー用ラテックス組成物を発泡させ、凝固させ、必要に応じて加硫することによって得ることができる。 <Foam rubber>
The foam rubber of the present invention is obtained using the above-described latex composition for foam rubber of the present invention.
Specifically, the foam rubber of the present invention can be obtained by foaming the above latex composition for foam rubber of the present invention, coagulating it, and vulcanizing it if necessary.
アルミ皿(重量:X1)に試料2gを精秤し(重量:X2)、これを105℃の熱風乾燥器内で2時間乾燥させた。次いで、デシケーター内で冷却した後、アルミ皿ごと重量を測定し(重量:X3)、下記の計算式にしたがって、固形分濃度を算出した。
固形分濃度(重量%)=(X3-X1)×100/X2 <Solid Content Concentration of Copolymer Rubber Latex and Latex Composition for Foam Rubber>
2 g of the sample was accurately weighed (weight: X2) in an aluminum dish (weight: X1) and dried in a hot air dryer at 105°C for 2 hours. Next, after cooling in a desiccator, the weight of each aluminum dish was measured (weight: X3), and the solid content concentration was calculated according to the following formula.
Solid content concentration (% by weight) = (X3-X1) x 100/X2
共重合体ゴムラテックスの粘度は、温度25℃の条件下、B型粘度計を用いて、回転数60rpmにて測定した。 <Viscosity of Copolymer Rubber Latex>
The viscosity of the copolymer rubber latex was measured at a temperature of 25° C. using a Brookfield viscometer at a rotation speed of 60 rpm.
密閉できる100mLの容器に、共重合体ゴムラテックスを、50mL入れて、25℃の条件下で24時間放置した後、開閉時の臭気の確認を5人で実施した。判定は以下の基準で実施した。
A:5人中全員が腐敗臭を感じない。
B:5人中1~4人が腐敗臭を感じる。
C:5人中5人とも腐敗臭を感じる。 <Odor of Copolymer Rubber Latex>
50 mL of the copolymer rubber latex was placed in a 100 mL container that can be sealed and left at 25° C. for 24 hours. Judgment was carried out according to the following criteria.
A: No putrid smell is felt by any of the five persons.
B: 1 to 4 out of 5 people felt putrid smell.
C: All 5 out of 5 people feel putrid smell.
厚みが0.8cmの円板状のフォームラバーを、直径約38mmの円形に打ち抜くことで試験片を得て、得られた試験片を、トルエンに、23℃で24時間浸漬させ、浸漬前の試験片に対する、浸漬後の試験片の直径の比率(膨潤率(%)=(浸漬後の試験片の直径)/(浸漬前の試験片の直径)×100)を算出した。なお、膨潤率が低いほど、耐油性に優れると判断できる。 <Oil resistance of foam rubber>
A test piece is obtained by punching a disk-shaped foam rubber having a thickness of 0.8 cm into a circle having a diameter of about 38 mm, and the obtained test piece is immersed in toluene at 23 ° C. for 24 hours. The ratio of the diameter of the test piece after immersion to the test piece (swelling rate (%)=(diameter of test piece after immersion)/(diameter of test piece before immersion)×100) was calculated. In addition, it can be judged that the lower the swelling rate, the better the oil resistance.
アスカーゴム硬度計F型(高分子計器社製)を用いて、フォームラバーの硬度を測定した。値が低いほどフォームラバーは柔らかく、肌触りは良好であると判断できる。 <F type hardness of foam rubber>
The hardness of the foam rubber was measured using an Asker rubber hardness meter F type (manufactured by Kobunshi Keiki Co., Ltd.). It can be judged that the lower the value, the softer the foam rubber and the better the touch.
厚みが0.8cmの円板状のフォームラバーを、直径約38mmの円形に打ち抜くことで試験片を得て、得られた試験片について、繰り返し使用操作を行った。繰り返し使用操作としては、まず、試験片をシリコーンオイル(デカメチルシクロペンタシロキサン)に浸漬させた後、台所用中性洗剤で水洗を実施し、室温で24時間風乾した。この操作をまずは10回繰り返し、その後25℃で10日間放置して繰返し使用後の試験片を得た。繰り返し使用後の試験片を用いて、繰り返し使用時の変色、劣化、および臭気の評価を行った。
(繰り返し使用時の変色)
繰り返し使用時の変色については、繰り返し使用前後の試験片について、5人で目視にて確認を行い、繰り返し使用前のサンプルと比較して以下の基準で判定を行った。
A:5人とも明らかな変色は見られない。
B:1~4人が変色を感じた。
C:5人とも明らかに茶褐色の変色を感じた。
(繰り返し使用時の劣化)
繰り返し使用時の劣化については、5人による実際に手で触った触感評価により確認を行い、以下の基準で判定を行った。
A:5人とも明らかな触感変化を感じなかった。
B:1~4人が触感の変化を感じた。
C:5人とも明らかに硬く、ボソボソした触感を感じた。
(繰り返し使用時の臭気)
繰り返し使用時の臭気については、それぞれの試験片を100mLの容器に入れて、室温で24時間放置した後、5人で放置後の臭気の確認を行い、以下の基準で判定を行った。
A:5人とも臭気を全く感じない。
B:1~4人がわずかな臭気を感じる。
C:5人とも明らかに臭気を感じる。 <Discoloration, deterioration and odor during repeated use of foam rubber>
A disc-shaped foam rubber having a thickness of 0.8 cm was punched into a circle having a diameter of about 38 mm to obtain a test piece, and the obtained test piece was repeatedly used. As the repeated use operation, first, the test piece was immersed in silicone oil (decamethylcyclopentasiloxane), washed with a neutral kitchen detergent, and air-dried at room temperature for 24 hours. This operation was first repeated 10 times, and then left at 25° C. for 10 days to obtain a test piece after repeated use. Discoloration, deterioration, and odor during repeated use were evaluated using the test piece after repeated use.
(Discoloration after repeated use)
Regarding the discoloration during repeated use, the test pieces before and after repeated use were visually checked by 5 persons, and compared with the sample before repeated use, and judged according to the following criteria.
A: No clear discoloration was observed in any of the five persons.
B: 1 to 4 persons felt discoloration.
C: All 5 people clearly felt a dark brown discoloration.
(degradation during repeated use)
Deterioration during repeated use was confirmed by tactile evaluation by five persons who actually touched the material with their hands, and the evaluation was made according to the following criteria.
A: None of the five persons felt a clear tactile change.
B: 1 to 4 people felt a change in tactile sensation.
C: All 5 people felt a distinctly hard and crumbly tactile sensation.
(Odor during repeated use)
Regarding the odor during repeated use, each test piece was placed in a 100 mL container and left at room temperature for 24 hours.
A: None of the five feel any odor.
B: 1 to 4 people perceive a slight odor.
C: All 5 people clearly sense the odor.
(共重合体ゴムラテックスの調製)
耐圧反応容器に、イオン交換水200部、オレイン酸カリウム1.5部、アクリロニトリル35部、t-ドデシルメルカプタン0.5部、ソジウムホルムアルデヒドスルホキシレート0.03部、硫酸第一鉄0.003部、エチレンジアミン四酢酸・ナトリルム0.008部を添加し、十分に脱気した後、1,3-ブタジエン45部を添加した。次いで、重合開始剤としてクメンハイドロペルオキサイド0.05部、および適量の還元剤を添加して、反応温度5℃で乳化重合を開始した。そして、重合転化率が40%に達した時点で、1,3-ブタジエン10部を添加し、重合反応を継続した。さらに、重合転化率が60%に達した時点で、1,3-ブタジエン10部を添加し、重合反応を継続した。重合転化率が80%になった時点で、2,2,6,6-テトラメチルピペリジン-1-オキシル(TEMPO)を水分散液の状態で添加して重合反応を停止させた。なお、2,2,6,6-テトラメチルピペリジン-1-オキシル(TEMPO)の使用量は、最終的に得られるフォームラバー用ラテックス組成物中において、2,000重量ppmとなる量とした。そして、未反応単量体を除去した後、1,3-ブタジエン80部を添加し、系内の温度を15℃にして、パドル型攪拌翼を用いて1,000rpmの回転数で5時間攪拌し、粒径肥大化処理を行った。次いで、1,3-ブタジエンを除去した後、濃縮を行い、固形分濃度67重量%の共重合体ゴムラテックスを得た。得られた共重合体ゴムラテックスのpHは11.3、粘度(B型粘度)は280cpsであった。また、共重合体ゴムラテックスを構成する共重合体ゴム中に含まれる単量体単位の組成は、仕込み量とほぼ同一であった(後述する実施例2~5、比較例1~5においても同様。)。 <Example 1>
(Preparation of copolymer rubber latex)
200 parts of ion-exchanged water, 1.5 parts of potassium oleate, 35 parts of acrylonitrile, 0.5 parts of t-dodecyl mercaptan, 0.03 parts of sodium formaldehyde sulfoxylate, and 0.003 parts of ferrous sulfate are placed in a pressure-resistant reaction vessel. 0.008 part of ethylenediaminetetraacetic acid/sodium was added, and after sufficient degassing, 45 parts of 1,3-butadiene was added. Next, 0.05 parts of cumene hydroperoxide as a polymerization initiator and an appropriate amount of reducing agent were added to initiate emulsion polymerization at a reaction temperature of 5°C. When the polymerization conversion reached 40%, 10 parts of 1,3-butadiene was added to continue the polymerization reaction. Furthermore, when the polymerization conversion reached 60%, 10 parts of 1,3-butadiene was added to continue the polymerization reaction. When the polymerization conversion reached 80%, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) was added in the form of an aqueous dispersion to terminate the polymerization reaction. The amount of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) used was set to 2,000 ppm by weight in the final foam rubber latex composition. Then, after removing the unreacted monomer, 80 parts of 1,3-butadiene is added, the temperature in the system is set to 15° C., and the mixture is stirred for 5 hours at a rotation speed of 1,000 rpm using a paddle type stirring blade. Then, a grain size enlarging treatment was performed. Next, after removing 1,3-butadiene, concentration was carried out to obtain a copolymer rubber latex having a solid content concentration of 67% by weight. The resulting copolymer rubber latex had a pH of 11.3 and a viscosity (B type viscosity) of 280 cps. In addition, the composition of the monomer units contained in the copolymer rubber constituting the copolymer rubber latex was almost the same as the charged amount (also in Examples 2 to 5 and Comparative Examples 1 to 5 described later). Similarly.).
そして、上記にて得られた共重合体ゴムラテックスの固形分100部に対して、加硫系水分散液(コロイド硫黄/ジチオカルバミン酸塩系加硫促進剤ノクセラーEZ(大内新興化学工業株式会社製)/チアゾール系加硫促進剤ノクセラーMZ(大内新興化学工業株式会社製)=2/1/1(重量比):固形分濃度50重量%)4部、酸化亜鉛水分散液(固形分濃度重量50%)3部、気泡安定剤(トリメンベース:Crompton Corp製)1部、および1,2-ベンゾイソチアゾリン-3-オン(BIT)を添加し十分に分散させ、固形分濃度67重量%のフォームラバー用共重合体ラテックス組成物を得た。なお、1,2-ベンゾイソチアゾリン-3-オン(BIT)の添加量は、フォームラバー用共重合体ラテックス組成物中において、100重量ppmとなる量とした。 (Preparation of latex composition for foam rubber)
Then, with respect to 100 parts of the solid content of the copolymer rubber latex obtained above, a vulcanization-based aqueous dispersion (colloidal sulfur/dithiocarbamate-based vulcanization accelerator Noccellar EZ (Ouchi Shinko Kagaku Kogyo Co., Ltd. (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) / thiazole-based vulcanization accelerator Noxceler MZ (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) = 2/1/1 (weight ratio): solid content concentration 50% by weight) 4 parts, zinc oxide aqueous dispersion (solid content 3 parts (concentration weight 50%), 1 part foam stabilizer (trimene base: manufactured by Crompton Corp.), and 1,2-benzisothiazolin-3-one (BIT) were added and sufficiently dispersed to obtain a solid content concentration of 67% by weight. A copolymer latex composition for foam rubber was obtained. The amount of 1,2-benzisothiazolin-3-one (BIT) added was set to 100 ppm by weight in the copolymer latex composition for foam rubber.
そして、上記にて得られたフォームラバー用共重合体ラテックス組成物を、スタンドミキサー(エレクトロラックス社製ESM945)を用いて攪拌し、体積で5倍程度になるよう発泡させた後、珪フッ化ソーダ水分散液(固形分濃度20重量%)1.5部添加しさらに1分間攪拌することで、発泡物を得た。次いで、得られた発泡物を成型用型枠(直径7cm、高さ8cm)に流し入れ、凝固させた後、110℃で1時間加硫することで、フォームラバーを得た。型枠から取り出したフォームラバーを40℃のお湯で10分間水洗し、60℃のオーブンで4時間乾燥した後、厚みが0.8cmとなるように、円板状に切断し、円板状のフォームラバーを得て、上記方法にしたがって、耐油性、F型硬度、ならびに、繰り返し使用時の変色、劣化および臭気の各測定、評価を行った。結果を表1に示す。 (Manufacture of foam rubber)
Then, the copolymer latex composition for foam rubber obtained above is stirred using a stand mixer (ESM945 manufactured by Electrolux Co., Ltd.) and foamed so as to be about five times its volume, and then silicified. A foamed product was obtained by adding 1.5 parts of an aqueous soda dispersion (solid concentration: 20% by weight) and further stirring for 1 minute. Next, the resulting foam was poured into a mold (7 cm in diameter, 8 cm in height), solidified, and vulcanized at 110° C. for 1 hour to obtain a foam rubber. The foam rubber removed from the mold was washed with hot water at 40°C for 10 minutes, dried in an oven at 60°C for 4 hours, and then cut into discs with a thickness of 0.8 cm. A foam rubber was obtained, and oil resistance, F-type hardness, and discoloration, deterioration and odor during repeated use were measured and evaluated according to the above methods. Table 1 shows the results.
アクリロニトリルの使用量を45部に変更し、重合開始時に用いる1,3-ブタジエンの量を35部に変更し、かつ、2,2,6,6-テトラメチルピペリジン-1-オキシル(TEMPO)の使用量を、最終的に得られるフォームラバー用ラテックス組成物中において、1,000重量ppmとなる量とした以外は、実施例1と同様にして、固形分濃度65重量%の共重合体ゴムラテックスを調製した。得られた共重合体ゴムラテックスのpHおよび粘度(B型粘度)は表1に示す通りであった。
そして、上記にて得られた共重合体ゴムラテックスを使用した以外は、実施例1と同様にして、フォームラバー用ラテックス組成物(固形分濃度65重量%)の調製、およびフォームラバーの製造を行い、同様に評価した。結果を表1に示す。 <Example 2>
The amount of acrylonitrile used was changed to 45 parts, the amount of 1,3-butadiene used at the start of polymerization was changed to 35 parts, and 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) A copolymer rubber having a solid content concentration of 65% by weight was prepared in the same manner as in Example 1, except that the amount used was adjusted to 1,000 ppm by weight in the final foam rubber latex composition. A latex was prepared. The pH and viscosity (B-type viscosity) of the obtained copolymer rubber latex were as shown in Table 1.
Then, in the same manner as in Example 1, except that the copolymer rubber latex obtained above was used, a latex composition for foam rubber (65% by weight of solid content) was prepared and a foam rubber was produced. performed and evaluated in the same way. Table 1 shows the results.
重合開始時に用いる1,3-ブタジエンの量を30部に変更し、重合開始時に、さらに、イソプレン5部を配合した以外は、実施例2と同様にして、固形分濃度67重量%の共重合体ゴムラテックスを調製した。得られた共重合体ゴムラテックスのpHおよび粘度(B型粘度)は表1に示す通りであった。
そして、上記にて得られた共重合体ゴムラテックスを使用した以外は、実施例1と同様にして、フォームラバー用ラテックス組成物(固形分濃度67重量%)の調製、およびフォームラバーの製造を行い、同様に評価した。結果を表1に示す。 <Example 3>
In the same manner as in Example 2, except that the amount of 1,3-butadiene used at the start of polymerization was changed to 30 parts, and 5 parts of isoprene was further blended at the start of polymerization, a copolymer having a solid content concentration of 67% by weight was prepared. A coalesced rubber latex was prepared. The pH and viscosity (B-type viscosity) of the obtained copolymer rubber latex were as shown in Table 1.
Then, in the same manner as in Example 1, except that the copolymer rubber latex obtained above was used, a latex composition for foam rubber (67% by weight of solid content) was prepared and a foam rubber was produced. performed and evaluated in the same way. Table 1 shows the results.
2,2,6,6-テトラメチルピペリジン-1-オキシル(TEMPO)の使用量を、最終的に得られるフォームラバー用ラテックス組成物中において、500重量ppmとなる量とした以外は、実施例2と同様にして、固形分濃度65重量%の共重合体ゴムラテックスを調製した。得られた共重合体ゴムラテックスのpHおよび粘度(B型粘度)は表1に示す通りであった。
そして、上記にて得られた共重合体ゴムラテックスを使用した以外は、実施例1と同様にして、フォームラバー用ラテックス組成物(固形分濃度65重量%)の調製、およびフォームラバーの製造を行い、同様に評価した。結果を表1に示す。 <Example 4>
Example except that the amount of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) used was 500 ppm by weight in the finally obtained foam rubber latex composition. A copolymer rubber latex having a solid concentration of 65% by weight was prepared in the same manner as in Example 2. The pH and viscosity (B-type viscosity) of the obtained copolymer rubber latex were as shown in Table 1.
Then, in the same manner as in Example 1, except that the copolymer rubber latex obtained above was used, a latex composition for foam rubber (65% by weight of solid content) was prepared and a foam rubber was produced. performed and evaluated in the same way. Table 1 shows the results.
実施例2と同様にして得られた共重合体ゴムラテックスを使用する一方で、1,2-ベンゾイソチアゾリン-3-オン(BIT)に代えて、同量の2-メチル-4-イソチアゾリン-3-オン(MIT)を使用した以外は、実施例2と同様にして、フォームラバー用ラテックス組成物(固形分濃度65重量%)の調製、およびフォームラバーの製造を行い、同様に評価した。結果を表1に示す。 <Example 5>
While using a copolymer rubber latex obtained in the same manner as in Example 2, instead of 1,2-benzisothiazolin-3-one (BIT), the same amount of 2-methyl-4-isothiazolin-3 A latex composition for foam rubber (solid concentration: 65% by weight) was prepared and foam rubber was produced in the same manner as in Example 2, except that MIT was used, and evaluated in the same manner. Table 1 shows the results.
アクリロニトリルの使用量を47部に変更し、重合開始時に用いる1,3-ブタジエンの量を18部に変更するとともに、重合開始時に、さらに、イソプレン15部を配合し、かつ、2,2,6,6-テトラメチルピペリジン-1-オキシル(TEMPO)の水分散液に代えて、ジエチルヒドロキシアミン(HAS)の水分散液を使用した以外は、実施例1と同様にして、固形分濃度65重量%の共重合体ゴムラテックスを調製した。なお、ジエチルヒドロキシアミン(HAS)の使用量は、最終的に得られるフォームラバー用ラテックス組成物中において、2,000重量ppmとなる量とした。また、得られた共重合体ゴムラテックスのpHおよび粘度(B型粘度)は表1に示す通りであった。
そして、上記にて得られた共重合体ゴムラテックスを使用した以外は、実施例1と同様にして、フォームラバー用ラテックス組成物(固形分濃度65重量%)の調製、およびフォームラバーの製造を行い、同様に評価した。結果を表1に示す。 <Comparative Example 1>
The amount of acrylonitrile used was changed to 47 parts, and the amount of 1,3-butadiene used at the start of polymerization was changed to 18 parts. ,6-Tetramethylpiperidine-1-oxyl (TEMPO) was replaced with an aqueous dispersion of diethylhydroxyamine (HAS) in the same manner as in Example 1, except that a solid content concentration of 65 wt. % copolymer rubber latex was prepared. The amount of diethylhydroxyamine (HAS) used was set to 2,000 ppm by weight in the finally obtained latex composition for foam rubber. The pH and viscosity (B-type viscosity) of the obtained copolymer rubber latex were as shown in Table 1.
Then, in the same manner as in Example 1, except that the copolymer rubber latex obtained above was used, a latex composition for foam rubber (65% by weight of solid content) was prepared and a foam rubber was produced. performed and evaluated in the same way. Table 1 shows the results.
2,2,6,6-テトラメチルピペリジン-1-オキシル(TEMPO)の水分散液に代えて、ジエチルヒドロキシアミン(HAS)の水分散液を使用した以外は、実施例2と同様にして、固形分濃度65重量%の共重合体ゴムラテックスを調製した。なお、ジエチルヒドロキシアミン(HAS)の使用量は、最終的に得られるフォームラバー用ラテックス組成物中において、2,000重量ppmとなる量とした。また、得られた共重合体ゴムラテックスのpHおよび粘度(B型粘度)は表1に示す通りであった。
そして、上記にて得られた共重合体ゴムラテックスを使用した以外は、実施例1と同様にして、フォームラバー用ラテックス組成物(固形分濃度65重量%)の調製、およびフォームラバーの製造を行い、同様に評価した。結果を表1に示す。 <Comparative Example 2>
In the same manner as in Example 2, except that an aqueous dispersion of diethylhydroxyamine (HAS) was used instead of the aqueous dispersion of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO). A copolymer rubber latex having a solids concentration of 65% by weight was prepared. The amount of diethylhydroxyamine (HAS) used was set to 2,000 ppm by weight in the finally obtained latex composition for foam rubber. The pH and viscosity (B-type viscosity) of the obtained copolymer rubber latex were as shown in Table 1.
Then, in the same manner as in Example 1, except that the copolymer rubber latex obtained above was used, a latex composition for foam rubber (65% by weight of solid content) was prepared and a foam rubber was produced. performed and evaluated in the same way. Table 1 shows the results.
2,2,6,6-テトラメチルピペリジン-1-オキシル(TEMPO)を使用しなかった以外は、実施例2と同様にして、固形分濃度65重量%の共重合体ゴムラテックスを調製した。なお、比較例3においては、乳化重合の重合停止剤は使用しなかった。得られた共重合体ゴムラテックスのpHおよび粘度(B型粘度)は表1に示す通りであった。
そして、上記にて得られた共重合体ゴムラテックスを使用した以外は、実施例1と同様にして、フォームラバー用ラテックス組成物(固形分濃度66重量%)の調製、およびフォームラバーの製造を行い、同様に評価した。結果を表1に示す。 <Comparative Example 3>
A copolymer rubber latex having a solid concentration of 65% by weight was prepared in the same manner as in Example 2, except that 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) was not used. In Comparative Example 3, no polymerization terminator for emulsion polymerization was used. The pH and viscosity (B-type viscosity) of the obtained copolymer rubber latex were as shown in Table 1.
Then, in the same manner as in Example 1 except that the copolymer rubber latex obtained above was used, a latex composition for foam rubber (66% by weight of solid content) was prepared and foam rubber was produced. performed and evaluated in the same way. Table 1 shows the results.
実施例2と同様にして得られた共重合体ゴムラテックスを使用する一方で、1,2-ベンゾイソチアゾリン-3-オン(BIT)を使用しなかった以外は、実施例2と同様にして、フォームラバー用ラテックス組成物(固形分濃度65重量%)の調製、およびフォームラバーの製造を行い、同様に評価した。結果を表1に示す。 <Comparative Example 4>
In the same manner as in Example 2, except that the copolymer rubber latex obtained in the same manner as in Example 2 was used, and 1,2-benzisothiazolin-3-one (BIT) was not used, A latex composition for foam rubber (solid concentration: 65% by weight) was prepared, and foam rubber was produced and evaluated in the same manner. Table 1 shows the results.
アクリロニトリルの使用量を20部に変更し、重合開始時に用いる1,3-ブタジエンの量を55部に変更した以外は、実施例3と同様にして、固形分濃度65重量%の共重合体ゴムラテックスを調製した。得られた共重合体ゴムラテックスのpHおよび粘度(B型粘度)は表1に示す通りであった。
そして、上記にて得られた共重合体ゴムラテックスを使用した以外は、実施例1と同様にして、フォームラバー用ラテックス組成物(固形分濃度65重量%)の調製、およびフォームラバーの製造を行い、同様に評価した。結果を表1に示す。 <Comparative Example 5>
A copolymer rubber having a solid content concentration of 65% by weight was prepared in the same manner as in Example 3, except that the amount of acrylonitrile used was changed to 20 parts and the amount of 1,3-butadiene used at the start of polymerization was changed to 55 parts. A latex was prepared. The pH and viscosity (B-type viscosity) of the obtained copolymer rubber latex were as shown in Table 1.
Then, in the same manner as in Example 1, except that the copolymer rubber latex obtained above was used, a latex composition for foam rubber (65% by weight of solid content) was prepared and a foam rubber was produced. performed and evaluated in the same way. Table 1 shows the results.
ニトロキシルラジカル化合物を使用しなかった場合には、得られるフォームラバーは、繰り返し使用時の変色および劣化が発生し、繰り返し使用時における臭気の発生の抑制効果も不十分であった(比較例3)。
また、ニトロキシルラジカル化合物を含有している一方で、チアゾリン系化合物を含有しない場合には、得られるフォームラバーは、繰り返し使用時に臭気が発生する結果となった(比較例4)。
さらに、共重合体ゴムラテックスを構成する共重合体ゴムの組成が、本発明所定の範囲外である場合には、得られるフォームラバーは、耐油性に劣り、しかも、F型硬度も低くなり、やわらかい感触が得られないものであった(比較例5)。 On the other hand, when diethylhydroxyamine (HAS) is used instead of the nitroxyl radical compound, it contains 1,2-benzisothiazolin-3-one (BIT) as a thiazoline compound. The resulting foam rubber resulted in the generation of odor during repeated use (Comparative Examples 1 and 2).
When no nitroxyl radical compound was used, the obtained foam rubber was discolored and deteriorated during repeated use, and the effect of suppressing odor generation during repeated use was insufficient (Comparative Example 3). ).
Further, when the nitroxyl radical compound was contained but the thiazoline compound was not contained, the resulting foam rubber produced an odor during repeated use (Comparative Example 4).
Furthermore, if the composition of the copolymer rubber constituting the copolymer rubber latex is outside the range specified by the present invention, the resulting foam rubber will be inferior in oil resistance and will also have a low F-type hardness. A soft feel could not be obtained (Comparative Example 5).
Claims (9)
- シアノ基含有エチレン性不飽和単量体単位30~60重量%、および脂肪族共役ジエン系単量体単位40~70重量%を含有する共重合体ゴムラテックスと、
ニトロキシルラジカル化合物と、
チアゾリン系化合物とを含有し、
固形分濃度が55~75重量%であるフォームラバー用ラテックス組成物。 a copolymer rubber latex containing 30 to 60% by weight of cyano group-containing ethylenically unsaturated monomer units and 40 to 70% by weight of aliphatic conjugated diene monomer units;
a nitroxyl radical compound;
containing a thiazoline-based compound,
A latex composition for foam rubber having a solid content concentration of 55 to 75% by weight. - 前記ニトロキシルラジカル化合物の含有量が100~10,000重量ppmである請求項1に記載のフォームラバー用ラテックス組成物。 The latex composition for foam rubber according to claim 1, wherein the content of the nitroxyl radical compound is 100 to 10,000 ppm by weight.
- 前記チアゾリン系化合物の含有量が10~1,000重量ppmである請求項1または2に記載のフォームラバー用ラテックス組成物。 The latex composition for foam rubber according to claim 1 or 2, wherein the content of the thiazoline compound is 10 to 1,000 ppm by weight.
- 前記ニトロキシルラジカル化合物が、2,2,6,6-テトラメチルピペリジン-1-オキシル(TEMPO)である請求項1~3のいずれかに記載のフォームラバー用ラテックス組成物。 The latex composition for foam rubber according to any one of claims 1 to 3, wherein the nitroxyl radical compound is 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO).
- 前記チアゾリン系化合物が、2-メチル-4-イソチアゾリン-3-オン(MIT)または1,2-ベンゾイソチアゾリン-3-オン(BIT)である請求項1~4のいずれかに記載のフォームラバー用ラテックス組成物。 The foam rubber according to any one of claims 1 to 4, wherein the thiazoline compound is 2-methyl-4-isothiazolin-3-one (MIT) or 1,2-benzisothiazolin-3-one (BIT). latex composition.
- 固形分濃度が60~70重量%である請求項1~5のいずれかに記載のフォームラバー用ラテックス組成物。 The latex composition for foam rubber according to any one of claims 1 to 5, which has a solid content concentration of 60 to 70% by weight.
- 固形分濃度が63~69重量%である請求項1~6のいずれかに記載のフォームラバー用ラテックス組成物。 The latex composition for foam rubber according to any one of claims 1 to 6, which has a solid content concentration of 63 to 69% by weight.
- 固形分濃度が64.5~67.5重量%である請求項1~7のいずれかに記載のフォームラバー用ラテックス組成物。 The latex composition for foam rubber according to any one of claims 1 to 7, which has a solid content concentration of 64.5 to 67.5% by weight.
- 請求項1~8のいずれかに記載のフォームラバー用ラテックス組成物を用いて得られるフォームラバー。 A foam rubber obtained using the latex composition for foam rubber according to any one of claims 1 to 8.
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JPH10237329A (en) * | 1996-12-24 | 1998-09-08 | Sumitomo Chem Co Ltd | Antimicrobial resin composition |
JP2005097475A (en) * | 2003-09-26 | 2005-04-14 | Nippon A & L Kk | Copolymer latex with high long-term storage stability |
US20080184642A1 (en) * | 2007-02-05 | 2008-08-07 | Laura Sebastian | Latex foam insulation and method of making and using same |
JP5186992B2 (en) * | 2008-04-30 | 2013-04-24 | 日本ゼオン株式会社 | Copolymer latex for foam rubber, copolymer latex composition for foam rubber, and farm rubber |
WO2019065400A1 (en) * | 2017-09-28 | 2019-04-04 | 日本ゼオン株式会社 | Method for producing nitrile group-containing copolymer rubber |
JP2020503401A (en) * | 2016-12-15 | 2020-01-30 | シントマー スンディリアン ブルハド | Curable polymer latex compositions for rubber product manufacture |
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JPH10237329A (en) * | 1996-12-24 | 1998-09-08 | Sumitomo Chem Co Ltd | Antimicrobial resin composition |
JP2005097475A (en) * | 2003-09-26 | 2005-04-14 | Nippon A & L Kk | Copolymer latex with high long-term storage stability |
US20080184642A1 (en) * | 2007-02-05 | 2008-08-07 | Laura Sebastian | Latex foam insulation and method of making and using same |
JP5186992B2 (en) * | 2008-04-30 | 2013-04-24 | 日本ゼオン株式会社 | Copolymer latex for foam rubber, copolymer latex composition for foam rubber, and farm rubber |
JP2020503401A (en) * | 2016-12-15 | 2020-01-30 | シントマー スンディリアン ブルハド | Curable polymer latex compositions for rubber product manufacture |
WO2019065400A1 (en) * | 2017-09-28 | 2019-04-04 | 日本ゼオン株式会社 | Method for producing nitrile group-containing copolymer rubber |
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