JPH02151640A - Polymer latex composition and adhesive for rubber and fiber - Google Patents
Polymer latex composition and adhesive for rubber and fiberInfo
- Publication number
- JPH02151640A JPH02151640A JP30532188A JP30532188A JPH02151640A JP H02151640 A JPH02151640 A JP H02151640A JP 30532188 A JP30532188 A JP 30532188A JP 30532188 A JP30532188 A JP 30532188A JP H02151640 A JPH02151640 A JP H02151640A
- Authority
- JP
- Japan
- Prior art keywords
- latex
- weight
- copolymer latex
- copolymer
- rubber
- 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
- 229920000126 latex Polymers 0.000 title claims abstract description 96
- 239000004816 latex Substances 0.000 title claims abstract description 94
- 239000000853 adhesive Substances 0.000 title claims abstract description 42
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 42
- 229920000642 polymer Polymers 0.000 title claims abstract description 30
- 239000000835 fiber Substances 0.000 title claims abstract description 27
- 229920001971 elastomer Polymers 0.000 title claims abstract description 15
- 239000005060 rubber Substances 0.000 title claims abstract description 15
- 239000000203 mixture Substances 0.000 title claims description 33
- 239000000178 monomer Substances 0.000 claims abstract description 49
- 229920001577 copolymer Polymers 0.000 claims abstract description 44
- 150000001993 dienes Chemical class 0.000 claims abstract description 15
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 11
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 claims description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 abstract description 6
- 125000004076 pyridyl group Chemical group 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 description 17
- 229920000728 polyester Polymers 0.000 description 14
- 238000000034 method Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- -1 sulfopropyl Chemical group 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 239000012783 reinforcing fiber Substances 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 2
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229920006173 natural rubber latex Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 238000010058 rubber compounding Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- IRFSXVIRXMYULF-UHFFFAOYSA-N 1,2-dihydroquinoline Chemical compound C1=CC=C2C=CCNC2=C1 IRFSXVIRXMYULF-UHFFFAOYSA-N 0.000 description 1
- QOVCUELHTLHMEN-UHFFFAOYSA-N 1-butyl-4-ethenylbenzene Chemical compound CCCCC1=CC=C(C=C)C=C1 QOVCUELHTLHMEN-UHFFFAOYSA-N 0.000 description 1
- OUSXYCTXXLYBGJ-UHFFFAOYSA-N 1-ethenyl-2,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(C=C)C(C(C)C)=C1 OUSXYCTXXLYBGJ-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-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
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- YQUDMNIUBTXLSX-UHFFFAOYSA-N 2-ethenyl-5-ethylpyridine Chemical compound CCC1=CC=C(C=C)N=C1 YQUDMNIUBTXLSX-UHFFFAOYSA-N 0.000 description 1
- KBKNKFIRGXQLDB-UHFFFAOYSA-N 2-fluoroethenylbenzene Chemical compound FC=CC1=CC=CC=C1 KBKNKFIRGXQLDB-UHFFFAOYSA-N 0.000 description 1
- GQTFHSAAODFMHB-UHFFFAOYSA-N 2-prop-2-enoyloxyethanesulfonic acid Chemical compound OS(=O)(=O)CCOC(=O)C=C GQTFHSAAODFMHB-UHFFFAOYSA-N 0.000 description 1
- DPZYLEIWHTWHCU-UHFFFAOYSA-N 3-ethenylpyridine Chemical compound C=CC1=CC=CN=C1 DPZYLEIWHTWHCU-UHFFFAOYSA-N 0.000 description 1
- IZUVGRMMRWJVKU-UHFFFAOYSA-N 3-ethoxycarbonylbut-3-enoic acid Chemical compound CCOC(=O)C(=C)CC(O)=O IZUVGRMMRWJVKU-UHFFFAOYSA-N 0.000 description 1
- MHKLKWCYGIBEQF-UHFFFAOYSA-N 4-(1,3-benzothiazol-2-ylsulfanyl)morpholine Chemical compound C1COCCN1SC1=NC2=CC=CC=C2S1 MHKLKWCYGIBEQF-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-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
- 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
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- DZZKHFZCOSCMMU-UHFFFAOYSA-N CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O.S Chemical compound CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O.S DZZKHFZCOSCMMU-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001447 alkali salts 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
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical class CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- OOCCDEMITAIZTP-UHFFFAOYSA-N cinnamyl alcohol Chemical compound OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- REOJLIXKJWXUGB-UHFFFAOYSA-N mofebutazone Chemical group O=C1C(CCCC)C(=O)NN1C1=CC=CC=C1 REOJLIXKJWXUGB-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- AAYRWMCIKCRHIN-UHFFFAOYSA-N propane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CCCS(O)(=O)=O AAYRWMCIKCRHIN-UHFFFAOYSA-N 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はゴムと繊維の接着剤として好適な重合体ラテッ
クス組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a polymer latex composition suitable as an adhesive for rubber and fibers.
（従来の技術）
従来からポリアミド、ポリエステル等の補強用繊維とゴ
ムを接着するためにレゾルシノール−ホルムアルデヒド
樹脂とラテックスを主成分とする水性分散液に繊維を浸
漬処理して使用している。(Prior Art) Conventionally, fibers have been immersed in an aqueous dispersion containing resorcinol-formaldehyde resin and latex as main components in order to bond reinforcing fibers such as polyamide or polyester to rubber.
ラテックスとしてはブタジェン−ビニルピリジン−スチ
レン共重合体ラテックスもしくは該ラテックスとスチレ
ン−ブタジェン共重合体ラテックスあるいは天然ゴムラ
テックス等との混合ラテックスが一般に使用されている
。As the latex, butadiene-vinylpyridine-styrene copolymer latex or a mixed latex of this latex with styrene-butadiene copolymer latex, natural rubber latex, or the like is generally used.
自動車タイヤ、ベルト、ホース等におけるゴム補強用繊
維としてポリエステル繊維は低伸度であることが特徴で
あり、広く使用されているが、使用条件によっては繊維
が著しく劣化するためその用途に制約を受けている。す
なわち成型品のゴム中にチウラム系、スルフェンアミド
系、あるいはグアニジン系等の加硫促進剤やアミン系老
化防止剤あるいは天然ゴム等が配合されている場合には
、例えば自動車タイヤ製造時の長時間にわたる加硫工程
において、あるいは自動車タイヤの高速走行中において
ポリエステル繊維が劣化し補強用繊維としての性能が著
しく低下するという欠点を有しているためである。Polyester fiber is characterized by its low elongation and is widely used as a rubber reinforcing fiber for automobile tires, belts, hoses, etc. However, depending on the conditions of use, the fiber deteriorates significantly, so its use is limited. ing. In other words, if the rubber of the molded product contains vulcanization accelerators such as thiuram-based, sulfenamide-based, or guanidine-based, amine-based anti-aging agents, natural rubber, etc., This is because the polyester fibers deteriorate during the time-consuming vulcanization process or during high-speed running of automobile tires, and their performance as reinforcing fibers is significantly reduced.
この欠点を改善するために、■好ましい加硫促進剤、老
化防止剤などの選定によるゴム配合方法による改良、■
ポリエステル繊維に含まれる末端カルボキシル基量の低
減等によるポリエステル繊維自身の改良などが工夫され
てきたが、■の方法ではゴムの配合が制約され目的とす
る加硫ゴムと繊維の接着力（以下耐熱接着力という）の
改良が十分でなく、■の方法では繊維自身の熱劣化は改
良されるが耐熱接着力は改良されない。In order to improve this drawback, we have: (1) improved the rubber compounding method by selecting preferable vulcanization accelerators, anti-aging agents, etc.;
Efforts have been made to improve the polyester fiber itself, such as by reducing the amount of terminal carboxyl groups contained in the polyester fiber. (referred to as adhesive strength) is not sufficiently improved, and method (2) improves heat deterioration of the fiber itself but does not improve heat-resistant adhesive strength.
（発明が解決しようとする問題点）
本発明者等は上記の欠点を改善すべく鋭意検討した結果
、従来のビニルピリジン系重合体ラテックスに代えて、
エチレン系不飽和酸単量体を共重合したビニルピリジン
系重合体ラテックスを使用することにより耐熱接着力が
著しく改善されることを見い出した（特開昭６１−２６
６２９号公報）。(Problems to be Solved by the Invention) As a result of intensive studies to improve the above-mentioned drawbacks, the present inventors have found that, in place of the conventional vinyl pyridine polymer latex,
It has been discovered that heat-resistant adhesive strength is significantly improved by using a vinyl pyridine polymer latex copolymerized with an ethylenically unsaturated acid monomer (Japanese Patent Laid-Open No. 61-26
Publication No. 629).
さらに耐熱接着力を改善すべく検討を重ねた結果、エチ
レン系不飽和酸単量体を共重合したビニルピリジン系重
合体ラテックスと共役ジエン系単量体を多用した重合体
ラテックスを混合した重合体ラテックス組成物を使用す
ることにより目的が達成されることを見い出し、本発明
を完成するに到った。Furthermore, as a result of repeated studies to improve heat-resistant adhesive strength, we developed a polymer that is a mixture of a vinyl pyridine polymer latex copolymerized with an ethylenically unsaturated acid monomer and a polymer latex that uses a large amount of conjugated diene monomers. The inventors have discovered that the object can be achieved by using a latex composition, and have completed the present invention.
本発明の目的はタイヤ、ベルトホース等のゴム製品に、
特にポリエステル繊維が補強用に使用される場合にその
耐熱接着力が改良されると共に、ポリエステル以外の繊
維に対しても従来のビニルピリジン系ラテックスと同様
に使用することができるゴムと繊維との接着剤として特
に適した重合体ラテックス組成物及びゴムと繊維との接
着剤を提供することにある。The purpose of the present invention is to provide rubber products such as tires, belt hoses, etc.
In particular, when polyester fibers are used for reinforcement, their heat-resistant adhesive strength is improved, and they can also be used for fibers other than polyester in the same way as conventional vinyl pyridine latex. An object of the present invention is to provide a polymer latex composition particularly suitable as an adhesive for rubber and fibers.
（問題点を解決するための手段）
かくして、本発明によれば、共役ジエン系単量体４５〜
８５重量％、エチレン系不飽和酸単量体０．１〜２５１
ＥＩ％、ビニルピリジン１０〜４５重量％及びこれらと
共重合可能な他の単量体０〜３０重量％を乳化重合して
得られる共重合体ラテックスであって、該ラテックス粒
子表面のカルボキシル基の量が該共重合体１ｇ当り少な
くとも０．０１ミリ当量であることを特徴とする共重合
体ラテックス（イ）１３〜９５重量％と、共重合体ラテ
ックス（イ）以外の、共役ジエン単量体８０〜９５重量
％、及びこれと共重合可能な他の単量体５〜２０重量％
重量化重合して得られる共重合体ラテックス（ロ）５〜
８７重量％、とから成る重合体ラテックス組成物、及び
該重合体ラテックス組成物とレゾルシノール−ホルムア
ルデヒド樹脂を主成分とするゴムと繊維との接着剤が提
供される。(Means for Solving the Problems) Thus, according to the present invention, the conjugated diene monomers 45-
85% by weight, ethylenically unsaturated acid monomer 0.1-251
A copolymer latex obtained by emulsion polymerization of EI%, vinylpyridine 10 to 45% by weight, and other monomers copolymerizable with these 0 to 30% by weight, wherein the carboxyl groups on the surface of the latex particles are 13 to 95% by weight of a copolymer latex (a) characterized in that the amount is at least 0.01 milliequivalent per 1 g of the copolymer, and a conjugated diene monomer other than the copolymer latex (i) 80-95% by weight, and 5-20% by weight of other monomers copolymerizable with this
Copolymer latex obtained by weighted polymerization (b) 5~
and a rubber-to-fiber adhesive based on the polymer latex composition and a resorcinol-formaldehyde resin.
本発明の重合体ラテックス組成物は同一ラテックス粒子
にカルボキシル基と、ピリジル基が存在する共重合体ラ
テックス（イ）と、共重合体ラテックス（イ）以外の、
共役ジエン単量体８０〜９５重量％を含む共重合体ラテ
ックス（ロ）の混合物から成る点に特徴を有するもので
ある。The polymer latex composition of the present invention includes a copolymer latex (a) in which a carboxyl group and a pyridyl group are present in the same latex particles, and a copolymer latex other than the copolymer latex (i),
It is characterized in that it consists of a mixture of copolymer latex (b) containing 80 to 95% by weight of conjugated diene monomer.
本発明で使用する共重合体ラテックス（イ）は以下の単
量体を乳化重合して得られるものである。The copolymer latex (a) used in the present invention is obtained by emulsion polymerization of the following monomers.
共役ジエン単量体としては、例えば１，３−ブタジェン
、２−メチル−１，３−ブタジェン、２，３−ジメチル
−１，３−ブタジェン、２，３−ジメチル−１，３−ブ
タジェン、ハロゲン置換ブタジェンなどの脂肪族共役ジ
エン系単量体の１種もしくは２種以上が使用される。ビ
ニルピリジンとしては２−ビニルピリジンが望ましいが
、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、５−エチル−２−ビニルピリ
ジンなどの１種または２種以上で代替することができる
。Examples of the conjugated diene monomer include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, and halogen. One or more aliphatic conjugated diene monomers such as substituted butadiene are used. 2-vinylpyridine is preferable as vinylpyridine, but one or more of 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, 5-ethyl-2-vinylpyridine, etc. may be substituted. be able to.
エチレン系不飽和酸単量体としては、アクリル酸、メタ
クリル酸、クロトン酸、ケイ良酸、イタコン酸、フマル
酸、マレイン酸、ブテントリカルボン酸などの不飽和カ
ルボン酸；イタコン酸モノエチルエステル、フマル酸モ
ノブチルエステル、マレイン酸モノブチルエステルなど
の不飽和ジカルボン酸のモノアルキルエステル：アクリ
ル酸スルホエチルＮａ塩、タメクリル酸スルホプロピル
Ｎａ塩、アクリルアミドプロパンスルホン酸などの不飽
和スルホン酸又はそのアルカリ塩などの１種もしくは２
種以上が使用される。Examples of ethylenically unsaturated acid monomers include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, celiac acid, itaconic acid, fumaric acid, maleic acid, and butenetricarboxylic acid; itaconic acid monoethyl ester, fumaric acid, etc. Monoalkyl esters of unsaturated dicarboxylic acids such as acid monobutyl esters and maleic acid monobutyl esters: unsaturated sulfonic acids or their alkali salts such as sulfoethyl acrylate Na salt, sulfopropyl Na tamacrylate salt, acrylamide propane sulfonic acid, etc. Type 1 or 2
More than one species is used.
さらに所望により上記各単量体と共重合可能な他の単量
体を共重合させることができる。このような単量体とし
ては、例えばスチレン、α−メチルスチレン、２−メチ
ルスチレン、３−メチルスチレン、４−メチルスチレン
、２．４−ジイソプロピルスチレン、２Ｉ４−ジメチル
スチレン、４−を−ブチルスチレン、５−Ｌ−ブチル−
２−メチルスチレン、モノクロロスチレン、ジクロロス
チレン、モノフルオロスチレン、ヒドロキシメチルスチ
レンなどの芳香族ビニル化合物およびエチレン、プロピ
レン、アクリロニトリル、塩化ビニルなどの脂肪族ビニ
ル化合物などが例示され、これらの１種または２種以上
を共重合することができる。Furthermore, if desired, other monomers copolymerizable with each of the above monomers may be copolymerized. Examples of such monomers include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2I4-dimethylstyrene, and 4-butylstyrene. , 5-L-butyl-
Examples include aromatic vinyl compounds such as 2-methylstyrene, monochlorostyrene, dichlorostyrene, monofluorostyrene, and hydroxymethylstyrene, and aliphatic vinyl compounds such as ethylene, propylene, acrylonitrile, and vinyl chloride. More than one species can be copolymerized.
共重合体ラテックス（イ）の製造に用いられる共役ジエ
ン系単量体は通常全単量体に対しく以下も同様）４５〜
８５重量％で重量、この範囲をはずれると接着力が低下
する。望ましくは６０〜７５重量％である。The conjugated diene monomer used in the production of copolymer latex (a) is usually 45 to
The weight is 85% by weight, and the adhesive strength decreases outside this range. It is preferably 60 to 75% by weight.
エチレン系不飽和単量体の使用量は０．１〜２５重量％
であり、０．１重量体未満ではポリエステルタイヤコー
ドの耐熱接着力改良効果が小さく、また２５５重量を超
えても耐熱接着力はそれ以上に向上することなく、初期
接着力が低下するため好ましくない。望ましくは０．２
〜１２重量％であり、さらに望ましくは０．５〜８重量
％である。The amount of ethylenically unsaturated monomer used is 0.1 to 25% by weight.
If it is less than 0.1 weight, the effect of improving the heat resistant adhesive strength of polyester tire cord is small, and if it exceeds 255 weight, the heat resistant adhesive strength will not be improved any further and the initial adhesive strength will decrease, which is not preferable. . Preferably 0.2
~12% by weight, more preferably 0.5~8% by weight.
ビニルピリジン単量体の使用量は通常１０〜４５重量％
であり、この範囲をはずれると接着力は低下する。望ま
しくは１５〜４０重量％である。The amount of vinyl pyridine monomer used is usually 10 to 45% by weight.
, and outside this range, the adhesive strength decreases. It is preferably 15 to 40% by weight.
所望により、上記単量体と共重合可能な他の単量体を３
０重量％以下の範囲で使用することができる。If desired, 3 other monomers copolymerizable with the above monomers may be added.
It can be used in a range of 0% by weight or less.
共重合体ラテックス（ロ）の製造に用いる共役ジエン系
単量体（具体的例示は前記と同じ）は全単量体に対しく
以下も同様）通常８０〜９５重量％である。この範囲を
はずれると共重合体ラテックス（イ）と混合しても耐熱
接着力は改善されない。好ましくは８０〜９０重量％で
ある。The amount of the conjugated diene monomer (specific examples are the same as above) used in the production of the copolymer latex (b) is usually 80 to 95% by weight based on the total monomers. If it is outside this range, the heat-resistant adhesive strength will not be improved even if it is mixed with copolymer latex (a). Preferably it is 80 to 90% by weight.
共役ジエン系単量体と共重合させる他の単量体は特に限
定されず、共役ジエン系単量体以外の前記の他の単量体
の１種または２種以上が使用される。特に好ましいのは
芳香族ビニル化合物である。Other monomers to be copolymerized with the conjugated diene monomer are not particularly limited, and one or more of the above-mentioned other monomers other than the conjugated diene monomer are used. Particularly preferred are aromatic vinyl compounds.
使用割合は５〜２０重量％である。The proportion used is 5 to 20% by weight.
本発明の重合体ラテックス組成物は以上に説明した共重
合体ラテックス（イ）を１３〜９５重量％と共重合体ラ
テックス（ロ）を５〜８７重量％の割合で混合したもの
である。この混合割合をはずれると耐熱接着力及び初期
接着力は改善されない。The polymer latex composition of the present invention is a mixture of 13 to 95% by weight of the above-described copolymer latex (a) and 5 to 87% by weight of the copolymer latex (b). If the mixing ratio is outside this range, the heat-resistant adhesive strength and initial adhesive strength will not be improved.
好ましい共重合体ラテックス（イ）の使用割合は２０〜
９０重量％、さらに好ましくは３０〜９０重量％である
。The preferred proportion of copolymer latex (a) used is 20 to
It is 90% by weight, more preferably 30 to 90% by weight.
本発明の共重合体ラテックスは以上の単量体を乳化重合
することによって得られるが、共重合体ラテックス（イ
）の粒子表面のカルボキシル基の量が重合体１ｇ当り少
なくとも０．０１ミリ当量存在する点に特徴がある。０
．０１ミリ当量未満ではポリエステル繊維の耐熱接着力
は改良されない。The copolymer latex of the present invention is obtained by emulsion polymerization of the above monomers, and the amount of carboxyl groups on the particle surface of the copolymer latex (a) is at least 0.01 milliequivalent per 1 g of the polymer. It is characterized by the fact that 0
．． If the amount is less than 0.01 milliequivalent, the heat-resistant adhesive strength of the polyester fiber will not be improved.
望ましくは０．０２ミリ当量以上、さらに望ましくは０
．０５ミリ当量以上である。２．５ミリ当量以上になる
と耐熱接着力の改良効果は変わらなくなるが、ラテンク
スが増粘するため使いにくくなる。Desirably 0.02 milliequivalent or more, more preferably 0
．． 0.05 milliequivalent or more. When the amount exceeds 2.5 milliequivalents, the effect of improving heat-resistant adhesive strength remains the same, but the viscosity of the Latinx increases, making it difficult to use.
ラテックス粒子表面のカルボキシル基の定量は実施例記
載の方法によるものである。The amount of carboxyl groups on the surface of latex particles was determined by the method described in Examples.
ラテックス粒子表面にカルボキシル基が存在する本発明
の共重合体ラテックス（イ）の製造方法としては以下に
記載する二段重合方法が特に適している。The two-stage polymerization method described below is particularly suitable as a method for producing the copolymer latex (a) of the present invention in which carboxyl groups are present on the surface of the latex particles.
二段重合を行うには、先ず、第一段階の重合において、
使用する全単量体の内掛なくともエチレン系不飽和酸の
８０重量％以上及び共役ジエン系単量体の一部を含む全
単量体の２．５〜６０重量％重量る単量体を乳化重合す
る。エチレン系不飽和酸はその全使用量の８０重量％未
満の量では重合中の凝固物の発生を抑制するのが困難と
なり好ましくない。望ましくは９０重量％以上、さらに
望ましくは全量を第一段の重合で使用する。ビニルピリ
ジンは第一段の重合では重合中の凝固物の発生を抑制す
るうえで使用しないことが望ましいが、その全使用量の
５０重量％以下であれば使用しても構わない。To perform two-stage polymerization, first, in the first stage polymerization,
Monomers weighing at least 2.5 to 60% by weight of the total monomers used, including at least 80% by weight of ethylenically unsaturated acids and a part of conjugated diene monomers. emulsion polymerization. If the amount of ethylenically unsaturated acid is less than 80% by weight of the total amount used, it will be difficult to suppress the generation of coagulum during polymerization, which is not preferred. Desirably 90% by weight or more, more preferably the entire amount, is used in the first stage polymerization. Vinylpyridine is desirably not used in the first stage polymerization in order to suppress the generation of coagulum during polymerization, but it may be used as long as it is not more than 50% by weight of the total amount used.
第一段階の重合で使用する単量体の量が全単量体の２．
５重量％未満では重合反応時間が長くなり過ぎ、６０重
量％を超えると接着力が低下する。The amount of monomer used in the first stage polymerization is 2.2% of the total monomer.
If it is less than 5% by weight, the polymerization reaction time will be too long, and if it exceeds 60% by weight, the adhesive strength will decrease.
望ましくは５〜５０重量％である。It is preferably 5 to 50% by weight.
また第一段階の重合では単量体の重合体転化率は６０％
以上になっているのが望ましく、６０％未満では６０％
以上のものに比べて接着力が劣る。In addition, in the first stage of polymerization, the conversion rate of monomer to polymer was 60%.
It is desirable that it is above 60%, and if it is less than 60%, 60%
Adhesive strength is inferior to those mentioned above.
望ましくは８０％以上である。第二段階の重合では、引
き続き残りの単量体を添加し乳化重合を継続する。Desirably it is 80% or more. In the second stage of polymerization, the remaining monomers are subsequently added and emulsion polymerization is continued.
本発明においては第一段階および第二段階とも乳化重合
の様式自体は特に制限はなく、回分式乳化重合、半回分
式乳化重合、連続式乳化重合のいずれでもよく、重合温
度も低温、高温のいずれでもよい。又、重合に使用する
乳化剤、重合開始剤、分子量調整剤等も通常の乳化重合
に使用されるものでよく、特に制限されない。In the present invention, the mode of emulsion polymerization itself in the first and second stages is not particularly limited, and may be batch emulsion polymerization, semi-batch emulsion polymerization, or continuous emulsion polymerization, and the polymerization temperature can also be low or high temperature. Either is fine. Further, the emulsifier, polymerization initiator, molecular weight regulator, etc. used in the polymerization may be those used in ordinary emulsion polymerization, and are not particularly limited.
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
エーテル型等のノニオン性界面活性剤、高級アルコール
の硫酸エステル：アルキルベンゼンスルフォン酸塩、脂
肪族スルフォン酸塩等のアニオン性界面活性剤およびベ
タイン型等の両性界面活性剤の１種または２種以上が用
いられる。Examples of emulsifiers include nonionic surfactants such as alkyl esters, alkylphenyl ethers, and alkyl ethers of polyethylene glycol; anionic surfactants such as sulfuric esters of higher alcohols: alkylbenzene sulfonates, aliphatic sulfonates, etc. One or more types of amphoteric surfactants such as and betaine type are used.
重合開始剤としては例えば過硫酸カリウム、過硫酸アン
モニウム等の水溶性開始剤、あるいはレドックス系開始
剤、あるいは過酸化ベンゾイル等の油溶性開始剤が使用
できる。As the polymerization initiator, for example, a water-soluble initiator such as potassium persulfate or ammonium persulfate, a redox initiator, or an oil-soluble initiator such as benzoyl peroxide can be used.
分子量調整剤としてはメルカプタン類、キサントゲンジ
スルフィド類およびハロゲン化炭化水素類等が使用でき
る。As the molecular weight modifier, mercaptans, xanthogen disulfides, halogenated hydrocarbons, etc. can be used.
この様にして得られた本発明の共重合体ラテックス（イ
）はカルボキシル基とピリジル基とを含有し、カルボキ
シル基はラテックス粒子表面に存在している。The copolymer latex (a) of the present invention thus obtained contains a carboxyl group and a pyridyl group, and the carboxyl group is present on the surface of the latex particles.
共１重合体ラテックス（ロ）の製造方法には特別な方法
は必要とせず、従来から用いられている常法に従って製
造することが出来る。また、重合に使用する乳化剤、重
合開始剤、分子量調整剤等も通常の乳化重合に使用され
るものでよく、前記に示したものが使用される。The method for producing the comonopolymer latex (b) does not require any special method, and can be produced according to conventional methods. Further, the emulsifier, polymerization initiator, molecular weight regulator, etc. used in the polymerization may be those used in ordinary emulsion polymerization, and those shown above are used.
本発明においては共重合体ラテックス（イ）及び（ロ）
の平均粒子径は特に限定されないが、通常は０．０５Ｔ
ＬＩ１１以上である。In the present invention, copolymer latex (a) and (b)
Although the average particle size of is not particularly limited, it is usually 0.05T.
LI is 11 or higher.
本発明のゴムと繊維との接着剤は上記の重合体ラテック
スとレゾルシノール−ホルムアルデヒド樹脂を主成分と
するものである。The adhesive for rubber and fibers of the present invention is mainly composed of the above-mentioned polymer latex and resorcinol-formaldehyde resin.
本発明で使用するレゾルシノール−ホルムアルデヒド樹
脂は従来使用の該樹脂（例えば特開昭５５−１４２６３
５号公報開示のものなど）が使用でき、特に制限されな
い。又接着力を高めるために従来から使用されている２
、６−ビス（２，４−ジヒドロキシフェニルメチル）−
４−クロロフェノール組成物等の化合物との併用も差し
つかえない。The resorcinol-formaldehyde resin used in the present invention is a conventionally used resin (for example, JP-A-55-14263
(such as that disclosed in Japanese Patent No. 5) can be used, and there are no particular limitations. 2, which has been traditionally used to increase adhesive strength.
, 6-bis(2,4-dihydroxyphenylmethyl)-
It may also be used in combination with compounds such as 4-chlorophenol compositions.
本発明の接着剤は通常、本発明の重合体ラテックス組成
物固形分１００重量部に対してレゾルシノール−ホルム
アルデヒド樹脂を１０〜４０重量部（乾燥重量）混合し
たものが使用される。The adhesive of the present invention is usually a mixture of 10 to 40 parts by weight (dry weight) of a resorcinol-formaldehyde resin based on 100 parts by weight of the solid content of the polymer latex composition of the present invention.
また本発明の接着剤中の本発明の重合ラテックスの一部
をスチレン−ブタジェン共重合体ゴムラテックスおよび
その変性ラテックス、アクリロニトリル−ブタジェン共
重合体ゴムラテックスおよびその変性ラテックス、天然
ゴムラテックス等のうちの１種または２種以上で代替す
ることができる。In addition, a part of the polymer latex of the present invention in the adhesive of the present invention may be substituted with styrene-butadiene copolymer rubber latex and its modified latex, acrylonitrile-butadiene copolymer rubber latex and its modified latex, natural rubber latex, etc. One type or two or more types can be substituted.
本発明の接着剤の使用方法については特に制限は無く、
既知のレゾルシノール−ホルムアルデヒド−重合体ラテ
ックス系接着剤と同様にして適用することができる。通
常本発明の接着剤組成物を１０〜３０重量％の水溶液と
して、ゴム製品の製造時に、所望の形態の繊維を浸漬処
理し、乾燥、熱処理した後、未加硫ゴム配合物と共に成
形し、加硫することによって繊維とゴムを接着すること
ができる。また予め本発明の接着剤組成物を塗布した所
望形態の繊維を用いることもできる。There are no particular restrictions on the method of using the adhesive of the present invention.
It can be applied in the same manner as known resorcinol-formaldehyde-polymer latex adhesives. Usually, the adhesive composition of the present invention is made into an aqueous solution of 10 to 30% by weight, and during the production of rubber products, fibers of a desired form are immersed, dried, and heat treated, and then molded together with an unvulcanized rubber compound. Fibers and rubber can be bonded together by vulcanization. Further, it is also possible to use fibers in a desired form coated with the adhesive composition of the present invention in advance.
本発明の接着剤組成物が適用できる繊維も特に制限はな
く、レーヨン繊維、ポリエステル繊維、ポリアミド繊維
、アラミド繊維等に使用することができる。これらの繊
維は織物、コード、糸等いずれの形態であっても良い。The fibers to which the adhesive composition of the present invention can be applied are not particularly limited, and can be used for rayon fibers, polyester fibers, polyamide fibers, aramid fibers, and the like. These fibers may be in any form such as woven fabric, cord, or thread.
（発明の効果）
本発明の重合体ラテックスはゴムと繊維との接着剤用に
使用すると従来の該接着剤と同一の使用処方で該接着剤
を使用した場合より改善された接着力を与え、特にポリ
エステル繊維との耐熱接着力が改善されるので、タイヤ
、ベルト、ホース等の製造に使用することができる。(Effects of the Invention) When the polymer latex of the present invention is used as an adhesive between rubber and fibers, it provides an adhesive force that is improved compared to when the adhesive is used in the same formulation as the conventional adhesive. In particular, since the heat-resistant adhesive strength with polyester fibers is improved, it can be used for manufacturing tires, belts, hoses, etc.
（実施例）
実施例１
攪拌機付きオートクレーブに水１５０部、エチレンジア
ミンテトラ酢酸の４ナトリウム塩０．１部、ラウリル硫
酸ソーダ５部、重炭酸ソーダ０．５部、ｔ−ドデシルメ
ルカプタン０．５部、過硫酸カリウム０．３部と共に第
１表に示す単量体■を同表に記載の重量比率で合計１０
０部仕込み、回転混合しながら６０°Ｃで１５時間反応
を行なった。転化率はいずれも６０％以上に達した。こ
れを種ラテツクスとする。続けて攪拌機付きオートクレ
ーブに種ラテツクスを４０部仕込み、エチレンジアミン
テトラ酢酸の４ナトリウム塩０．１部、ラウリル硫酸ソ
ーダ２部、乞−ドデシルメルカプタン０．５部、過硫酸
カリウム０．３部、水金計量１５０部になるように仕込
み、回転混合しながら６０°Ｃで反応させた。重合転化
率９５％に達した時にハイドロキノン０．０５部を添加
して反応を停止し、減圧にして未反応単量体を除去し、
共重合ラテックス（イ）を得た。(Example) Example 1 In an autoclave with a stirrer, 150 parts of water, 0.1 part of tetrasodium salt of ethylenediaminetetraacetic acid, 5 parts of sodium lauryl sulfate, 0.5 part of sodium bicarbonate, 0.5 part of t-dodecylmercaptan, and persulfuric acid. A total of 10 monomers shown in Table 1, together with 0.3 parts of potassium, were added at the weight ratios listed in the same table.
0 part was added, and the reaction was carried out at 60°C for 15 hours with rotational mixing. The conversion rates reached 60% or more in all cases. This is called seed latex. Subsequently, 40 parts of seed latex was charged into an autoclave equipped with a stirrer, and 0.1 part of tetrasodium salt of ethylenediaminetetraacetic acid, 2 parts of sodium lauryl sulfate, 0.5 part of dodecyl mercaptan, 0.3 part of potassium persulfate, and water were added. A total of 150 parts was added, and the mixture was reacted at 60°C with rotational mixing. When the polymerization conversion rate reached 95%, 0.05 part of hydroquinone was added to stop the reaction, and unreacted monomers were removed by reducing the pressure.
A copolymer latex (a) was obtained.
ラテックス粒子表面のカルボキシル基およびピリジル基
の分析はＫａｗａｇｕｃｈｉの方法（Ｊ、Ａｐｐｌ、Ｐ
ｏ１３１゜Ｓｃｉ、、Ｖｏｌ ２６．２０１５〜２０２
２．１９８１年）を参考にして次のように行なった。Analysis of carboxyl groups and pyridyl groups on the surface of latex particles was performed using the method of Kawaguchi (J, Appl, P.
o131゜Sci,, Vol 26.2015-202
2.1981), the following procedure was carried out.
ラテックスをセルロース製チューブに入れ、流水中に１
週間浸漬し、ラテックスセラム中の溶解物質を透析精製
する。次にポリオキシエチレンラウリルエーテルをラテ
ックス固形分の１／１０量添加する。この試料を固形分
濃度４％、固形分２ｇ相当量精秤し、０．５Ｎ塩酸を３
ｇ添加してマグネチックスクーラーで攪拌する。１５分
間経過後に、０．ＩＮ水酸化ナトリウム水溶液で滴定し
、電気型導度曲線を画き、屈曲点よりラテックス粒子表
面のカルボキシル基およびピリジル基の量を求めた。Place the latex in a cellulose tube and place it under running water for 1 hour.
After soaking for a week, the dissolved substances in the latex serum are purified by dialysis. Next, polyoxyethylene lauryl ether is added in an amount of 1/10 of the solid content of the latex. An amount of this sample with a solid content concentration of 4% and an equivalent of 2 g of solid content was accurately weighed, and 0.5N hydrochloric acid was added with 3
g and stir with a magnetic cooler. After 15 minutes, 0. Titration was performed with an IN aqueous sodium hydroxide solution, an electrical conductivity curve was drawn, and the amounts of carboxyl groups and pyridyl groups on the surface of the latex particles were determined from the inflection point.
ラテックス粒径はレーザー光源散乱法〔英国マルバーン
（Ｍａｌｖｅｒｎ）社製モデル４６００ ）によって測
定した。以上の結果を第１表に併記した。The latex particle size was measured by a laser light source scattering method (Model 4600, manufactured by Malvern, UK). The above results are also listed in Table 1.
次に、攪拌機付きオートクレーブに水１５０部、エチレ
ンジアミンテトラ酢酸の４ナトリウム塩０、１部、ラウ
リル硫酸ソーダ５部、重炭酸ソーダ０．５部、ｔ−ドデ
シルメルカプタン０．５部、加硫酸カリウム０．３部と
共に第１表記載の単量体を合計１００部仕込み、回転混
合しなから６０°Ｃで反応させた。重合添加率９５％に
達した時に冷却して反応を停止し、未反応単量体を除去
し共重合体ラテックス（ロ）を得た。Next, in an autoclave equipped with a stirrer, 150 parts of water, 0.1 part of tetrasodium salt of ethylenediaminetetraacetic acid, 5 parts of sodium lauryl sulfate, 0.5 parts of sodium bicarbonate, 0.5 parts of t-dodecylmercaptan, and 0.3 parts of potassium sulfate. A total of 100 parts of the monomers shown in Table 1 were added together with the following parts, and the mixture was mixed by rotation and reacted at 60°C. When the polymerization addition rate reached 95%, the reaction was stopped by cooling, and unreacted monomers were removed to obtain a copolymer latex (b).
第 １ 表 注）（１）ケルプール法による窒素量より求めた。Part 1 table Note) (1) Determined from the nitrogen content using the Kelpool method.
（２）ラテックス粒子表面のピリジル基量（ミリ当量／
ｇ共重合体）を表わす。(2) Amount of pyridyl groups on the surface of latex particles (milliequivalent/
g copolymer).
共重合体ラテックス（イ）を５０重量％と共重合体ラテ
ックス（ロ）を５０重量％を混合し、重合体ラテックス
組成物Ａを製造した。A polymer latex composition A was prepared by mixing 50% by weight of copolymer latex (a) and 50% by weight of copolymer latex (b).
比較例として市販のビニルピリジン系重合体ラテックス
（ビニルピリジン／スチレン／ブタジェン＝ １５／１
５／７０重量％）５０重量％と市販のスチレン−ブタジ
ェン共重合体ラテックス（スチレン／ブタジェン＝３０
／７０重量％）５０重量％を混合して重合体ラテックス
組成物Ｂを作成した。As a comparative example, commercially available vinylpyridine polymer latex (vinylpyridine/styrene/butadiene = 15/1
5/70% by weight) and commercially available styrene-butadiene copolymer latex (styrene/butadiene = 30
/70% by weight) to prepare a polymer latex composition B.
重合体ラテックス組成物Ａ、Ｂ及び共重合体ラテックス
（イ）のそれぞれを用いてポリエステルタイヤコードと
天然ゴム配合物（第２表）との加硫接着を行った。Polyester tire cords and natural rubber compounds (Table 2) were vulcanized and bonded using each of the polymer latex compositions A and B and the copolymer latex (a).
レゾルシノール１６．６部、ホルマリン水溶液（３７％
濃度）１４．６部、水酸化ナトリウム１．３部を水３３
３．５部に溶解し、撹拌下に２５“Ｃで２時間反応させ
た。次いでこの中へ上記のラテックス１００部を添加し
、攪拌下に２５°Ｃで２００時間反応せた。次いでバル
カボンドＥ （Ｖｕｌｎａｘ社製品Ｖｕｌｃａｂｏｎｄ
Ｅ”）を３０部添加した。この水溶液を固形分濃度２０
％に調整した後試験用シングルコードディッピングマシ
ンを用いてポリエステルタイヤコード（１５０００／２
）を浸漬処理した。浸漬処理後２４０°Ｃで１分間熱
処理を行った。この処理されたポリエステルタイヤコー
ドを第２表の配合処理により製造した天然ゴム配合物で
はさみ、プレス加硫した。該タイヤコードとゴムとの接
着力をＴ接着力試験法により評価した（測定温度２０°
Ｃ１相対湿度６５％、２４本の引き抜き試験）。結果を
第３表に示す。16.6 parts of resorcinol, formalin aqueous solution (37%
Concentration) 14.6 parts, 1.3 parts of sodium hydroxide and 33 parts of water
Then, 100 parts of the above latex was added thereto and reacted for 200 hours at 25°C with stirring.Next, VALKABOND E (Vulnax product Vulcabond
30 parts of E") were added. This aqueous solution was mixed with a solid content of 20 parts.
After adjusting the polyester tire cord (15000/2
) was immersed. After the immersion treatment, heat treatment was performed at 240°C for 1 minute. This treated polyester tire cord was sandwiched between natural rubber compounds prepared according to the compounding process shown in Table 2 and press-vulcanized. The adhesion between the tire cord and rubber was evaluated by the T adhesion test method (measurement temperature: 20°
C1 relative humidity 65%, 24 pull test). The results are shown in Table 3.
第２表
天然ゴム
亜 鉛 華
ステアリン酸
硫 黄
ＰＥＦカーボンブラック
プロセス油
ゴム配合処方
Ｎ−オキシジエチレン−２−
ベンゾチアジルスルフェンアミ
ド
２．２．４− ）ジメチル−１，２〜
ジヒドロキノリン重合物
１００部
２．５
■
０．２
本発明の共重合体ラテックス（イ）のみを用いた場合に
は従来の重合体ラテックス（共重合体ラテックス組成物
Ｂ）を使用した場合と初期接着力は同等であるが、耐熱
接着力は改善される。Table 2 Natural Rubber Zinc Sulfur Flower Stearate Sulfur PEF Carbon Black Process Oil Rubber Compounding Formula N-oxydiethylene-2-benzothiazylsulfenamide 2.2.4-) Dimethyl-1,2~ Dihydroquinoline polymer 100 parts 2.5 ■ 0.2 When only the copolymer latex (A) of the present invention is used, the initial adhesive strength is equivalent to that when a conventional polymer latex (copolymer latex composition B) is used. However, the heat-resistant adhesive strength is improved.
ところが、本発明の重合ラテックス組成物（共重合体ラ
テックス組成物Ａ）を使用した場合には初期接着力も改
善されると共に耐熱接着力も著しく改善される。However, when the polymerized latex composition of the present invention (copolymer latex composition A) is used, the initial adhesive strength is improved and the heat-resistant adhesive strength is also significantly improved.
実施例２
共重合体ラテックス（ロ）として第４表記載のものを使
用する以外は実施例１と同じ条件で重合体ラテックス組
成物Ｃ−Ｌを製造した。Example 2 A polymer latex composition CL was produced under the same conditions as in Example 1, except that the copolymer latex (b) shown in Table 4 was used.
これらの重合体ラテックス組成物を用い、実施例１と同
じ処方で接着剤を調整し、実施例１と同じ加硫接着試験
を行った。結果を第５表に示す。Using these polymer latex compositions, adhesives were prepared with the same formulation as in Example 1, and the same vulcanization adhesion test as in Example 1 was conducted. The results are shown in Table 5.
第
表
実施例３
レゾルシノール１１部、ホルマリン水溶液（３７％濃度
）１６．２部、水酸化ナトリウム０．３部を水２３８．
５部に溶解し、攪拌下に２５℃で６時間反応させた。次
いでこの中へ実施例１の重合体ラテックス組成物Ａ又は
Ｂ１００部を添加し、攪拌下に２５℃で２００時間反応
せた。この水溶液を固型分濃度１５％に調整した後、試
験用シングルコードディッピングマシンを用いてナイロ
ン６タイヤコード（１２６０ｄ／２）を浸漬処理した。Table 1 Example 3 11 parts of resorcinol, 16.2 parts of formalin aqueous solution (37% concentration), and 0.3 parts of sodium hydroxide were added to 238 parts of water.
The mixture was dissolved in 5 parts and reacted at 25° C. for 6 hours with stirring. Next, 100 parts of the polymer latex composition A or B of Example 1 was added thereto, and the mixture was reacted at 25° C. for 200 hours with stirring. After adjusting this aqueous solution to a solid content concentration of 15%, a nylon 6 tire cord (1260 d/2) was dipped using a single cord dipping machine for testing.
浸漬後、２００°Ｃで１分間熱処理を行った。接着力試
験は実施例１と同じ方法により行った。結果を第６表に
示す。After dipping, heat treatment was performed at 200°C for 1 minute. The adhesion test was conducted in the same manner as in Example 1. The results are shown in Table 6.
Claims (1)
不飽和酸単量体０．１〜２５重量％、ビニルピリジン１
０〜４５重量％及びこれらと共重合可能な他の単量体０
〜３０重量％を乳化重合して得られる共重合体ラテック
スであって、該ラテックス粒子表面のカルボキシル基の
量が該共重合体１ｇ当り少なくとも０．０１ミリ当量で
あることを特徴とする共重合体ラテックス（イ）１３〜
９５重量％と、共重合体ラテックス（イ）以外の、共役
ジエン単量体８０〜９５重量％、及びこれと共重合可能
な他の単量体５〜２０重量％を乳化重合して得られる共
重合体ラテックス（ロ）５〜８７重量％、とから成る重
合体ラテックス組成物。 ２、請求項第１記載の重合体ラテックス組成物とレゾル
シノール−ホルムアルデヒド樹脂を主成分とするゴムと
繊維との接着剤。[Claims] 1. Conjugated diene monomer 45-85% by weight, ethylenically unsaturated acid monomer 0.1-25% by weight, vinylpyridine 1.
0 to 45% by weight and other monomers copolymerizable with these 0
A copolymer latex obtained by emulsion polymerization of ~30% by weight, characterized in that the amount of carboxyl groups on the surface of the latex particles is at least 0.01 milliequivalent per 1 g of the copolymer. Combined latex (a) 13~
obtained by emulsion polymerization of 95% by weight, 80 to 95% by weight of a conjugated diene monomer other than copolymer latex (a), and 5 to 20% by weight of other monomers copolymerizable with this. A polymer latex composition comprising 5 to 87% by weight of copolymer latex (b). 2. An adhesive between rubber and fibers, the main component of which is the polymer latex composition according to claim 1 and a resorcinol-formaldehyde resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30532188A JPH0757829B2 (en) | 1988-12-02 | 1988-12-02 | Polymer latex composition and rubber-fiber adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30532188A JPH0757829B2 (en) | 1988-12-02 | 1988-12-02 | Polymer latex composition and rubber-fiber adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02151640A true JPH02151640A (en) | 1990-06-11 |
| JPH0757829B2 JPH0757829B2 (en) | 1995-06-21 |
Family
ID=17943702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30532188A Expired - Fee Related JPH0757829B2 (en) | 1988-12-02 | 1988-12-02 | Polymer latex composition and rubber-fiber adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0757829B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02206630A (en) * | 1989-02-06 | 1990-08-16 | Nippon Zeon Co Ltd | Latex composition, adhesive composition, bonding method and composite of rubber and fiber |
-
1988
- 1988-12-02 JP JP30532188A patent/JPH0757829B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02206630A (en) * | 1989-02-06 | 1990-08-16 | Nippon Zeon Co Ltd | Latex composition, adhesive composition, bonding method and composite of rubber and fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0757829B2 (en) | 1995-06-21 |
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