JP2021008575A - Copolymer latex for adhesive and adhesive composition - Google Patents
Copolymer latex for adhesive and adhesive composition Download PDFInfo
- Publication number
- JP2021008575A JP2021008575A JP2019123495A JP2019123495A JP2021008575A JP 2021008575 A JP2021008575 A JP 2021008575A JP 2019123495 A JP2019123495 A JP 2019123495A JP 2019123495 A JP2019123495 A JP 2019123495A JP 2021008575 A JP2021008575 A JP 2021008575A
- Authority
- JP
- Japan
- Prior art keywords
- mass
- copolymer latex
- monomer
- less
- adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004816 latex Substances 0.000 title claims abstract description 184
- 229920000126 latex Polymers 0.000 title claims abstract description 184
- 229920001577 copolymer Polymers 0.000 title claims abstract description 160
- 239000000203 mixture Substances 0.000 title claims abstract description 112
- 239000000853 adhesive Substances 0.000 title claims abstract description 108
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 108
- 239000000178 monomer Substances 0.000 claims abstract description 127
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002245 particle Substances 0.000 claims abstract description 43
- 239000007787 solid Substances 0.000 claims abstract description 40
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 36
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000004908 Emulsion polymer Substances 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 claims description 10
- 229920001971 elastomer Polymers 0.000 description 27
- 239000005060 rubber Substances 0.000 description 27
- 238000006116 polymerization reaction Methods 0.000 description 21
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- -1 fatty acid salt Chemical class 0.000 description 15
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 12
- 239000012783 reinforcing fiber Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 239000003505 polymerization initiator Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000003995 emulsifying agent Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 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 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- 239000012986 chain transfer agent Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 2
- CTMHWPIWNRWQEG-UHFFFAOYSA-N 1-methylcyclohexene Chemical compound CC1=CCCCC1 CTMHWPIWNRWQEG-UHFFFAOYSA-N 0.000 description 2
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical group C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-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
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- 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
- FSWCCQWDVGZMRD-UHFFFAOYSA-N 4-methylcyclohexene Chemical compound CC1CCC=CC1 FSWCCQWDVGZMRD-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-araboascorbic acid Natural products OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-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
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000002211 L-ascorbic acid Substances 0.000 description 2
- 235000000069 L-ascorbic acid Nutrition 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000000427 antigen Substances 0.000 description 2
- 102000036639 antigens Human genes 0.000 description 2
- 108091007433 antigens Proteins 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000004318 erythorbic acid Substances 0.000 description 2
- 235000010350 erythorbic acid Nutrition 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229940026239 isoascorbic acid Drugs 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 2
- 238000001256 steam distillation Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 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
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical class CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- ZUDLIFVTNPYZJH-UHFFFAOYSA-N 1,1,2,2-tetraphenylethylbenzene Chemical compound C1=CC=CC=C1C(C(C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 ZUDLIFVTNPYZJH-UHFFFAOYSA-N 0.000 description 1
- QIDUHGHFWAMMPV-UHFFFAOYSA-N 1,1-diphenylethylbenzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(C)C1=CC=CC=C1 QIDUHGHFWAMMPV-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- BIRJAUKLRAMLEV-UHFFFAOYSA-N 1-phenylethenoxymethylbenzene Chemical compound C=1C=CC=CC=1C(=C)OCC1=CC=CC=C1 BIRJAUKLRAMLEV-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- QZLAEIZEPJAELS-UHFFFAOYSA-N 2,4,4-trimethylpentane-2-thiol Chemical compound CC(C)(C)CC(C)(C)S QZLAEIZEPJAELS-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- OWHSTLLOZWTNTQ-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS OWHSTLLOZWTNTQ-UHFFFAOYSA-N 0.000 description 1
- MIRQGKQPLPBZQM-UHFFFAOYSA-N 2-hydroperoxy-2,4,4-trimethylpentane Chemical compound CC(C)(C)CC(C)(C)OO MIRQGKQPLPBZQM-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- NYVPRWODADOGAO-UHFFFAOYSA-N 2-phenylmethoxyprop-2-enenitrile Chemical compound N#CC(=C)OCC1=CC=CC=C1 NYVPRWODADOGAO-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- DPZYLEIWHTWHCU-UHFFFAOYSA-N 3-ethenylpyridine Chemical compound C=CC1=CC=CN=C1 DPZYLEIWHTWHCU-UHFFFAOYSA-N 0.000 description 1
- FXNREMQIVSLLHN-UHFFFAOYSA-N 4-[[5-chloro-3-[(2,4-dihydroxyphenyl)methyl]-2-hydroxyphenyl]methyl]benzene-1,3-diol Chemical compound OC1=CC(O)=CC=C1CC1=CC(Cl)=CC(CC=2C(=CC(O)=CC=2)O)=C1O FXNREMQIVSLLHN-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- VJOWMORERYNYON-UHFFFAOYSA-N 5-ethenyl-2-methylpyridine Chemical compound CC1=CC=C(C=C)C=N1 VJOWMORERYNYON-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- FVCPXLWAKNJIKK-UHFFFAOYSA-N Dimexano Chemical compound COC(=S)SSC(=S)OC FVCPXLWAKNJIKK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 150000004808 allyl alcohols Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 208000018747 cerebellar ataxia with neuropathy and bilateral vestibular areflexia syndrome Diseases 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 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
- 239000008121 dextrose Substances 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
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 235000013681 dietary sucrose Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- REQPQFUJGGOFQL-UHFFFAOYSA-N dimethylcarbamothioyl n,n-dimethylcarbamodithioate Chemical class CN(C)C(=S)SC(=S)N(C)C REQPQFUJGGOFQL-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical class CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 1
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 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
- 238000001035 drying Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229940079826 hydrogen sulfite Drugs 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 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
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000012285 osmium tetroxide Substances 0.000 description 1
- 229910000489 osmium tetroxide Inorganic materials 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 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
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229960004793 sucrose Drugs 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
- C09J109/06—Copolymers with styrene
- C09J109/08—Latex
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/06—Butadiene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
- C09J109/02—Copolymers with acrylonitrile
- C09J109/04—Latex
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09J161/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、接着剤用共重合体ラテックス、詳しくは、ゴムと繊維とを接着する接着剤用共重合体ラテックス、および、接着剤用共重合体ラテックスを含有する接着剤組成物に関する。 The present invention relates to a copolymer latex for an adhesive, specifically, a copolymer latex for an adhesive that adheres rubber and a fiber, and an adhesive composition containing a copolymer latex for an adhesive.
従来、共重合体ラテックス（Ａ）５０〜９０質量％と、共重合体ラテックス（Ｂ）１０〜５０質量％とを含有する接着剤用共重合体ラテックスが知られている。 Conventionally, a copolymer latex for an adhesive containing 50 to 90% by mass of the copolymer latex (A) and 10 to 50% by mass of the copolymer latex (B) is known.
共重合体ラテックス（Ａ）は、ブタジエン系単量体３５〜７５質量％、ビニルピリジン系単量体１０〜３０質量％およびスチレン系単量体１０〜５５質量％を含む単量体組成物（ａ）を乳化重合して得られる。共重合体ラテックス（Ｂ）は、ブタジエン系単量体３〜２５質量％、ビニルピリジン系単量体０〜５質量％、スチレン系単量体５５〜９７質量％、エチレン系不飽和カルボン酸０〜１０質量％、および、共重合可能な他の単量体０〜２０質量％を含む単量体組成物（ｂ）を乳化重合して得られる（例えば、下記特許文献１参照。）。 The copolymer latex (A) is a monomer composition containing 35 to 75% by mass of a butadiene monomer, 10 to 30% by mass of a vinyl pyridine monomer, and 10 to 55% by mass of a styrene monomer. It is obtained by emulsion polymerization of a). The copolymer latex (B) contains 3 to 25% by mass of a butadiene-based monomer, 0 to 5% by mass of a vinylpyridine-based monomer, 55 to 97% by mass of a styrene-based monomer, and 0 ethylene-based unsaturated carboxylic acid. It is obtained by emulsion polymerization of a monomer composition (b) containing 10% by mass and 0 to 20% by mass of another copolymerizable monomer (see, for example, Patent Document 1 below).
しかし、上記した特許文献１に記載の接着剤用共重合体ラテックスでは、接着力と、タイヤコードの柔軟性との両立を図ることが困難である。 However, with the copolymer latex for adhesives described in Patent Document 1 described above, it is difficult to achieve both adhesive strength and flexibility of the tire cord.
そこで、本発明の目的は、接着力と、タイヤコードの柔軟性との両立を図ることができる接着剤用共重合体ラテックスおよび接着剤組成物を提供することにある。 Therefore, an object of the present invention is to provide a copolymer latex for an adhesive and an adhesive composition capable of achieving both adhesive strength and flexibility of a tire cord.
本発明［１］は、ブタジエン単量体３５質量％以上７５質量％以下と、ビニルピリジン単量体１０質量％以上３０質量％以下と、スチレン単量体１０質量％以上５５質量％以下とを含有する単量体組成物（ａ）の乳化重合物である共重合体ラテックス（Ａ）と、前記ブタジエン単量体３質量％以上３０質量％以下を含有する単量体組成物（ｂ）の乳化重合物である共重合体ラテックス（Ｂ）とを含有し、前記共重合体ラテックス（Ａ）の固形分と前記共重合体ラテックス（Ｂ）の固形分との総量に対する前記共重合体ラテックス（Ｂ）の固形分の割合が、５質量％以上１５質量％以下であり、前記共重合体ラテックス（Ｂ）中のラテックス粒子の個数基準の平均粒子径が、１５０ｎｍ以上である、接着剤用共重合体ラテックスを含む。 In the present invention [1], butadiene monomer is 35% by mass or more and 75% by mass or less, vinylpyridine monomer is 10% by mass or more and 30% by mass or less, and styrene monomer is 10% by mass or more and 55% by mass or less. A copolymer latex (A) which is an emulsified polymer of the monomer composition (a) contained, and a monomer composition (b) containing 3% by mass or more and 30% by mass or less of the butadiene monomer. The copolymer latex (B) containing the copolymer latex (B), which is an emulsified polymer, with respect to the total amount of the solid content of the copolymer latex (A) and the solid content of the copolymer latex (B). The solid content ratio of B) is 5% by mass or more and 15% by mass or less, and the average particle size based on the number of latex particles in the copolymer latex (B) is 150 nm or more. Contains polymer latex.
本発明［２］は、前記単量体組成物（ｂ）が、前記スチレン単量体５０質量％以上８５質量％以下と、前記ビニルピリジン単量体３０質量％以下とを、さらに含有する、上記［１］の接着剤用共重合体ラテックスを含む。 In the present invention [2], the monomer composition (b) further contains 50% by mass or more and 85% by mass or less of the styrene monomer and 30% by mass or less of the vinylpyridine monomer. The copolymer latex for the adhesive of the above [1] is contained.
本発明［３］は、前記単量体組成物（ａ）が、前記ブタジエン単量体を、５０質量％以上含有する、上記［１］または［２］の接着剤用共重合体ラテックスを含む。 The present invention [3] includes the copolymer latex for an adhesive of the above [1] or [2], wherein the monomer composition (a) contains 50% by mass or more of the butadiene monomer. ..
本発明［４］は、前記共重合体ラテックス（Ａ）と前記共重合体ラテックス（Ｂ）との総量に対する前記共重合体ラテックス（Ｂ）の割合が、１０質量％以上である、上記［１］〜［３］のいずれか１つの接着剤用共重合体ラテックスを含む。 In the present invention [4], the ratio of the copolymer latex (B) to the total amount of the copolymer latex (A) and the copolymer latex (B) is 10% by mass or more. ] To [3], the copolymer latex for an adhesive is included.
本発明［５］は、ブタジエン単量体３５質量％以上７５質量％以下と、ビニルピリジン単量体１０質量％以上３０質量％以下と、スチレン単量体１０質量％以上５５質量％以下とを含有する単量体組成物（ａ）の乳化重合物である共重合体ラテックス（Ａ）と、前記ブタジエン単量体３質量％以上３０質量％以下を含有する単量体組成物（ｂ）の乳化重合物である共重合体ラテックス（Ｂ）と、レゾルシン−ホルマリン樹脂とを含有し、前記共重合体ラテックス（Ａ）の固形分と前記共重合体ラテックス（Ｂ）の固形分との総量に対する前記共重合体ラテックス（Ｂ）の固形分の割合が、５質量％以上１５質量％以下であり、前記共重合体ラテックス（Ｂ）中のラテックス粒子の個数基準の平均粒子径が、１５０ｎｍ以上である、接着剤組成物を含む。 The present invention [5] comprises 35% by mass or more and 75% by mass or less of the butadiene monomer, 10% by mass or more and 30% by mass or less of the vinylpyridine monomer, and 10% by mass or more and 55% by mass or less of the styrene monomer. A copolymer latex (A) which is an emulsified polymer of the monomer composition (a) contained, and a monomer composition (b) containing 3% by mass or more and 30% by mass or less of the butadiene monomer. It contains a copolymer latex (B) which is an emulsified polymer and a resorcin-formalin resin, and is based on the total amount of the solid content of the copolymer latex (A) and the solid content of the copolymer latex (B). When the solid content ratio of the copolymer latex (B) is 5% by mass or more and 15% by mass or less, and the average particle size based on the number of latex particles in the copolymer latex (B) is 150 nm or more. Includes an adhesive composition.
本発明の接着剤用共重合体ラテックスおよび接着剤組成物によれば、接着力と、タイヤコードの柔軟性との両立を図ることができる。 According to the copolymer latex for adhesives and the adhesive composition of the present invention, it is possible to achieve both adhesive strength and flexibility of the tire cord.
１．接着剤用共重合体ラテックス
接着剤用共重合体ラテックスは、共重合体ラテックス（Ａ）と共重合体ラテックス（Ｂ）とを含有する。接着剤用共重合体ラテックスは、好ましくは、共重合体ラテックス（Ａ）および共重合体ラテックス（Ｂ）からなる。
1. 1. Copolymer Latex for Adhesives The copolymer latex for adhesives contains a copolymer latex (A) and a copolymer latex (B). The copolymer latex for adhesives preferably comprises the copolymer latex (A) and the copolymer latex (B).
（１）共重合体ラテックス（Ａ）
共重合体ラテックス（Ａ）は、単量体組成物（ａ）の乳化重合物である。単量体組成物（ａ）は、ブタジエン単量体、ビニルピリジン単量体、およびスチレン単量体を含有する。言い換えると、共重合体ラテックス（Ａ）中のラテックス粒子は、ブタジエン単量体に由来する構造単位と、ビニルピリジン単量体に由来する構造単位と、スチレン単量体に由来する構造単位とを有する。
(1) Copolymer latex (A)
The copolymer latex (A) is an emulsion polymer of the monomer composition (a). The monomer composition (a) contains a butadiene monomer, a vinylpyridine monomer, and a styrene monomer. In other words, the latex particles in the copolymer latex (A) have a structural unit derived from a butadiene monomer, a structural unit derived from a vinylpyridine monomer, and a structural unit derived from a styrene monomer. Have.
ブタジエン単量体としては、例えば、１，３−ブタジエン、２−メチル−１，３−ブタジエン、２，３−ジメチル−１，３−ブタジエンなどが挙げられる。ブタジエン単量体は、好ましくは、１，３−ブタジエンである。単量体組成物（ａ）は、１種類のブタジエン単量体を含んでもよい。単量体組成物（ａ）は、複数種類のブタジエン単量体を含んでもよい。 Examples of the butadiene monomer include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene and the like. The butadiene monomer is preferably 1,3-butadiene. The monomer composition (a) may contain one kind of butadiene monomer. The monomer composition (a) may contain a plurality of types of butadiene monomers.
ビニルピリジン単量体としては、例えば、２−ビニルピリジン、３−ビニルピリジン、４−ビニルピリジン、２−メチル−５−ビニルピリジンなどが挙げられる。ビニルピリジン単量体は、好ましくは、２−ビニルピリジンである。単量体組成物（ａ）は、１種類のビニルピリジン単量体を含有してもよい。単量体組成物（ａ）は、複数種類のビニルピリジン単量体を含有してもよい。 Examples of the vinylpyridine monomer include 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine and the like. The vinylpyridine monomer is preferably 2-vinylpyridine. The monomer composition (a) may contain one kind of vinylpyridine monomer. The monomer composition (a) may contain a plurality of types of vinylpyridine monomers.
スチレン単量体としては、例えば、スチレン、α−メチルスチレン、モノクロロスチレンなどが挙げられる。スチレン単量体は、好ましくは、スチレンである。単量体組成物（ａ）は、１種類のスチレン単量体を含有してもよい。単量体組成物（ａ）は、複数種類のスチレン単量体を含有してもよい。 Examples of the styrene monomer include styrene, α-methylstyrene, monochlorostyrene and the like. The styrene monomer is preferably styrene. The monomer composition (a) may contain one kind of styrene monomer. The monomer composition (a) may contain a plurality of types of styrene monomers.
単量体組成物（ａ）は、ブタジエン単量体を、３５質量％以上、好ましくは、４５質量％以上、より好ましくは、５０質量％以上、７５質量％以下、好ましくは、７０質量％以下含有する。言い換えると、共重合体ラテックス（Ａ）中のラテックス粒子は、ブタジエン単量体に由来する構造単位を、３５質量％以上、好ましくは、４５質量％以上、より好ましくは、５０質量％以上、７５質量％以下、好ましくは、７０質量％以下含有する。 The monomer composition (a) contains 35% by mass or more, preferably 45% by mass or more, more preferably 50% by mass or more, 75% by mass or less, and preferably 70% by mass or less of the butadiene monomer. contains. In other words, the latex particles in the copolymer latex (A) contain 35% by mass or more, preferably 45% by mass or more, more preferably 50% by mass or more, 75 of structural units derived from the butadiene monomer. It is contained in an amount of 70% by mass or less, preferably 70% by mass or less.
単量体組成物（ａ）中のブタジエン単量体の割合が３５質量％以上７５質量％以下であると、接着力と、タイヤコードの柔軟性とを両立できる。 When the proportion of the butadiene monomer in the monomer composition (a) is 35% by mass or more and 75% by mass or less, both the adhesive strength and the flexibility of the tire cord can be achieved.
ここで、接着力とは、接着剤用共重合体ラテックスを含有する接着剤組成物で処理されたタイヤコードとゴムとの接着力である。接着剤組成物については、後で説明する。接着力は、初期接着力および耐熱接着力である。初期接着力および耐熱接着力は、ＡＳＴＭ Ｄ２１３８−６７（Ｈ ＰＵＬＬ Ｔｅｓｔ）で測定される。 Here, the adhesive force is the adhesive force between the tire cord and the rubber treated with the adhesive composition containing the copolymer latex for the adhesive. The adhesive composition will be described later. The adhesive strength is the initial adhesive strength and the heat-resistant adhesive strength. The initial adhesive strength and heat resistant adhesive strength are measured by ASTM D2138-67 (H PULL Test).
タイヤコードの柔軟性とは、接着剤用共重合体ラテックスを含有する接着剤組成物で処理されたタイヤコードの柔軟性である。 The flexibility of the tire cord is the flexibility of the tire cord treated with an adhesive composition containing a copolymer latex for an adhesive.
単量体組成物（ａ）中のブタジエン単量体の割合が５０質量％以上７５質量％以下であると、タイヤコードの柔軟性を向上させることができる。なお、単量体組成物（ａ）中のブタジエン単量体の割合が３５質量％未満であると、初期接着力が低下し、タイヤコードの柔軟性が低下する。単量体組成物（ａ）中のブタジエン単量体の割合が７５質量％を超えると、耐熱接着力が低下する。 When the proportion of the butadiene monomer in the monomer composition (a) is 50% by mass or more and 75% by mass or less, the flexibility of the tire cord can be improved. If the proportion of the butadiene monomer in the monomer composition (a) is less than 35% by mass, the initial adhesive force is lowered and the flexibility of the tire cord is lowered. When the proportion of the butadiene monomer in the monomer composition (a) exceeds 75% by mass, the heat-resistant adhesive force is lowered.
また、単量体組成物（ａ）は、ビニルピリジン単量体を、１０質量％以上、好ましくは、１５質量％以上、３０質量％以下、好ましくは、２５質量％以下含有する。言い換えると、共重合体ラテックス（Ａ）中のラテックス粒子は、ビニルピリジン単量体に由来する構造単位を、１０質量％以上、好ましくは、１５質量％以上、３０質量％以下、好ましくは、２５質量％以下含有する。 In addition, the monomer composition (a) contains a vinylpyridine monomer in an amount of 10% by mass or more, preferably 15% by mass or more, 30% by mass or less, preferably 25% by mass or less. In other words, the latex particles in the copolymer latex (A) contain 10% by mass or more, preferably 15% by mass or more, and 30% by mass or less, preferably 25, of structural units derived from the vinylpyridine monomer. Contains less than% by mass.
単量体組成物（ａ）が、ビニルピリジン単量体を、１０質量％以上３０質量％以下含有していると、接着力と、タイヤコードの柔軟性との両立を図ることができる。一方、単量体組成物（ａ）中のビニルピリジン単量体の割合が１０質量％未満であると、初期接着力が低下する。単量体組成物（ａ）中のビニルピリジン単量体の割合が３０質量％を超えると、初期接着力および耐熱接着力が低下し、タイヤコードの柔軟性が低下する。 When the monomer composition (a) contains 10% by mass or more and 30% by mass or less of the vinylpyridine monomer, both the adhesive strength and the flexibility of the tire cord can be achieved. On the other hand, if the proportion of the vinylpyridine monomer in the monomer composition (a) is less than 10% by mass, the initial adhesive force is lowered. If the proportion of the vinylpyridine monomer in the monomer composition (a) exceeds 30% by mass, the initial adhesive strength and the heat-resistant adhesive strength are lowered, and the flexibility of the tire cord is lowered.
また、単量体組成物（ａ）は、スチレン単量体を、１０質量％以上、５５質量％以下、好ましくは、５０質量％以下、より好ましくは、３０質量％以下含有する。言い換えると、共重合体ラテックス（Ａ）中のラテックス粒子は、スチレン単量体に由来する構造単位を、例えば、１０質量％以上、５５質量％以下、好ましくは、５０質量％以下、より好ましくは、３０質量％以下含有する。 Further, the monomer composition (a) contains 10% by mass or more, 55% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less of the styrene monomer. In other words, the latex particles in the copolymer latex (A) contain structural units derived from the styrene monomer, for example, 10% by mass or more, 55% by mass or less, preferably 50% by mass or less, more preferably. , 30% by mass or less.
単量体組成物（ａ）中のスチレン単量体の割合が１０質量％以上５５質量％以下であると、接着力と、タイヤコードの柔軟性との両立を図ることができる。さらに、単量体組成物（ａ）中のスチレン単量体の割合が１０質量％以上３０質量％以下であると、タイヤコードの柔軟性を向上させることができる。一方、単量体組成物（ａ）中のスチレン単量体の割合が１０質量％未満であると、耐熱接着力が低下する。 When the proportion of the styrene monomer in the monomer composition (a) is 10% by mass or more and 55% by mass or less, both the adhesive strength and the flexibility of the tire cord can be achieved. Further, when the proportion of the styrene monomer in the monomer composition (a) is 10% by mass or more and 30% by mass or less, the flexibility of the tire cord can be improved. On the other hand, if the proportion of the styrene monomer in the monomer composition (a) is less than 10% by mass, the heat-resistant adhesive strength is lowered.
なお、単量体組成物（ａ）は、ブタジエン単量体、ビニルピリジン単量体およびスチレン単量体と共重合可能な他の単量体を含有してもよい。 The monomer composition (a) may contain a butadiene monomer, a vinylpyridine monomer, and another monomer copolymerizable with the styrene monomer.
他の単量体としては、例えば、アクリロニトリル、メタクリロニトリルなどのシアン化ビニル単量体、例えば、アクリル酸、メタクリル酸、イタコン酸、フマル酸、マレイン酸などのエチレン性不飽和カルボン酸単量体、例えば、メチルメタクリレート、エチルアクリレート、ブチルアクリレートなどのエチレン性不飽和カルボン酸アルキルエステル単量体、例えば、β−ヒドロキシエチルアクリレート、β−ヒドロキシエチルメタクリレートなどのエチレン性不飽和カルボン酸ヒドロキシアルキルエステル単量体、例えば、アクリルアミド、メタクリルアミドなどのアミド単量体などが挙げられる。単量体組成物（ａ）は、１種類の他の単量体を含有してもよい。単量体組成物（ａ）は、複数種類の他の単量体を含有してもよい。 Other monomers include, for example, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, for example, a single amount of ethylenically unsaturated carboxylic acid such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid. Body, eg, ethylenically unsaturated carboxylic acid alkyl ester monomers such as methyl methacrylate, ethyl acrylate, butyl acrylate, eg, ethylenically unsaturated carboxylic acid hydroxyalkyl esters such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate. Monomers such as amide monomers such as acrylamide and methacrylamide can be mentioned. The monomer composition (a) may contain one other monomer. The monomer composition (a) may contain a plurality of other types of monomers.
単量体組成物（ａ）は、好ましくは、ブタジエン単量体、ビニルピリジン単量体およびスチレン単量体からなる。 The monomer composition (a) preferably comprises a butadiene monomer, a vinylpyridine monomer and a styrene monomer.
共重合体ラテックス（Ａ）中のラテックス粒子の個数基準の平均粒子径は、例えば、５０ｎｍ以上、好ましくは、９０ｎｍ以上であり、例えば、２００ｎｍ以下、好ましくは、１５０ｎｍ以下である。 The average particle size based on the number of latex particles in the copolymer latex (A) is, for example, 50 nm or more, preferably 90 nm or more, and for example, 200 nm or less, preferably 150 nm or less.
平均粒子径は、共重合体ラテックスを四酸化オスミウムで染色後、透過型電子顕微鏡写真を撮影して、画像解析処理装置（装置名：旭化成（株）製ＩＰ−１０００ＰＣ）を用いて粒子１０００個の直径を計測し、個数平均によって測定される。 The average particle size is 1000 particles using an image analysis processing device (device name: IP-1000PC manufactured by Asahi Kasei Co., Ltd.) after dyeing the copolymer latex with osmium tetroxide and taking a transmission electron micrograph. The diameter of the particle is measured and measured by the number average.
（２）共重合体ラテックス（Ｂ）
共重合体ラテックス（Ｂ）は、単量体組成物（ｂ）の乳化重合物である。単量体組成物（ｂ）は、ブタジエン単量体と、スチレン単量体と、必要により、ビニルピリジン単量体とを含有する。言い換えると、共重合体ラテックス（Ｂ）中のラテックス粒子は、ブタジエン単量体に由来する構造単位と、スチレン単量体に由来する構造単位と、必要により、ビニルピリジン単量体に由来する構造単位とを有する。また、単量体組成物（ｂ）は、ブタジエン単量体、ビニルピリジン単量体およびスチレン単量体と共重合可能な他の単量体を含有してもよい。好ましくは、単量体組成物（ｂ）は、ブタジエン単量体、スチレン単量体、ビニルピリジン単量体からなる。
(2) Copolymer latex (B)
The copolymer latex (B) is an emulsion polymer of the monomeric composition (b). The monomer composition (b) contains a butadiene monomer, a styrene monomer, and if necessary, a vinylpyridine monomer. In other words, the latex particles in the copolymer latex (B) have a structural unit derived from a butadiene monomer, a structural unit derived from a styrene monomer, and, if necessary, a structure derived from a vinylpyridine monomer. Has a unit. Further, the monomer composition (b) may contain a butadiene monomer, a vinylpyridine monomer and another monomer copolymerizable with the styrene monomer. Preferably, the monomer composition (b) comprises a butadiene monomer, a styrene monomer, and a vinylpyridine monomer.
ブタジエン単量体、スチレン単量体、ビニルピリジン単量体、および他の単量体としては、それぞれ、共重合体ラテックス（Ａ）において挙げられた単量体と同じ単量体が挙げられる。 Examples of the butadiene monomer, the styrene monomer, the vinylpyridine monomer, and the other monomer include the same monomers as those mentioned in the copolymer latex (A).
単量体組成物（ｂ）は、ブタジエン単量体を、３質量％以上、好ましくは、１０質量％以上、より好ましくは、１５質量％以上、３０質量％以下含有する。言い換えると、共重合体ラテックス（Ｂ）のラテックス粒子は、ブタジエン単量体に由来する構造単位を、３質量％以上、好ましくは、１０質量％以上、より好ましくは、１５質量％以上、３０質量％以下含有する。 The monomer composition (b) contains 3% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, and 30% by mass or less of the butadiene monomer. In other words, the latex particles of the copolymer latex (B) contain 3% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, and 30% by mass of structural units derived from the butadiene monomer. % Or less.
単量体組成物（ｂ）中のブタジエン単量体の割合が３質量％以上３０質量％以下であると、接着力と、タイヤコードの柔軟性との両立を図ることができる。一方、単量体組成物（ｂ）中のブタジエン単量体の割合が３質量％未満であると、初期接着力が低下する。単量体組成物（ｂ）中のブタジエン単量体の割合が３０質量％を超えると、耐熱接着力が低下する。 When the ratio of the butadiene monomer in the monomer composition (b) is 3% by mass or more and 30% by mass or less, both the adhesive strength and the flexibility of the tire cord can be achieved. On the other hand, if the proportion of the butadiene monomer in the monomer composition (b) is less than 3% by mass, the initial adhesive force is lowered. When the proportion of the butadiene monomer in the monomer composition (b) exceeds 30% by mass, the heat-resistant adhesive force is lowered.
また、単量体組成物（ｂ）は、スチレン単量体を、例えば、５０質量％以上、好ましくは、５５質量％以上、例えば、８５質量％以下、好ましくは、８２質量％以下含有する。言い換えると、共重合体ラテックス（Ｂ）のラテックス粒子は、スチレン単量体に由来する構造単位を、例えば、５０質量％以上、好ましくは、５５質量％以上、例えば、８５質量％以下、好ましくは、８２質量％以下含有する。 Further, the monomer composition (b) contains, for example, 50% by mass or more, preferably 55% by mass or more, for example, 85% by mass or less, preferably 82% by mass or less of the styrene monomer. In other words, the latex particles of the copolymer latex (B) contain structural units derived from the styrene monomer, for example, 50% by mass or more, preferably 55% by mass or more, for example, 85% by mass or less, preferably 85% by mass or less. , 82% by mass or less.
単量体組成物（ｂ）中のスチレン単量体の割合が５０質量％以上８５質量％以下（すなわち、５０〜８５質量％）であると、接着力と、タイヤコードの柔軟性との両立を図ることができる。 When the proportion of the styrene monomer in the monomer composition (b) is 50% by mass or more and 85% by mass or less (that is, 50 to 85% by mass), both the adhesive strength and the flexibility of the tire cord are compatible. Can be planned.
また、単量体組成物（ｂ）は、ビニルピリジン単量体を含有する場合、ビニルピリジン単量体を、例えば、３０質量％以下、好ましくは、１５質量％以下、例えば、３質量％以上含有する。言い換えると、共重合体ラテックス（Ｂ）のラテックス粒子は、ビニルピリジン単量体に由来する構造単位を、例えば、３０質量％以下、好ましくは、１５質量％以下、例えば、３質量％以上含有する。 When the monomer composition (b) contains a vinylpyridine monomer, the vinylpyridine monomer is, for example, 30% by mass or less, preferably 15% by mass or less, for example, 3% by mass or more. contains. In other words, the latex particles of the copolymer latex (B) contain structural units derived from the vinylpyridine monomer, for example, 30% by mass or less, preferably 15% by mass or less, for example, 3% by mass or more. ..
単量体組成物（ｂ）中のビニルピリジン単量体の割合が３０質量％以下であると、接着力と、タイヤコードの柔軟性との両立を図ることができる。 When the proportion of the vinylpyridine monomer in the monomer composition (b) is 30% by mass or less, it is possible to achieve both the adhesive strength and the flexibility of the tire cord.
共重合体ラテックス（Ｂ）中のラテックス粒子の個数基準の平均粒子径は、共重合体ラテックス（Ａ）中のラテックス粒子の個数基準の平均粒子径と異なる。共重合体ラテックス（Ｂ）中のラテックス粒子の個数基準の平均粒子径は、共重合体ラテックス（Ａ）中のラテックス粒子の個数基準の平均粒子径よりも大きい。共重合体ラテックス（Ｂ）中のラテックス粒子の個数基準の平均粒子径は、１５０ｎｍ以上であり、例えば、２５０ｎｍ以下、好ましくは、２００ｎｍ以下、より好ましくは、１８０ｎｍ以下である。 The average particle size based on the number of latex particles in the copolymer latex (B) is different from the average particle size based on the number of latex particles in the copolymer latex (A). The average particle size based on the number of latex particles in the copolymer latex (B) is larger than the average particle size based on the number of latex particles in the copolymer latex (A). The average particle size based on the number of latex particles in the copolymer latex (B) is 150 nm or more, for example, 250 nm or less, preferably 200 nm or less, and more preferably 180 nm or less.
共重合体ラテックス（Ｂ）中のラテックス粒子の個数基準の平均粒子径が１５０ｎｍ以上であると、接着力と、タイヤコードの柔軟性との両立を図ることができる。一方、共重合体ラテックス（Ｂ）中のラテックス粒子の個数基準の平均粒子径が１５０ｎｍ未満であると、接着力（初期接着力および耐熱接着力）が低下する。 When the average particle diameter based on the number of latex particles in the copolymer latex (B) is 150 nm or more, it is possible to achieve both adhesive strength and flexibility of the tire cord. On the other hand, if the average particle size based on the number of latex particles in the copolymer latex (B) is less than 150 nm, the adhesive strength (initial adhesive strength and heat-resistant adhesive strength) decreases.
（３）共重合体ラテックス（Ａ）と共重合体ラテックス（Ｂ）との配合割合
接着剤用共重合体ラテックス中において、共重合体ラテックス（Ａ）の固形分と共重合体ラテックス（Ｂ）の固形分との総量に対する共重合体ラテックス（Ａ）の固形分の割合は、８５質量％以上、好ましくは、８８質量％以上、９５質量％以下、好ましくは、９２質量％以下である。
(3) Blending ratio of copolymer latex (A) and copolymer latex (B) In the copolymer latex for adhesives, the solid content of the copolymer latex (A) and the copolymer latex (B) The ratio of the solid content of the copolymer latex (A) to the total amount of the solid content of the copolymer latex (A) is 85% by mass or more, preferably 88% by mass or more, 95% by mass or less, and preferably 92% by mass or less.
接着剤用共重合体ラテックス中において、共重合体ラテックス（Ａ）の固形分と共重合体ラテックス（Ｂ）の固形分との総量に対する共重合体ラテックス（Ｂ）の固形分の割合は、５質量％以上、好ましくは、８質量％以上、１５質量％以下、好ましくは、１２質量％以下である。 In the copolymer latex for adhesives, the ratio of the solid content of the copolymer latex (B) to the total amount of the solid content of the copolymer latex (A) and the solid content of the copolymer latex (B) is 5. By mass% or more, preferably 8% by mass or more, 15% by mass or less, preferably 12% by mass or less.
共重合体ラテックス（Ａ）の固形分と共重合体ラテックス（Ｂ）の固形分との総量に対する共重合体ラテックス（Ｂ）の固形分の割合が５質量％以上１５質量％以下であると、接着力と、タイヤコードの柔軟性との両立を図ることができる。さらに、共重合体ラテックス（Ａ）の固形分と共重合体ラテックス（Ｂ）の固形分との総量に対する共重合体ラテックス（Ｂ）の固形分の割合が１０質量％以上１５質量％以下であると、タイヤコードの柔軟性を向上させることができる。一方、共重合体ラテックス（Ａ）の固形分と共重合体ラテックス（Ｂ）の固形分との総量に対する共重合体ラテックス（Ｂ）の固形分の割合が５質量％未満であると、耐熱接着力が低下する。共重合体ラテックス（Ａ）の固形分と共重合体ラテックス（Ｂ）の固形分との総量に対する共重合体ラテックス（Ｂ）の固形分の割合が１５質量％を超えると、タイヤコードの柔軟性が低下する。 When the ratio of the solid content of the copolymer latex (B) to the total amount of the solid content of the copolymer latex (A) and the solid content of the copolymer latex (B) is 5% by mass or more and 15% by mass or less. It is possible to achieve both adhesive strength and flexibility of the tire cord. Further, the ratio of the solid content of the copolymer latex (B) to the total amount of the solid content of the copolymer latex (A) and the solid content of the copolymer latex (B) is 10% by mass or more and 15% by mass or less. And, the flexibility of the tire cord can be improved. On the other hand, when the ratio of the solid content of the copolymer latex (B) to the total amount of the solid content of the copolymer latex (A) and the solid content of the copolymer latex (B) is less than 5% by mass, heat-resistant adhesion is performed. Power decreases. When the ratio of the solid content of the copolymer latex (B) to the total solid content of the copolymer latex (A) and the solid content of the copolymer latex (B) exceeds 15% by mass, the flexibility of the tire cord Decreases.
２．接着剤用共重合体ラテックスの製造
（１）共重合体ラテックスの製造
接着剤用共重合体ラテックスを製造するには、まず、共重合体ラテックス（Ａ）と共重合体ラテックス（Ｂ）とを製造する。
2. 2. Production of Copolymer Latex for Adhesive (1) Production of Copolymer Latex In order to produce copolymer latex for adhesive, first, the copolymer latex (A) and the copolymer latex (B) are mixed. To manufacture.
共重合体ラテックス（Ａ）を得るには、単量体組成物（ａ）を乳化重合する。共重合体ラテックス（Ｂ）を得るには、単量体組成物（ｂ）を乳化重合する。 To obtain the copolymer latex (A), the monomer composition (a) is emulsion-polymerized. To obtain the copolymer latex (B), the monomer composition (b) is emulsion-polymerized.
単量体組成物（ａ）または単量体組成物（ｂ）を乳化重合するには、例えば、単量体組成物（ａ）または単量体組成物（ｂ）と、水と、必要により乳化剤とを混合して、単量体組成物（ａ）または単量体組成物（ｂ）を乳化する。 In order to emulsion-polymerize the monomer composition (a) or the monomer composition (b), for example, the monomer composition (a) or the monomer composition (b), water, and optionally The monomer composition (a) or the monomer composition (b) is emulsified by mixing with an emulsifier.
乳化剤としては、例えば、ポリエチレングリコールのアルキルエステル型、アルキルフェニルエーテル型、アルキルエーテル型などのノニオン性界面活性剤、例えば、ロジン酸塩、脂肪酸塩、高級アルコールの硫酸エステル塩、アルキルベンゼンスルホン酸塩、アルキルジフェニルエーテルスルホン酸塩、脂肪族スルホン酸塩、脂肪族カルボン酸塩、ノニオン性界面活性剤の硫酸エステル塩、ナフタレンスルホン酸塩のホルマリン縮合物などのアニオン性界面活性剤が挙げられ、好ましくは、アニオン性界面活性剤が挙げられ、より好ましくは、アルキルベンゼンスルホン酸塩、ロジン酸塩、ナフタレンスルホン酸塩のホルマリン縮合物が挙げられる。乳化剤は、１種類であってもよく、複数種類であってもよい。 Examples of the emulsifier include nonionic surfactants such as alkyl ester type, alkyl phenyl ether type and alkyl ether type of polyethylene glycol, for example, rosinate, fatty acid salt, sulfate ester salt of higher alcohol, alkylbenzene sulfonate, etc. Anionic surfactants such as alkyldiphenyl ether sulfonates, aliphatic sulfonates, aliphatic carboxylic acid salts, sulfate ester salts of nonionic surfactants, formalin condensates of naphthalene sulfonates are preferred. Anionic surfactants are mentioned, more preferably formalin condensates of alkylbenzene sulfonates, rosinates, naphthalene sulfonates. The emulsifier may be one kind or a plurality of kinds.
乳化剤は、一括添加、連続添加、分割添加のいずれの方法で重合系へ添加されてもよく、重合時の安定性等を考慮して重合初期だけではなく、重合途中や重合終了後にも添加することができる。 The emulsifier may be added to the polymerization system by any of batch addition, continuous addition, and split addition, and is added not only at the initial stage of polymerization but also during or after the completion of polymerization in consideration of stability during polymerization and the like. be able to.
次に、単量体組成物（ａ）または単量体組成物（ｂ）の乳化物に、重合開始剤を添加する。 Next, a polymerization initiator is added to the monomer composition (a) or the emulsion of the monomer composition (b).
重合開始剤は、ラジカル重合開始剤であって、例えば、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウムなどの水溶性重合開始剤、例えば、クメンハイドロパーオキサイド、過酸化ベンゾイル、t−ブチルハイドロパーオキサイド、アセチルパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、１，１，３，３−テトラメチルブチルハイドロパーオキサイドなどの油溶性重合開始剤が挙げられる。好ましくは、水溶性重合開始剤としては、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウムが挙げられ、油溶性重合開始剤としては、クメンハイドロパーオキサイドが挙げられる。 The polymerization initiator is a radical polymerization initiator, for example, a water-soluble polymerization initiator such as potassium persulfate, sodium persulfate, ammonium persulfate, for example, cumene hydroperoxide, benzoyl peroxide, t-butyl hydroperoxide. , Acetyl peroxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutylhydroperoxide and other oil-soluble polymerization initiators. Preferably, the water-soluble polymerization initiator includes potassium persulfate, sodium persulfate, and ammonium persulfate, and the oil-soluble polymerization initiator includes cumene hydroperoxide.
なお、単量体組成物（ａ）または単量体組成物（ｂ）の乳化重合において、必要により、還元剤、連鎖移動剤、炭化水素系溶剤、その他の添加剤を添加してもよい。 In the emulsion polymerization of the monomer composition (a) or the monomer composition (b), a reducing agent, a chain transfer agent, a hydrocarbon solvent, or other additives may be added, if necessary.
還元剤としては、例えば、亜硫酸塩、亜硫酸水素塩、ピロ亜硫酸塩、亜ニチオン酸塩、ニチオン酸塩、チオ硫酸塩、ホルムアルデヒドスルホン酸塩、ベンズアルデヒドスルホン酸塩、例えば、Ｌ−アスコルビン酸、エリソルビン酸、酒石酸、クエン酸などのカルボン酸類およびその塩、例えば、デキストロース、サッカロースなどの還元糖類、例えば、ジメチルアニリン、トリエタノールアミンなどのアミン類が挙げられる。好ましくは、カルボン酸類およびその塩が挙げられ、より好ましくは、Ｌ−アスコルビン酸、エリソルビン酸が挙げられる。 Examples of the reducing agent include sulfite, hydrogen sulfite, pyrosulfite, nitionate, nithionate, thiosulfate, formaldehyde sulfonate, benzaldehyde sulfonate, for example, L-ascorbic acid and erythorbic acid. , Sulfonic acids such as tartrate and citrate and salts thereof, such as reducing saccharides such as dextrose and saccharose, and amines such as dimethylaniline and triethanolamine. Preferred examples include carboxylic acids and salts thereof, and more preferably L-ascorbic acid and erythorbic acid.
連鎖移動剤としては、例えば、ｎ−ヘキシルメルカプタン、ｎ−オクチルメルカプタン、ｔ−オクチルメルカプタン、ｎ−ドデシルメルカプタン、ｔ−ドデシルメルカプタン、ｎ−ステアリルメルカプタンなどのアルキルメルカプタン、例えば、ジメチルキサントゲンジサルファイド、ジイソプロピルキサントゲンジサルファイドなどのキサントゲン化合物、例えば、テトラメチルチウラムジスルフィド、テトラエチルチウラムジスルフィド、テトラメチルチウラムモノスルフィドなどのチウラム化合物、例えば、２，６−ジ−ｔ−ブチル−４−メチルフェノール、スチレン化フェノールなどのフェノール化合物、例えば、アリルアルコールなどのアリル化合物、例えば、ジクロルメタン、ジブロモメタン、四臭化炭素などのハロゲン化炭化水素化合物、例えば、α−ベンジルオキシスチレン、α−ベンジルオキシアクリロニトリル、α−ベンジルオキシアクリルアミドなどのビニルエーテル、例えば、トリフェニルエタン、ペンタフェニルエタン、アクロレイン、メタアクロレイン、チオグリコール酸、チオリンゴ酸、２−エチルヘキシルチオグリコレート、α−メチルスチレンダイマーなどが挙げられ、好ましくは、アルキルメルカプタンが挙げられ、より好ましくは、ｎ−オクチルメルカプタン、ｔ−ドデシルメルカプタンが挙げられる。連鎖移動剤は、１種類であってもよく、複数種類であってもよい。 Examples of the chain transfer agent include alkyl mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and n-stearyl mercaptan, for example, dimethylxanthogen disulfide and diisopropyl. Xanthogen compounds such as xanthogen disulfide, such as tetramethylthiuram disulfides, tetraethylthiuram disulfides, tetramethylthiuram monosulfides and other thiuram compounds, such as 2,6-di-t-butyl-4-methylphenol, styrated phenols, etc. Phenol compounds, eg, allyl compounds such as allyl alcohols, eg, halogenated hydrocarbon compounds such as dichloromethane, dibromomethane, carbon tetrabromide, eg α-benzyloxystyrene, α-benzyloxyacrylonitrile, α-benzyloxy. Vinyl ethers such as acrylamide, such as triphenylethane, pentaphenylethane, achlorein, metaacrolein, thioglycolic acid, thioapple acid, 2-ethylhexylthioglycolate, α-methylstyrene dimer and the like, preferably alkyl mercaptan. More preferably, n-octyl mercaptan and t-dodecyl mercaptan can be mentioned. The chain transfer agent may be one type or a plurality of types.
連鎖移動剤は、例えば、単量体組成物（ａ）１００質量部に対して、例えば、１０質量部以下、好ましくは、７質量部以下、例えば、０．０５質量部以上の割合で添加される。 The chain transfer agent is added, for example, at a ratio of, for example, 10 parts by mass or less, preferably 7 parts by mass or less, for example, 0.05 parts by mass or more, based on 100 parts by mass of the monomer composition (a). To.
炭化水素系溶剤としては、例えば、ペンタン、ヘキサン、ヘプタン、オクタン、シクロヘキサン、シクロヘプタンなどの飽和炭化水素、例えば、ペンテン、ヘキセン、ヘプテン、シクロペンテン、シクロヘキセン、シクロヘプテン、４−メチルシクロヘキセン、１−メチルシクロヘキセンなどの不飽和炭化水素などが挙げられ、好ましくは、シクロヘキセンが挙げられる。シクロへキセンは、低沸点で重合終了後に水蒸気蒸留などによって回収、再利用しやすく、環境負荷の観点から好適である。 Hydrocarbon-based solvents include saturated hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, and cyclohexene, such as penten, hexene, heptene, cyclopentene, cyclohexene, cyclohexene, 4-methylcyclohexene, and 1-methylcyclohexene. Unsaturated hydrocarbons such as, and preferably cyclohexene. Cyclohexene is suitable from the viewpoint of environmental load because it has a low boiling point and is easily recovered and reused by steam distillation or the like after the completion of polymerization.
その他の添加剤としては、例えば、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウムなどの電解質、例えば、ハイドロキノンなどの重合禁止剤、例えば、重合促進剤、例えば、キレート剤などが挙げられる。 Other additives include, for example, electrolytes such as sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, for example, polymerization inhibitors such as hydroquinone, for example, polymerization accelerators, for example, chelating agents and the like.
共重合体ラテックス（Ａ）または共重合体ラテックス（Ｂ）の製造において、重合方法は限定されず、バッチ重合、セミバッチ重合、シード重合などを適用できる。また、各種成分の添加方法も限定されず、一括添加方法、分割添加方法、連続添加方法、パワーフィード法などを適用できる。 In the production of the copolymer latex (A) or the copolymer latex (B), the polymerization method is not limited, and batch polymerization, semi-batch polymerization, seed polymerization and the like can be applied. Further, the method of adding various components is not limited, and a batch addition method, a divided addition method, a continuous addition method, a power feed method and the like can be applied.
（２）接着剤用共重合体ラテックスの調製
接着剤用共重合体ラテックスは、共重合体ラテックス（Ａ）と共重合体ラテックス（Ｂ）とが上記した割合で混合されることにより、調製される。なお、接着剤用共重合体ラテックスは、共重合体ラテックス（Ａ）と共重合体ラテックス（Ｂ）との混合物が水で希釈されることにより、調製されてもよい。
(2) Preparation of Copolymer Latex for Adhesive The copolymer latex for adhesive is prepared by mixing the copolymer latex (A) and the copolymer latex (B) in the above ratio. To. The copolymer latex for an adhesive may be prepared by diluting a mixture of the copolymer latex (A) and the copolymer latex (B) with water.
３．接着剤組成物
接着剤用共重合体ラテックスは、接着剤組成物に配合される。接着剤組成物は、好ましくは、ゴムとゴム補強繊維とを接着するために用いられる。
3. 3. Adhesive Composition Copolymer Latex for Adhesives is incorporated into the Adhesive Composition. The adhesive composition is preferably used to bond the rubber to the rubber reinforcing fibers.
ゴムとしては、特に限定されず、例えば、天然ゴム、ＳＢＲ、ＮＢＲ、クロロプレンゴム、ポリブタジエンゴム、ポリイソプレンゴム、それらの各種変性ゴムなどが挙げられる。また、ゴムには、例えば、充填剤、軟化剤、加硫剤、加硫促進剤などの公知の添加剤を配合することができる。 The rubber is not particularly limited, and examples thereof include natural rubber, SBR, NBR, chloroprene rubber, polybutadiene rubber, polyisoprene rubber, and various modified rubbers thereof. Further, known additives such as a filler, a softener, a vulcanizing agent, and a vulcanization accelerator can be added to the rubber.
ゴム補強繊維としては、例えば、ナイロン繊維、ポリエステル繊維、アラミド繊維などが挙げられる。また、これらの繊維の形態としては、特に限定されず、例えば、コード、ケーブル、織物、帆布、短繊維などが挙げられる。 Examples of the rubber reinforcing fiber include nylon fiber, polyester fiber, aramid fiber and the like. The form of these fibers is not particularly limited, and examples thereof include cords, cables, woven fabrics, canvases, and short fibers.
接着剤組成物は、接着剤用共重合体ラテックスとレゾルシン−ホルマリン樹脂とを含有する。言い換えると、接着剤組成物は、共重合体ラテックス（Ａ）と、共重合体ラテックス（Ｂ）と、レゾルシン−ホルマリン樹脂とを含有する。接着剤組成物は、接着剤用共重合体ラテックスとレゾルシン−ホルマリン樹脂とが混合されることにより、調製される。なお、接着剤組成物は、共重合体ラテックス（Ａ）と、共重合体ラテックス（Ｂ）と、レゾルシン−ホルマリン樹脂とが混合されることにより、調製されてもよい。 The adhesive composition contains a copolymer latex for an adhesive and a resorcin-formalin resin. In other words, the adhesive composition contains the copolymer latex (A), the copolymer latex (B), and the resorcin-formalin resin. The adhesive composition is prepared by mixing a copolymer latex for an adhesive and a resorcin-formalin resin. The adhesive composition may be prepared by mixing the copolymer latex (A), the copolymer latex (B), and the resorcin-formalin resin.
接着剤組成物中のレゾルシン−ホルマリン樹脂の割合は、固形分換算で、接着剤用共重合体ラテックス１００質量部に対して、例えば、５質量部以上、例えば、１００質量部以下、好ましくは、９０質量部以下である。 The ratio of the resorcin-formalin resin in the adhesive composition is, for example, 5 parts by mass or more, for example, 100 parts by mass or less, preferably 100 parts by mass or less, relative to 100 parts by mass of the copolymer latex for adhesive in terms of solid content. It is 90 parts by mass or less.
また、接着剤組成物には、必要に応じて、イソシアネート、ブロックドイソシアネート、エチレン尿素、２，６−ビス（２，４−ジヒドロキシフェニルメチル）−４−クロロフェノール、一塩化イオウとレゾルシンの縮合物およびレゾルシン−ホルマリン縮合物との混合物などの変性レゾルシン−ホルマリン樹脂、ポリエポキシド、変性ポリ塩化ビニル、カーボンブラックなどの接着助剤、充填剤、架橋剤、加硫剤、加硫促進剤などを含有してもよい。 Further, in the adhesive composition, if necessary, isocyanate, blocked isocyanate, ethylene urea, 2,6-bis (2,4-dihydroxyphenylmethyl) -4-chlorophenol, sulfur monochloride and vulcanization are condensed. Contains modified isocyanates such as isocyanates and mixtures with isocyanates-formalin condensates, adhesive aids such as polyepoxides, modified polyvinyl chlorides, carbon blacks, fillers, crosslinkers, vulcanizers, vulcanization accelerators, etc. You may.
そして、ゴムとゴム補強繊維とを接着するには、まず、接着剤組成物がゴム補強繊維に処理される。 Then, in order to bond the rubber and the rubber reinforcing fiber, first, the adhesive composition is treated into the rubber reinforcing fiber.
詳しくは、接着剤組成物は、例えば、ディッピングマシンなどによって接着剤組成物にゴム補強繊維が浸漬される。次に、接着剤組成物に浸漬されたゴム補強繊維は、例えば、１００℃以上、好ましくは、１１０℃以上、例えば、１５０℃以下、好ましくは、１３０℃以下で、例えば、８０秒以上、好ましくは、１００秒以上、例えば、２００秒以下、好ましくは、１５０秒以下、乾燥される。その後、乾燥されたゴム補強繊維は、例えば、１８０℃以上、好ましくは、２００℃以上、例えば、３００℃以下、好ましくは、２６０℃以下で、例えば、３０秒以上、好ましくは、５０秒以上、例えば、１００秒以下、好ましくは、８０秒以下、加熱（焼き付け）される。これにより、ゴム補強繊維に対する接着剤組成物の処理が完了する。 Specifically, in the adhesive composition, the rubber reinforcing fibers are immersed in the adhesive composition by, for example, a dipping machine. Next, the rubber reinforcing fiber immersed in the adhesive composition is, for example, 100 ° C. or higher, preferably 110 ° C. or higher, for example, 150 ° C. or lower, preferably 130 ° C. or lower, for example, 80 seconds or longer, preferably. Is dried for 100 seconds or longer, for example, 200 seconds or shorter, preferably 150 seconds or shorter. After that, the dried rubber reinforcing fiber is, for example, 180 ° C. or higher, preferably 200 ° C. or higher, for example, 300 ° C. or lower, preferably 260 ° C. or lower, for example, 30 seconds or longer, preferably 50 seconds or longer. For example, it is heated (baked) for 100 seconds or less, preferably 80 seconds or less. This completes the treatment of the adhesive composition on the rubber reinforcing fibers.
上記処理の後、接着剤組成物が処理されたゴム補強繊維とゴムとを接触させて、ゴムとゴム補強繊維とを加熱および加圧することにより、ゴムとゴム補強繊維とが、接着される。 After the above treatment, the rubber and the rubber reinforcing fiber are adhered by bringing the treated rubber reinforcing fiber and the rubber into contact with each other and heating and pressurizing the rubber and the rubber reinforcing fiber.
４．効果
上記した接着剤用共重合体ラテックスおよび接着剤組成物は、共重合体ラテックス（Ａ）と、共重合体ラテックス（Ｂ）とを含有する。共重合体ラテックス（Ａ）は、ブタジエン単量体３５質量％以上７５質量％以下と、ビニルピリジン単量体１０質量％以上３０質量％以下と、スチレン単量体１０質量％以上５５質量％以下とを含有する単量体組成物（ａ）の乳化重合物である。共重合体ラテックス（Ｂ）は、ブタジエン単量体３質量％以上３０質量％以下を含有する単量体組成物（ｂ）の乳化重合物である。そして、共重合体ラテックス（Ａ）の固形分と共重合体ラテックス（Ｂ）の固形分との総量に対する共重合体ラテックス（Ｂ）の固形分の割合が、５質量％以上１５質量％以下であり、共重合体ラテックス（Ｂ）の個数基準の平均粒子径が、１５０ｎｍ以上である。
4. Effect The above-mentioned copolymer latex for adhesives and the adhesive composition contain the copolymer latex (A) and the copolymer latex (B). The copolymer latex (A) contains 35% by mass or more and 75% by mass or less of the butadiene monomer, 10% by mass or more and 30% by mass or less of the vinylpyridine monomer, and 10% by mass or more and 55% by mass or less of the styrene monomer. It is an emulsion polymer of the monomer composition (a) containing. The copolymer latex (B) is an emulsion polymer of the monomer composition (b) containing 3% by mass or more and 30% by mass or less of the butadiene monomer. Then, the ratio of the solid content of the copolymer latex (B) to the total amount of the solid content of the copolymer latex (A) and the solid content of the copolymer latex (B) is 5% by mass or more and 15% by mass or less. Yes, the average particle size of the copolymer latex (B) based on the number is 150 nm or more.
そのため、接着力と、タイヤコードの柔軟性との両立を図ることができる。 Therefore, it is possible to achieve both the adhesive strength and the flexibility of the tire cord.
次に、本発明を、実施例および比較例に基づいて説明するが、本発明は、下記の実施例によって限定されるものではない。また、以下の記載において用いられる配合割合または含有割合の具体的数値は、上記の「発明を実施するための形態」において記載されている、それらに対応する配合割合または含有割合の上限値または下限値に代替することができる。 Next, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, the specific numerical values of the blending ratio or the content ratio used in the following description are the upper limit value or the lower limit of the blending ratio or the content ratio corresponding to them described in the above "mode for carrying out the invention". Can be replaced with a value.
１．共重合体ラテックス（Ａ）の製造
（１）合成例１、２および比較合成例１〜３
攪拌機付きオートクレーブに、水１３０質量部を仕込み、ナフタレンスルホン酸ナトリウムのホルマリン縮合物（乳化剤）１質量部、水酸化ナトリウム（電解質）０．５質量部およびロジン酸カリウム（乳化剤）４質量部を溶解させた。
1. 1. Production of Copolymer Latex (A) (1) Synthesis Examples 1 and 2 and Comparative Synthesis Examples 1 to 3
130 parts by mass of water was charged into an autoclave with a stirrer to dissolve 1 part by mass of formalin condensate (emulsifier) of sodium naphthalene sulfonate, 0.5 part by mass of sodium hydroxide (electrolyte) and 4 parts by mass of potassium rosinate (emulsifier). I let you.
次に、表１に示す単量体組成物（ａ）とｔ−ドデシルメルカプタン（連鎖移動剤）０．５５質量部とを加えて、乳化した。 Next, the monomer composition (a) shown in Table 1 and 0.55 parts by mass of t-dodecyl mercaptan (chain transfer agent) were added and emulsified.
その後、乳化物に過硫酸カリウム（重合開始剤）０．５質量部を加え、内温を５０℃に保ち、単量体組成物（ａ）を重合した。 Then, 0.5 part by mass of potassium persulfate (polymerization initiator) was added to the emulsion, the internal temperature was kept at 50 ° C., and the monomer composition (a) was polymerized.
重合転化率が９３％に到達した時点で、ハイドロキノン（重合禁止剤）０．１質量部を加えて重合を停止させ、その後、減圧蒸留により未反応単量体を除去して、合成例１、２および比較合成例１〜３の共重合体ラテックス（Ａ）を得た。 When the polymerization conversion rate reaches 93%, 0.1 part by mass of hydroquinone (polymerization inhibitor) is added to terminate the polymerization, and then the unreacted monomer is removed by vacuum distillation to remove the unreacted monomer. The copolymer latex (A) of No. 2 and Comparative Synthesis Examples 1 to 3 was obtained.
共重合体ラテックス（Ａ）中のラテックス粒子の平均粒子径を表１に示す。 Table 1 shows the average particle size of the latex particles in the copolymer latex (A).
（２）合成例３
攪拌機付きオートクレーブに、水１３５質量部を仕込み、ナフタレンスルホン酸ナトリウムのホルマリン縮合物１質量部、水酸化ナトリウム０．５質量部およびロジン酸カリウム５．０質量部を溶解させた。
(2) Synthesis example 3
135 parts by mass of water was charged into an autoclave equipped with a stirrer, and 1 part by mass of a formalin condensate of sodium naphthalene sulfonate, 0.5 part by mass of sodium hydroxide and 5.0 parts by mass of potassium loginate were dissolved.
次に、表１に示す１段目の単量体組成物（ａ）とｔ−ドデシルメルカプタン０．３質量部とを加えて、乳化した。 Next, the first-stage monomer composition (a) shown in Table 1 and 0.3 parts by mass of t-dodecyl mercaptan were added and emulsified.
その後、乳化物に過硫酸カリウム０．５質量部を加え、内温を５５℃に保ち、１段目の単量体組成物（ａ）を重合した。 Then, 0.5 part by mass of potassium persulfate was added to the emulsion, the internal temperature was kept at 55 ° C., and the first-stage monomer composition (a) was polymerized.
１段目の単量体組成物（ａ）の重合転化率が８２％に到達した時点で、表１に示す２段目の単量体組成物（ａ）とｔ−ドデシルメルカプタン０．２５質量部とを連続的に添加して、引き続き重合した。 When the polymerization conversion rate of the first-stage monomer composition (a) reaches 82%, the weight of the second-stage monomer composition (a) and t-dodecyl mercaptan shown in Table 1 is 0.25. Part was added continuously and the polymerization was continued.
重合転化率が９３％に到達した時点で、ハイドロキノン（重合禁止剤）０．１質量部を加えて重合を停止させ、その後、減圧蒸留により未反応単量体を除去して、合成例３の共重合体ラテックス（Ａ）を得た。 When the polymerization conversion rate reaches 93%, 0.1 part by mass of hydroquinone (polymerization inhibitor) is added to terminate the polymerization, and then the unreacted monomer is removed by vacuum distillation to remove the unreacted monomer in Synthesis Example 3. A copolymer latex (A) was obtained.
共重合体ラテックス（Ａ）中のラテックス粒子の平均粒子径を表１に示す。 Table 1 shows the average particle size of the latex particles in the copolymer latex (A).
２．共重合体ラテックス（Ｂ）の製造
攪拌機付きオートクレーブに、表２に示す量の水を仕込み、表２に示す量の乳化剤（具体的には、ドデシルベンゼンスルホン酸ナトリウムもしくはロジン酸ナトリウム）、電解質、重合開始剤（具体的には、過硫酸カリウム）を加えて、攪拌した。
2. 2. Production of Copolymer Latex (B) Add the amount of water shown in Table 2 to an autoclave with a stirrer, and add the amount of emulsifier (specifically, sodium dodecylbenzenesulfonate or sodium loginate), electrolyte, etc. shown in Table 2. A polymerization initiator (specifically, potassium persulfate) was added and stirred.
次いで、表２に示す量の単量体組成物（ｂ）、連鎖移動剤（具体的には、ｔ−ドデシルメルカプタン）、炭化水素系溶媒（具体的には、シクロヘキセン）を加えて、内温を表２に示す温度に保って重合し、重合転化率が９８％に達した時点で重合を終了した。 Next, the amount of the monomer composition (b) shown in Table 2, the chain transfer agent (specifically, t-dodecyl mercaptan), and the hydrocarbon solvent (specifically, cyclohexene) were added, and the internal temperature was increased. Was polymerized at the temperature shown in Table 2, and the polymerization was terminated when the polymerization conversion rate reached 98%.
次いで、水酸化ナトリウム水溶液を添加してｐＨ８に調整した後、水蒸気蒸留により未反応単量体等を除去して、合成例４〜７および比較合成例４〜７の共重合体ラテックス（Ｂ）を得た。 Next, after adjusting the pH to 8 by adding an aqueous sodium hydroxide solution, unreacted monomers and the like were removed by steam distillation to remove the copolymer latex (B) of Synthesis Examples 4 to 7 and Comparative Synthesis Examples 4 to 7. Got
共重合体ラテックス（Ｂ）中のラテックス粒子の平均粒子径を表２に示す。 Table 2 shows the average particle size of the latex particles in the copolymer latex (B).
３．接着剤用共重合体ラテックスの調製
共重合体ラテックス（Ａ）と共重合体ラテックス（Ｂ）とを表３、表４に示した配合割合で配合して混合し、各実施例および各比較例の接着剤用共重合体ラテックスを得た。
3. 3. Preparation of Copolymer Latex for Adhesive The copolymer latex (A) and the copolymer latex (B) were mixed in the blending ratios shown in Tables 3 and 4, and each Example and each comparative example were mixed. A copolymer latex for an adhesive was obtained.
４．接着剤組成物の調製
水２６０質量部に１０％水酸化ナトリウム４質量部を添加して攪拌した後、レゾルシン７．９質量部、および、３７％ホルマリン８．６質量部を加えて攪拌混合し、３０℃にて６時間熟成し、レゾルシン−ホルマリン樹脂を合成した。レゾルシン−ホルマリン樹脂の固形分（蒸発残分）は、４．１質量％であった。
4. Preparation of Adhesive Composition After adding 4 parts by mass of 10% sodium hydroxide to 260 parts by mass of water and stirring, 7.9 parts by mass of resorcin and 8.6 parts by mass of 37% formalin were added and mixed by stirring. , Aged at 30 ° C. for 6 hours to synthesize a resorcin-formalin resin. The solid content (evaporation residue) of the resorcin-formalin resin was 4.1% by mass.
次いで、各実施例および各比較例の接着剤用共重合体ラテックス１００質量部に、接着剤組成物の固形分濃度が１６．５質量％になるように水を添加して攪拌した後、レゾルシン−ホルマリン樹脂を全量（２８０．５質量部）と、２８％アンモニア水１１．４質量部とを添加して攪拌混合した。 Next, water was added to 100 parts by mass of the copolymer latex for adhesives of each Example and each comparative example so that the solid content concentration of the adhesive composition was 16.5% by mass, and the mixture was stirred and then resorcin. -The total amount (280.5 parts by mass) of the formalin resin and 11.4 parts by mass of 28% aqueous ammonia were added and mixed by stirring.
接着剤組成物中のレゾルシン−ホルマリン樹脂の割合は、固形分換算で、接着剤用共重合体ラテックス１００質量部に対して、１１．５質量部であった。 The ratio of the resorcin-formalin resin in the adhesive composition was 11.5 parts by mass with respect to 100 parts by mass of the copolymer latex for the adhesive in terms of solid content.
その後、２７％ブロックドイソシアネート分散液（明成化学工業（株）製ＳＵ−１２５Ｆ）４６．３質量部を添加して、３０℃にて４８時間熟成させ、接着剤組成物を得た。 Then, 46.3 parts by mass of a 27% blocked isocyanate dispersion (SU-125F manufactured by Meisei Chemical Industry Co., Ltd.) was added and aged at 30 ° C. for 48 hours to obtain an adhesive composition.
５．評価
（１）評価試料の作製
試験用シングルコードディッピングマシンを用いて、各実施例および各比較例の接着剤組成物に、前処理されたポリエステル・タイヤコード（１５００Ｄ／２）を浸漬し、１２０℃で１２０秒間乾燥した後、２４０℃で６０秒間、焼き付けた。
5. Evaluation (1) Preparation of evaluation sample Using a test single cord dipping machine, the pretreated polyester tire cord (1500D / 2) was dipped in the adhesive composition of each Example and each Comparative Example, and 120 After drying at ° C. for 120 seconds, it was baked at 240 ° C. for 60 seconds.
（２）タイヤコードの柔軟性の測定
各実施例および各比較例の接着剤組成物で処理されたポリエステル・タイヤコードを、１１ｃｍに裁断し、ハンドルオメーターで測定した。ハンドルオメーターのスリット幅は２０ｍｍに設定した。１０本の平均値を柔軟性とした。
(2) Measurement of Tire Cord Flexibility A polyester tire cord treated with the adhesive composition of each Example and each Comparative Example was cut into 11 cm and measured with a handle ometer. The slit width of the handle ometer was set to 20 mm. The average value of 10 pieces was taken as the flexibility.
結果を表３、表４に示す。 The results are shown in Tables 3 and 4.
（３）接着力の測定
各実施例および各比較例の接着剤組成物で処理されたポリエステル・タイヤコードを、下記の配合処方により準備されたゴムではさみ、１６０℃で２０分（初期接着力評価条件）、または、１７０℃で５０分（耐熱接着力評価条件）の条件で加硫プレスした。
(3) Measurement of Adhesive Strength The polyester tire cord treated with the adhesive composition of each example and each comparative example is sandwiched between rubbers prepared according to the following formulation, and at 160 ° C. for 20 minutes (initial adhesive strength). Vulcanization press was performed under the conditions of (evaluation conditions) or 170 ° C. for 50 minutes (heat-resistant adhesive strength evaluation conditions).
＜ゴム処方＞
天然ゴム ７０質量部
ＳＢＲゴム ３０質量部
ＦＥＦカーボン ４０質量部
プロセスオイル ４質量部
アンチゲンＲＤ（住友化学（株）社製） ２質量部
ステアリン酸 １．５質量部
亜鉛華 ５質量部
ジベンゾチアジルジスルフィド ０．９質量部
硫黄 ２．７質量部
なお、アンチゲンＲＤは、２，２，４−トリメチル−１，２−ジヒドロキノリン重合物である。
<Rubber prescription>
Natural rubber 70 parts by mass SBR rubber 30 parts by mass FEF carbon 40 parts by mass Process oil 4 parts by mass Antigen RD (manufactured by Sumitomo Chemical Co., Ltd.) 2 parts by mass Stealic acid 1.5 parts by mass Zinc oxide 5 parts by mass Dibenzothiazyl disulfide 0.9 parts by mass Sulfur 2.7 parts by mass Antigen RD is a 2,2,4-trimethyl-1,2-dihydroquinoline polymer.
ゴムとゴム補強繊維との初期接着力および耐熱接着力を、ＡＳＴＭ Ｄ２１３８−６７（Ｈ Ｐｕｌｌ Ｔｅｓｔ）に準じて測定した。 The initial adhesive force and the heat-resistant adhesive force between the rubber and the rubber reinforcing fiber were measured according to ASTM D2138-67 (H Pull Test).
結果を表３、表４に示す。 The results are shown in Tables 3 and 4.
Claims (5)
前記ブタジエン単量体３質量％以上３０質量％以下を含有する単量体組成物（ｂ）の乳化重合物である共重合体ラテックス（Ｂ）と
を含有し、
前記共重合体ラテックス（Ａ）の固形分と前記共重合体ラテックス（Ｂ）の固形分との総量に対する前記共重合体ラテックス（Ｂ）の固形分の割合が、５質量％以上１５質量％以下であり、
前記共重合体ラテックス（Ｂ）中のラテックス粒子の個数基準の平均粒子径が、１５０ｎｍ以上であることを特徴とする、接着剤用共重合体ラテックス。 A monomer composition containing 35% by mass or more and 75% by mass or less of a butadiene monomer, 10% by mass or more and 30% by mass or less of a vinylpyridine monomer, and 10% by mass or more and 55% by mass or less of a styrene monomer. The copolymer latex (A), which is the emulsion polymer of (a), and
It contains the copolymer latex (B) which is an emulsion polymer of the monomer composition (b) containing 3% by mass or more and 30% by mass or less of the butadiene monomer.
The ratio of the solid content of the copolymer latex (B) to the total amount of the solid content of the copolymer latex (A) and the solid content of the copolymer latex (B) is 5% by mass or more and 15% by mass or less. And
A copolymer latex for an adhesive, wherein the average particle size based on the number of latex particles in the copolymer latex (B) is 150 nm or more.
前記ブタジエン単量体３質量％以上３０質量％以下を含有する単量体組成物（ｂ）の乳化重合物である共重合体ラテックス（Ｂ）と、
レゾルシン−ホルマリン樹脂と
を含有し、
前記共重合体ラテックス（Ａ）の固形分と前記共重合体ラテックス（Ｂ）の固形分との総量に対する前記共重合体ラテックス（Ｂ）の固形分の割合が、５質量％以上１５質量％以下であり、
前記共重合体ラテックス（Ｂ）中のラテックス粒子の個数基準の平均粒子径が、１５０ｎｍ以上であることを特徴とする、接着剤組成物。 A monomer composition containing 35% by mass or more and 75% by mass or less of a butadiene monomer, 10% by mass or more and 30% by mass or less of a vinylpyridine monomer, and 10% by mass or more and 55% by mass or less of a styrene monomer. The copolymer latex (A), which is the emulsion polymer of (a), and
The copolymer latex (B), which is an emulsion polymer of the monomer composition (b) containing 3% by mass or more and 30% by mass or less of the butadiene monomer,
Contains resorcin-formalin resin,
The ratio of the solid content of the copolymer latex (B) to the total amount of the solid content of the copolymer latex (A) and the solid content of the copolymer latex (B) is 5% by mass or more and 15% by mass or less. And
An adhesive composition, wherein the average particle diameter based on the number of latex particles in the copolymer latex (B) is 150 nm or more.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019123495A JP7304753B2 (en) | 2019-07-02 | 2019-07-02 | Adhesive copolymer latex and adhesive composition |
| CN202080048544.9A CN114040931A (en) | 2019-07-02 | 2020-06-15 | Copolymer latex for adhesive and adhesive composition |
| KR1020217041783A KR20220029576A (en) | 2019-07-02 | 2020-06-15 | Copolymer Latex and Adhesive Composition for Adhesives |
| PCT/JP2020/023427 WO2021002181A1 (en) | 2019-07-02 | 2020-06-15 | Copolymer latex for adhesive and adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019123495A JP7304753B2 (en) | 2019-07-02 | 2019-07-02 | Adhesive copolymer latex and adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2021008575A true JP2021008575A (en) | 2021-01-28 |
| JP7304753B2 JP7304753B2 (en) | 2023-07-07 |
Family
ID=74100692
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2019123495A Active JP7304753B2 (en) | 2019-07-02 | 2019-07-02 | Adhesive copolymer latex and adhesive composition |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP7304753B2 (en) |
| KR (1) | KR20220029576A (en) |
| CN (1) | CN114040931A (en) |
| WO (1) | WO2021002181A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997013818A1 (en) * | 1995-10-13 | 1997-04-17 | Bridgestone Corporation | Adhesive composition and pneumatic tire |
| JP2009074182A (en) * | 2007-09-18 | 2009-04-09 | Bridgestone Corp | Method for producing adhesive composition for organic fiber cord, adhesive composition for organic fiber cord obtained by the method, reinforcement for tire, and tire using the same |
| WO2010055877A1 (en) * | 2008-11-12 | 2010-05-20 | 株式会社ブリヂストン | Adhesive composition |
| WO2011102003A1 (en) * | 2010-02-19 | 2011-08-25 | 日本エイアンドエル株式会社 | Copolymer latex for adhesives |
| JP2011231434A (en) * | 2010-04-28 | 2011-11-17 | Asahi Kasei Chemicals Corp | Adhesive composition for rubber and fiber |
Family Cites Families (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59113057A (en) * | 1982-12-21 | 1984-06-29 | Toyo Soda Mfg Co Ltd | Preparation of rubber-asphalt composition |
| JPH0921072A (en) * | 1995-06-30 | 1997-01-21 | Toray Ind Inc | Polyester fiber for reinforcing rubber and its production |
| JP3725923B2 (en) | 1995-11-20 | 2005-12-14 | 焼津水産化学工業株式会社 | Plant vitality agent |
| JP3978267B2 (en) * | 1997-09-24 | 2007-09-19 | 日本エイアンドエル株式会社 | Copolymer latex for rubber and polyester fiber adhesives |
| JP2001064112A (en) | 1999-08-26 | 2001-03-13 | Gun Ei Chem Ind Co Ltd | Plant activator and culture of crop using the plant activator |
| JP2002114610A (en) | 2000-04-14 | 2002-04-16 | Toyama Chem Co Ltd | Plant growth promoter |
| JP5000887B2 (en) * | 2005-12-08 | 2012-08-15 | 日本エイアンドエル株式会社 | Copolymer latex for rubber and fiber adhesives |
| JP4752614B2 (en) * | 2006-05-23 | 2011-08-17 | セントラル硝子株式会社 | Fiber coating solution and rubber reinforcing fiber using the same |
| JP5200279B2 (en) * | 2008-05-29 | 2013-06-05 | 日本エイアンドエル株式会社 | Method for producing copolymer latex for rubber and fiber adhesive |
| JP5238454B2 (en) * | 2008-10-29 | 2013-07-17 | 日本エイアンドエル株式会社 | Copolymer latex for rubber and polyester fiber adhesives |
| KR20110102003A (en) | 2010-03-10 | 2011-09-16 | 최기홍 | Illumimation apparatus |
| WO2011125224A1 (en) * | 2010-04-09 | 2011-10-13 | 日本エイアンドエル株式会社 | Copolymer latex for adhesive |
| JP5943418B2 (en) | 2012-01-24 | 2016-07-05 | 国立大学法人静岡大学 | Plant growth regulator |
| JP5715109B2 (en) * | 2012-11-06 | 2015-05-07 | 日本エイアンドエル株式会社 | Method for producing copolymer latex for adhesive |
| JP2014169403A (en) * | 2013-03-04 | 2014-09-18 | Nippon A&L Inc | Method for producing copolymer latex, and copolymer latex |
| JP2015048436A (en) | 2013-09-03 | 2015-03-16 | 公立大学法人福井県立大学 | Chitin inclusion derived from organism for improving disease resistance of plant, application method thereof, and manufacturing method thereof |
| CN107429002B (en) * | 2015-03-06 | 2020-01-24 | 株式会社普利司通 | Rubber composition and tire using same |
| EP3395824A4 (en) | 2015-12-18 | 2019-09-18 | Showa Denko K.K. | Method for manufacturing cellooligosaccharide |
| JP2017095352A (en) | 2017-01-12 | 2017-06-01 | 秀夫 草桶 | Chitin and/or chitosan, or chitin and/or chitosan-containing material, and fertilizer comprising culture of microorganism having chitin and/or chitosan decomposing ability, and method for producing the same and the like |
| JP7059119B2 (en) | 2017-06-26 | 2022-04-25 | 三洋化成工業株式会社 | Plant growth promoter |
-
2019
- 2019-07-02 JP JP2019123495A patent/JP7304753B2/en active Active
-
2020
- 2020-06-15 CN CN202080048544.9A patent/CN114040931A/en active Pending
- 2020-06-15 WO PCT/JP2020/023427 patent/WO2021002181A1/en active Application Filing
- 2020-06-15 KR KR1020217041783A patent/KR20220029576A/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997013818A1 (en) * | 1995-10-13 | 1997-04-17 | Bridgestone Corporation | Adhesive composition and pneumatic tire |
| JP2009074182A (en) * | 2007-09-18 | 2009-04-09 | Bridgestone Corp | Method for producing adhesive composition for organic fiber cord, adhesive composition for organic fiber cord obtained by the method, reinforcement for tire, and tire using the same |
| WO2010055877A1 (en) * | 2008-11-12 | 2010-05-20 | 株式会社ブリヂストン | Adhesive composition |
| WO2011102003A1 (en) * | 2010-02-19 | 2011-08-25 | 日本エイアンドエル株式会社 | Copolymer latex for adhesives |
| JP2011231434A (en) * | 2010-04-28 | 2011-11-17 | Asahi Kasei Chemicals Corp | Adhesive composition for rubber and fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| JP7304753B2 (en) | 2023-07-07 |
| KR20220029576A (en) | 2022-03-08 |
| CN114040931A (en) | 2022-02-11 |
| WO2021002181A1 (en) | 2021-01-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5481225B2 (en) | Copolymer latex for adhesive | |
| KR102141789B1 (en) | Producing method of copolymer latex for adhesives | |
| JP2004204147A (en) | Copolymer latex for adhesive between rubber and fiber | |
| WO2021002182A1 (en) | Copolymer latex for adhesive and adhesive composition | |
| JP5671188B1 (en) | Copolymer latex for adhesive and adhesive composition | |
| JP5000887B2 (en) | Copolymer latex for rubber and fiber adhesives | |
| JP2021008575A (en) | Copolymer latex for adhesive and adhesive composition | |
| JP5681169B2 (en) | Copolymer latex for adhesive | |
| JP4578077B2 (en) | Copolymer latex for rubber and fiber adhesives | |
| KR102166231B1 (en) | Copolymer latex for adhesive, and adhesive composition | |
| JPH1192730A (en) | Copolymer latex for adhesive for bonding rubber to polyester fiber | |
| JP4295961B2 (en) | Copolymer latex for rubber and fiber adhesives | |
| JP4578078B2 (en) | Copolymer latex for rubber and fiber adhesives | |
| JP4454053B2 (en) | Copolymer latex for rubber and fiber adhesives | |
| JP6113530B2 (en) | Copolymer latex for adhesive and adhesive composition | |
| JP2007186585A (en) | Latex composition for adhesive for ethylene-propylene rubber and fiber | |
| JPH1121414A (en) | Copolymer latex for adhesive used for adhering rubber to fiber | |
| JPH08209087A (en) | Adhesive composition between rubber and yarn | |
| TWI512068B (en) | Copolymer latex for adhesives | |
| JPH06184505A (en) | Adhesive composition for bonding rubber to fiber | |
| JPH11158289A (en) | Copolymer latex for rubber-to-fiber adhesive |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20220607 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20230322 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20230606 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20230627 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7304753 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |