JPS62230807A - Production of copolymer latex - Google Patents
Production of copolymer latexInfo
- Publication number
- JPS62230807A JPS62230807A JP7408486A JP7408486A JPS62230807A JP S62230807 A JPS62230807 A JP S62230807A JP 7408486 A JP7408486 A JP 7408486A JP 7408486 A JP7408486 A JP 7408486A JP S62230807 A JPS62230807 A JP S62230807A
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- weight
- latex
- monomers
- vinylpyridine
- 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 34
- 239000004816 latex Substances 0.000 title claims abstract description 34
- 229920001577 copolymer Polymers 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000000178 monomer Substances 0.000 claims abstract description 54
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 22
- 239000002253 acid Substances 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 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 150000001993 dienes Chemical class 0.000 claims abstract description 9
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 8
- 230000000379 polymerizing effect Effects 0.000 claims 2
- 239000000853 adhesive Substances 0.000 abstract description 15
- 230000001070 adhesive effect Effects 0.000 abstract description 15
- 239000000835 fiber Substances 0.000 abstract description 15
- 229920001971 elastomer Polymers 0.000 abstract description 10
- 239000005060 rubber Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 6
- -1 2-vinylpyridine Chemical compound 0.000 abstract description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 abstract description 4
- 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
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 abstract description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 abstract description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 abstract 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 abstract 1
- 239000000839 emulsion Substances 0.000 abstract 1
- 229920000728 polyester Polymers 0.000 description 16
- 239000000203 mixture Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- 244000043261 Hevea brasiliensis Species 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229920003052 natural elastomer Polymers 0.000 description 5
- 229920001194 natural rubber Polymers 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
- 239000000243 solution Substances 0.000 description 5
- 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 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
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- 150000001875 compounds Chemical class 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
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000007523 nucleic acids Chemical class 0.000 description 3
- 102000039446 nucleic acids Human genes 0.000 description 3
- 108020004707 nucleic acids Proteins 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000012783 reinforcing fiber Substances 0.000 description 3
- 238000010058 rubber compounding Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 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
- 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
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 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
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 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
- 238000007654 immersion Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 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
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-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
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 1
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-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
- YZBOVSFWWNVKRJ-UHFFFAOYSA-M 2-butoxycarbonylbenzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1C([O-])=O YZBOVSFWWNVKRJ-UHFFFAOYSA-M 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
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-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
- 239000004952 Polyamide Substances 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
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001298 alcohols Chemical class 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
- 125000000129 anionic group Chemical group 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 compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 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
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 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
- 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
- KETWBQOXTBGBBN-UHFFFAOYSA-N hex-1-enylbenzene Chemical compound CCCCC=CC1=CC=CC=C1 KETWBQOXTBGBBN-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 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
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 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
- 229920006173 natural rubber latex Polymers 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 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
- 238000007586 pull-out test Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 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
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 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
- 241000894007 species Species 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 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
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 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
- 230000007306 turnover Effects 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (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エチレン系
不飽和酸とビニルピリジンとを共重合させた共重合体ラ
テックスの製造方法に関するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for producing a copolymer latex made by copolymerizing an ethylenically unsaturated acid and vinylpyridine, which is suitable as an adhesive for rubber and fibers. It is.
（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ｎＩｉ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 nIi solution 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−ビニルビリジン−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
テフクス等との混合ラテ）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.
自動車用タイヤ、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
が著るしく劣化するためその用途に制約を受けている。Polyester fiber is characterized by its low elongation and is widely used as rubber reinforcing fiber in automobile tires, belts, hoses, etc. However, depending on the conditions of use, the fiber deteriorates significantly, which limits its use. Is receiving.
すなわち成形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。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、あるいは■ポリエ
ステル繊維をあらかじめカルボキシル基を含有する化合
物で処理する方法（例えば、特開昭５５−１６６２３５
号公報）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物性が得られないと
同時に、長時間加硫後の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、■や■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善され
ない。本発明者等は■の知見に基づき繊維とゴムの接着
に用いられる改良された重合体ラテックスを開発すべく
鋭意研究を重ねた結果、本発明に到達した。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, or natural rubber, for example, during long-term manufacturing of automobile tires. This is because polyester fibers have the disadvantage of deteriorating during the vulcanization process or during high-speed running of automobile tires, and their performance as reinforcing fibers is significantly reduced. In order to improve this drawback, it is possible to improve the rubber compounding method by selecting preferable vulcanization accelerators, anti-aging agents, etc., improve the polyester fiber itself by reducing the amount of terminal carboxyl groups contained in the polyester fiber, or A method in which polyester fibers are treated in advance with a compound containing a carboxyl group (for example, Japanese Patent Application Laid-Open No. 55-166235
However, method (2) restricts the rubber compounding and does not provide the desired physical properties of the vulcanized rubber. However, methods (1) and (2) improve the thermal deterioration of the fibers themselves, but do not improve the heat-resistant adhesive strength. The inventors of the present invention have conducted intensive research based on the knowledge in (1) to develop an improved polymer latex for use in adhering fibers and rubber, and as a result, they have arrived at the present invention.
（発明が解決しようとする問題点）
本発明の目的はタイヤ、ヘルド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エン系ラテックスと同
様に使用することができる繊維とゴムとの７接着剤とし
て特に適した共重合体ラテックスを提供することにある
。(Problems to be Solved by the Invention) The purpose of the present invention is to provide rubber products such as tires and heald hoses.
In particular, when polyester fiber is used for reinforcement, its heat-resistant adhesive strength is improved, and it can also be used for fibers other than polyester in the same way as conventional vinylpyridine latex. 7. It is an object of the present invention to provide a copolymer latex particularly suitable as an adhesive.
（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０．１〜２５重
量％、ビニルピリジン１０〜４５重量％及びこれらと共
重合可能な単量体０〜３０重量％を乳化重合して得られ
る共重合体ラテ・ノクスであって・
本共重合体ラテックスを製造するに際し、（ａ）少なく
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％
に当る単量体を重合転化率が少なくとも６０％に達する
まで７重合し、（ｂ）次いで、残りの単量体を重合する
ことを特徴とする共重合体ラテックスの製造方法が提供
される。(Means for Solving the Problems) Thus, according to the present invention, the conjugated diene monomers 45-
A copolymer obtained by emulsion polymerization of 85% by weight, 0.1 to 25% by weight of ethylenically unsaturated acid monomers, 10 to 45% by weight of vinylpyridine, and 0 to 30% by weight of monomers copolymerizable with these. When producing the present copolymer latex, (a) at least 80% by weight of the ethylenically unsaturated acid and a portion of the conjugated diene monomer, 2.5-60% by weight
There is provided a method for producing a copolymer latex, characterized in that (b) the remaining monomers are polymerized seven times until the polymerization conversion reaches at least 60%.
本発明の共重合体ラテックスの製造方法は重合を二段に
分けて実施する点に特徴を存するものである。The method for producing copolymer latex of the present invention is characterized in that the polymerization is carried out in two stages.
本発明の共重合体ラテックスの製造に使用される単量体
のうち共役ジエン系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、り以上が使用される。Among the monomers used in the production of the copolymer latex of the present invention, examples of conjugated diene monomers include 1,3-butadiene, 2-methyl-1,3-butadiene, and 2.3-butadiene.
Dimethyl-1,3-butadiene is used.
全単量体中の共役ジエン系単量体の使用量は通常４５〜
８５重量％であり、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 amount of conjugated diene monomer used in all monomers is usually 45~
It is 85% by weight, and if it is out of this range, the adhesive strength decreases. It is preferably 60 to 75% by weight.
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、メタ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 ester and maleic acid monobutyl ester; unsaturated sulfonic acids or their alkali salts such as sulfoethyl acrylate Na salt, sulfopropyl Na methacrylate salt, acrylamide propane sulfonic acid, etc. Type 1 or 2
More than one species is used.
全単量体中のエチレン系不飽和酸単量体の使用量は０．
１〜２５重量％であり、０．１重量％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
２５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。The amount of ethylenically unsaturated acid monomer used in all monomers is 0.
If it is less than 0.1% by weight, the effect of improving the heat-resistant adhesive strength of polyester tire cord is small, and even if it exceeds 25% by weight, the initial adhesive strength will not improve any further. This is not preferable because it lowers the temperature.
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 content is preferably 0.2 to 12% by weight, more preferably 0.5 to 8% by weight.
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。As vinylpyridine, 2-vinylpyridine is preferable, but it can be replaced with one or more of 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, 5-ethyl-2-vinylpyridine, etc. be able to.
ビニルピリジン単量体の使用量は全単量体中通常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 vinylpyridine monomer used is usually 10 to 10% of the total monomers.
The amount is 45% by weight, and the adhesive strength decreases outside this range. It is preferably 15 to 40% by weight.
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、２，４−ジメチル
スチレン、４−１−ブチルスチレン、５−ｔ−７’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、塩化ヒニルナトの脂肪族ビ
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, 2,4-dimethylstyrene, 4-1- Aromatic vinyl compounds such as butylstyrene, 5-t-7' thyl-2-methylstyrene, monochlorostyrene, dichlorostyrene, monofluorostyrene, hydroxymethylstyrene, and aliphatic vinyl compounds such as ethylene, propylene, acrylonitrile, and hinylnatochloride, etc. are exemplified, and one or more of these can be copolymerized.
全単量体中の使用量は３０重量％以下である。The amount used in the total monomers is 30% by weight or less.
本発明においては上記の単量体を用い二段重合により共
重合体ラテックスを製造する。In the present invention, a copolymer latex is produced by two-stage polymerization using the above monomers.
先ず、第１段の重合においては全単量体の２．５〜６０
重星％に当る単量体混合物を重合するが、この混合物中
にはエチレン系不飽和酸の８０重量％以上及び使用量は
特に制限はないが重合の安全性のうえから共役ジエン系
単量体の一部を含ませることが必要である。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。First, in the first stage polymerization, 2.5 to 60 of the total monomers are
Polymerizes a monomer mixture of 80% by weight or more, and this mixture contains at least 80% by weight of ethylenically unsaturated acids, and although there is no particular restriction on the amount used, from the viewpoint of polymerization safety, conjugated diene monomers are used. It is necessary to include parts of the body. 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.
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、第１段の重合で使用する単量体混合
物中のエチレン系不飽和酸の量が１０重四％未満の場合
にはビニルピリジンは核酸と等モル以下の債まで、また
核酸の量が単量体混合物中１０重量％以上の場合には核
酸のモル数の半分以下の量で使用することは構わない。Desirably 90% by weight or more, more preferably the entire amount, is used in the first stage polymerization. Vinylpyridine is preferably not used in the first stage polymerization in order to suppress the generation of coagulum during polymerization, but the amount of ethylenically unsaturated acid in the monomer mixture used in the first stage polymerization is If the amount is less than 10% by weight, vinylpyridine is used in an amount equal to or less than the equimolar amount of the nucleic acid, and if the amount of nucleic acid is 10% by weight or more in the monomer mixture, it is used in an amount of less than half the number of moles of the nucleic acid. It doesn't matter what you do.
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。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。In addition, in the first stage of polymerization, the monomer to polymer conversion rate was 60
% or more is desirable; less than 60% is 60%.
Adhesive strength is inferior to those with % or more. Preferably 80%
That's all. 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；アルキルヘ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, sulfuric esters of higher alcohols; anionic interfaces such as alkylhenzenesulfonates, aliphatic sulfonates, etc. One or more of an active agent and an amphoteric surfactant such as a 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.
（発明の効果）
この様にして得られた本発明の共重合体ラテフクスはカ
ルボキシル基とピリジル基とを含有する。(Effects of the Invention) The copolymer latefux of the present invention thus obtained contains a carboxyl group and a pyridyl group.
その結果本発明の共重合体ラテックスをゴムと繊維、特
にポリエステル繊維との接着剤として使用した場合には
従来の重合体ラテックスの使用に比して極めて著しい耐
熱接着力の改善が図られる。As a result, when the copolymer latex of the present invention is used as an adhesive between rubber and fibers, particularly polyester fibers, the heat-resistant adhesive strength is significantly improved compared to the use of conventional polymer latexes.
（実施例）
以下に実施例を挙げて本発明をさらに具体的に説明する
。なお、実施例、比較例中の部数及び％はとくに断りの
ないかぎり乾燥重量基準である。(Example) The present invention will be described in more detail with reference to Examples below. The numbers and percentages in Examples and Comparative Examples are based on dry weight unless otherwise specified.
実施例１
撹拌機付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、【−ドデシルメル
カプクン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１００
部仕込み、回転混合しながら６０℃で１５時間反応を行
なった。転回率はいずれも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、ｔ−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℃で反応させた０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Ａ及びＢを得た。Example 1 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 part of sodium bicarbonate, 0.5 part of [-dodecylmercapkun, 0 potassium persulfate] .1st part along with 3rd part
A total of 100 monomers shown in the table at the weight ratios shown in the table.
The reaction was carried out at 60° C. for 15 hours with rotational mixing. The turnover rate reached over 60% in all cases. This is called seed latex. Next, 40 parts of the seed latex was placed in an autoclave equipped with a stirrer, and 0.1 part of tetrasodium salt of ethylenediaminetetraacetic acid and 2 parts of sodium lauryl sulfate were added.
1 part, 0.5 part of t-dodecyl mercaptan, 0.3 part of potassium persulfate, and 150 parts of water were mixed and reacted at 60°C with rotational mixing.
When the reaction temperature reached 0.05 part of hydroquinone, the reaction was stopped, and the unreacted monomers were removed under reduced pressure to obtain copolymer latexes A and B.
第１表
ラテックスＡ及びＢ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との加硫接着を行った。Vulcanization adhesion between a polyester tire cord and a natural rubber compound was performed using each of Latex A and B in Table 1.
レゾルシノール１６６６部、ホルマリン水？８ ？＆（
３７％濃度）１４．６部、水酸化ナトリウム１．３部を
水３３３．５部に溶解し、撹拌下に２５℃で２時間反応
させた０次いでこの中へラテックスΔ又はラテックス８
１００部を添加し、攪拌下に２５℃で２００時間反応せ
た０次いでバルカボンドＥＣｌＣｌ Ｖｕｌｎａｘ社製
品ＶｕｌｃａｂｏｎｄＥ）を３０部添加した。この水溶
液を固型分濃度２０％に調整した後試験用シングルコー
ドディフピングマシンを用いてポリエステルタイヤコー
ド（１５００Ｄ／２）を浸漬処理した。浸漬処理後２４
０℃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℃、相対温度６５％、２４本の引き抜き試
験）、結果を第３表に示す。1666 parts of resorcinol, formalin water? 8? &(
37% concentration) 14.6 parts and 1.3 parts of sodium hydroxide were dissolved in 333.5 parts of water and reacted with stirring at 25°C for 2 hours.
Then, 30 parts of Vulcabond EClCl (Vulcabond E), a product of Vulnax, were added. After adjusting this aqueous solution to a solid content concentration of 20%, a polyester tire cord (1500D/2) was immersed using a single cord diffing machine for testing. 24 days after soaking
Heat treatment was performed at 0°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 using the T adhesion test method (
The results are shown in Table 3.
第２表 ゴム配合処方
天 然 ゴ ム １００部亜 鉛
華 ５ステアリン酸
２硫 黄
２．５ＦＥＦカーボンブランク
４５プロセス油 ５
実施例２
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
４表に示す単量体■を同表記載の重量の５倍ｆｆ１（１
００部）仕込み、回転混合しながら６０℃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。Table 2 Rubber compounding formula Natural rubber 100 parts Zinc
Hana 5 stearic acid
2 sulfur
2.5 FEF carbon blank 45 Process oil 5 Example 2 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 part of sodium bicarbonate, 0.0 parts of t-dodecyl mercaptan. 5 parts of monomer ■ shown in Table 4 along with 0.3 parts of potassium persulfate was added to 5 times the weight of ff1 (1
00 parts), 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.
これを種ラテツクスとする。続けて攪拌機付オートクレ
ーブに、種ラテツクス２０部と第４表の単量体■を同表
記載の量仕込み、更に、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、ｔ
−ドデシルメルカプタン０．５部、過硫酸カリウム０．
３部及び水を合計量が１５０部になるように仕込み、回
転混合しながら６０℃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Ｃ及びＤを得た。This is called seed latex. Subsequently, 20 parts of the seed latex and monomer (■) listed in Table 4 were charged in an autoclave equipped with a stirrer in the amounts listed in the same table, and further, 0.1 part of tetrasodium salt of ethylenediaminetetraacetic acid, 2 parts of sodium lauryl sulfate, and t
- 0.5 parts of dodecyl mercaptan, 0.5 parts of potassium persulfate.
3 parts and water were added so that the total amount was 150 parts, and the mixture was reacted at 60° C. with rotational mixing. Polymerization conversion rate 95%
When 0.05 part of hydroquinone was added to stop the reaction, the pressure was reduced to remove unreacted monomers, and copolymer latexes C and D were obtained.
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、攪拌下に２５℃で２時間反応させた
。これを（ａ）液とする。16.6 parts of resorcinol, formalin aqueous solution (37%
Concentration) 14.6 parts, 1.3 parts of sodium hydroxide and 33 parts of water
The solution was dissolved in 3.5 parts and reacted at 25° C. for 2 hours with stirring. This is called liquid (a).
次に（ａ）液の中へラテックスＣ又はラテックスＤ１０
０部を添加し、攪拌下に２５℃で２００時間反応せた。Next (a) put latex C or latex D10 into the liquid.
0 part was added thereto, and the reaction was carried out at 25° C. for 200 hours with stirring.
次いでバルカボンドＥ （ＩＣＩ Ｖｕｌｎａ社製品Ｖ
ｕｌｃａｂｏｎｄ Ｅ）を３５部添加した。この水溶液
を固型分濃度２０％に調整した。これらをそれぞれ（１
） −Ｃ液、（１）−Ｄ液とする。Next, Vulkabond E (ICI Vulna product V
35 parts of ulcabond E) were added. This aqueous solution was adjusted to a solid content concentration of 20%. Each of these (1
)-C solution, (1)-D solution.
これらの処理液を用いて、試験用シングルコードディソ
ビングマシンでポリエステルタイヤコード（１５００Ｄ
／２）を浸漬処理した。浸漬処理後２４０℃で１分間熱
処理を行った。Using these treatment solutions, polyester tire cord (1500D
/2) was subjected to immersion treatment. After the immersion treatment, heat treatment was performed at 240° C. for 1 minute.
次に、前記の（Ｉ）−Ｄ液で処理されたポリエステルタ
イヤコードを（１） −Ｃ液を用いて再度浸漬処理した
。処理後２４０℃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表の配合処方によ
り調製した天然ゴム配合物ではさみ、プレス加硫した。Next, the polyester tire cord treated with the liquid (I)-D was again immersed in the liquid (1)-C. After the 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 formulation shown in Table 2, and press vulcanized.
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℃、相対湿度６５％、２４本の
引抜き試験）。（１）−Ｃ液による１回処理のみの場合
との対比で結果を第５表に示す。The adhesion between the tire cord and the rubber was evaluated by the T adhesion test method (measurement temperature: 20° C., relative humidity: 65%, 24 wire pull-out test). (1) Table 5 shows the results in comparison with the case of only one treatment with liquid C.
第４表
実施例３
第１段及び第２段の重合で使用する単量体として第６表
記載のものを使用する以外は実施例１と同じ条件で本発
明ラテックスＥ〜■を製造した。Table 4 Example 3 Latexes E to ■ of the present invention were produced under the same conditions as Example 1 except that the monomers listed in Table 6 were used in the first and second stage polymerizations.
またラテックスＧの製造に使用する全単量体を一括仕込
んで重合体を行ったが、凝固物が多量発生し、実用に供
しうるラテックスは得られなかった。Furthermore, although all the monomers used in the production of Latex G were charged at once and polymerized, a large amount of coagulated material was generated, and no latex that could be put to practical use could be obtained.
さらに、ラテックスＧの製造における第６表の単量体■
中のメタクリル酸を１．５部とし、単量体■中に残りの
１．５部を加える以外はラテックスＧの製造と同じにし
て重合を実施したが、ラテックスの安定性が悪く、凝固
物が多量に発生し、実用に供しうるラテックスは得られ
なかった。これらのラテックスを用い、実施例１と同じ
処方で接着剤を調製し、実施例１と同じ加硫接着試験を
行った。Furthermore, the monomers in Table 6 in the production of latex G
Polymerization was carried out in the same manner as in the production of latex G, except that 1.5 parts of methacrylic acid was added and the remaining 1.5 parts were added to monomer A large amount of was generated, and a usable latex could not be obtained. Using these latexes, adhesives were prepared with the same formulation as in Example 1, and the same vulcanization adhesion test as in Example 1 was conducted.
結果を第７表に示す。The results are shown in Table 7.
実施例４
第８表の単量体を使用する以外は実施例１と同様にして
ラテックスＪ−Ｖを製造した。これらのラテックスを用
いて実施例１と同じ加硫接着試験を行った。結果を第９
表に示す。Example 4 Latex J-V was produced in the same manner as in Example 1 except that the monomers shown in Table 8 were used. The same vulcanization adhesion test as in Example 1 was conducted using these latexes. 9th result
Shown in the table.
第９表Table 9
Claims (1)
和酸単量体０．１〜２５重量％、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０〜３
０重量％を乳化重合して共重合体ラテックスを製造する
に際し、 （ａ）少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％に当る単量体を重合転化率が少なくとも６
０％に達するまで重合し、（ｂ）次いで、残りの単量体
を重合する ことを特徴とする共重合体ラテックスの製造方法。[Claims] Conjugated diene monomer 45-85% by weight, ethylenically unsaturated acid monomer 0.1-25% by weight, vinylpyridine 10-85% by weight
45% by weight and other monomers copolymerizable with these 0-3
When producing a copolymer latex by emulsion polymerization of 0 wt %, (a) 2. 5
~60% by weight of monomers with a polymerization conversion of at least 6
A method for producing a copolymer latex, which comprises polymerizing until the monomer reaches 0%, and (b) then polymerizing the remaining monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7408486A JPH0699487B2 (en) | 1986-03-31 | 1986-03-31 | Method for producing copolymer latex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7408486A JPH0699487B2 (en) | 1986-03-31 | 1986-03-31 | Method for producing copolymer latex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62230807A true JPS62230807A (en) | 1987-10-09 |
| JPH0699487B2 JPH0699487B2 (en) | 1994-12-07 |
Family
ID=13536951
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7408486A Expired - Fee Related JPH0699487B2 (en) | 1986-03-31 | 1986-03-31 | Method for producing copolymer latex |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0699487B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
1986
- 1986-03-31 JP JP7408486A patent/JPH0699487B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0699487B2 (en) | 1994-12-07 |
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