JPH02292338A - Short fiber-rubber composite - Google Patents
Short fiber-rubber compositeInfo
- Publication number
- JPH02292338A JPH02292338A JP10989689A JP10989689A JPH02292338A JP H02292338 A JPH02292338 A JP H02292338A JP 10989689 A JP10989689 A JP 10989689A JP 10989689 A JP10989689 A JP 10989689A JP H02292338 A JPH02292338 A JP H02292338A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- short fibers
- short fiber
- treated
- short
- 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.)
- Pending
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 99
- 239000005060 rubber Substances 0.000 title claims abstract description 99
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 239000000835 fiber Substances 0.000 claims abstract description 97
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 28
- 239000004593 Epoxy Substances 0.000 claims abstract description 22
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 8
- -1 isocyanate compound Chemical class 0.000 claims description 21
- 239000012948 isocyanate Substances 0.000 claims description 18
- 125000003277 amino group Chemical group 0.000 claims description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 7
- 238000011282 treatment Methods 0.000 abstract description 28
- 239000004760 aramid Substances 0.000 abstract description 11
- 229920003235 aromatic polyamide Polymers 0.000 abstract description 11
- 238000004073 vulcanization Methods 0.000 abstract description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 4
- 229920001084 poly(chloroprene) Polymers 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 235000021355 Stearic acid Nutrition 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 abstract description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 abstract description 2
- 229920000223 polyglycerol Polymers 0.000 abstract description 2
- 239000008117 stearic acid Substances 0.000 abstract description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 abstract 1
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000004898 kneading Methods 0.000 abstract 1
- 229920000647 polyepoxide Polymers 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 239000007788 liquid Substances 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 15
- 230000000704 physical effect Effects 0.000 description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 9
- 229910000077 silane Inorganic materials 0.000 description 9
- 229920001228 polyisocyanate Polymers 0.000 description 6
- 239000005056 polyisocyanate Substances 0.000 description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- 241000238557 Decapoda Species 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- CDULGHZNHURECF-UHFFFAOYSA-N 2,3-dimethylaniline 2,4-dimethylaniline 2,5-dimethylaniline 2,6-dimethylaniline 3,4-dimethylaniline 3,5-dimethylaniline Chemical group CC1=CC=C(N)C(C)=C1.CC1=CC=C(C)C(N)=C1.CC1=CC(C)=CC(N)=C1.CC1=CC=C(N)C=C1C.CC1=CC=CC(N)=C1C.CC1=CC=CC(C)=C1N CDULGHZNHURECF-UHFFFAOYSA-N 0.000 description 1
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- CNODSORTHKVDEM-UHFFFAOYSA-N 4-trimethoxysilylaniline Chemical compound CO[Si](OC)(OC)C1=CC=C(N)C=C1 CNODSORTHKVDEM-UHFFFAOYSA-N 0.000 description 1
- ZWLDNGJSJBLBFK-UHFFFAOYSA-N 4-trimethoxysilylbutane-2-thiol Chemical compound CO[Si](OC)(OC)CCC(C)S ZWLDNGJSJBLBFK-UHFFFAOYSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- JCELWOGDGMAGGN-UHFFFAOYSA-N N=C=O.N=C=O.C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 JCELWOGDGMAGGN-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010059 sulfur vulcanization Methods 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
Description
【発明の詳細な説明】 出」 本発明は、短繊維−ゴム複合体に関する。[Detailed description of the invention] "Out" The present invention relates to short fiber-rubber composites.
従来ｑ狡青
一般に、短繊維−ゴム複合体の破壊強度、疲労特性等の
力学的特性は、主として、短繊維の分散性及びマトリッ
クスゴムとの接着性によって決定される。従って、従来
、短繊維−ゴム複合体は、予め接着処理を施した短繊維
をゴム組成物中に添加分散させることによって製造され
ている。In general, the mechanical properties such as breaking strength and fatigue properties of short fiber-rubber composites are mainly determined by the dispersibility of the short fibers and the adhesion with the matrix rubber. Therefore, short fiber-rubber composites have conventionally been produced by adding and dispersing short fibers that have been previously subjected to adhesive treatment into a rubber composition.
一般に、芳香族ポリアミド繊維やポリエステル繊維は、
表面が不活性であるために、接着処理としては、通常、
イソシアネート化合物又はエポキシ化合物で繊維を処理
した後、更に、ＲＦＬ液にて処理することが行なわれて
いる。Generally, aromatic polyamide fibers and polyester fibers are
Due to the inert surface, adhesive treatments are usually
After the fibers are treated with an isocyanate compound or an epoxy compound, they are further treated with an RFL liquid.
しかし、かかる接着処理を短繊維に適用することによっ
て、短繊維とゴムとのとの間に良好な接着性を達成する
には、Ｒ Ｆ ｆ，液を短繊維の表面に被膜を形成する
程度に塗布することが必要であり、他方、このように、
ＲＦＬ液を短繊維の表面に被膜を形成する程度に塗布す
るときは、短繊維が相互に付着凝集し、延いては、マト
リックスゴム中において分散性が悪くなる。However, in order to achieve good adhesion between the short fibers and the rubber by applying such an adhesive treatment to the short fibers, it is necessary to On the other hand, in this way,
When the RFL liquid is applied to the surface of short fibers to such an extent that a film is formed, the short fibers adhere to each other and coagulate, resulting in poor dispersibility in the matrix rubber.
このように、従来の接着処理によれば、短繊維がゴム組
成物中に接着性よく、且つ、均一に分散されてなる短繊
維−ゴム複合体を得ることは困難である。As described above, according to the conventional adhesive treatment, it is difficult to obtain a short fiber-rubber composite in which short fibers have good adhesion and are uniformly dispersed in a rubber composition.
允皿寿弄り暮．糺恒ζ［玄課題
本発明者らは、従来の短繊維−ゴム複合体における問題
を解決するために、鋭意研究した結果、予め短繊維をエ
ポキシ化合物又はイソシアネート化合物にて処理し、次
いで、シランカップリング剤にて処理して、これをゴム
組成物中に分散させた後、ゴムを加硫することによって
、短繊維がゴム中に接着性よく、且つ、均一に分散され
てなる短繊維−ゴム複合体を得ることができることを見
出し、更に、別の方法として、予め短繊維をエポキシ化
合物又はイソシアネート化合物にて処理し、これをシラ
ンカツブリング剤と共にゴム組成物中に添加混入し、加
硫することによっても、同様に、短繊維がゴム中に接着
性よく、且つ、均一に分散されてなる短繊維−ゴム複合
体を得ることができることを見出して、本発明に至った
ものである。I'm playing with Yun Sarashou. In order to solve the problems with conventional short fiber-rubber composites, the present inventors conducted intensive research and found that the short fibers were treated with an epoxy compound or an isocyanate compound in advance, and then treated with silane. By treating with a coupling agent and dispersing it in a rubber composition, and then vulcanizing the rubber, the short fibers are uniformly dispersed in the rubber with good adhesion. They discovered that it is possible to obtain a rubber composite, and as another method, short fibers are treated in advance with an epoxy compound or an isocyanate compound, and this is added and mixed into a rubber composition together with a silane clumping agent, followed by vulcanization. The inventors have discovered that it is also possible to obtain a short fiber-rubber composite in which the short fibers have good adhesion and are uniformly dispersed in rubber by the same method, and have thus arrived at the present invention.
。 占を”冫 るための
本発明による第１の短繊維−ゴム複合体は、予め分子内
にエポキシ基を２以上有するエポキシ化合物にて処理し
、次いで、シランカツブリング剤にて処理した短繊維が
ゴム組成物中に分散されてなることを特徴とする。. The first short fiber-rubber composite according to the present invention for curing the pores is made of short fibers that have been treated in advance with an epoxy compound having two or more epoxy groups in the molecule, and then treated with a silane cobbling agent. are dispersed in a rubber composition.
本発明において、分子内に２以上のエポキシ基を有する
エポキシ化合物は、特に、限定されるものではないが、
好ましい具体例として、例えば、エチレングリコール、
グリセリン、ソルビトール、ペンタエリスリトール等の
多価アルコールや、ポリエチレングリコール等のポリア
ルキレングリコールとエビクロルヒドリンのようなハロ
ゲン含有エポキシ化合物との反応生成物や、レゾルシン
、ビス（４−ヒドロキシフエニル）ジメチルエタン、フ
ェノール・ホルムアミド樹脂、レゾルシン・ホルムアミ
ド樹脂等の多価フェノール類やフェノール樹脂とエビク
ロルヒドリンのようなハロゲン含有エポキシ化合物との
反応生成物を挙げることができる。In the present invention, epoxy compounds having two or more epoxy groups in the molecule are not particularly limited, but include:
Preferred specific examples include, for example, ethylene glycol,
Polyhydric alcohols such as glycerin, sorbitol, and pentaerythritol, reaction products of polyalkylene glycols such as polyethylene glycol, and halogen-containing epoxy compounds such as shrimp chlorohydrin, resorcinol, bis(4-hydroxyphenyl) dimethyl Examples include reaction products of polyhydric phenols such as ethane, phenol/formamide resin, and resorcinol/formamide resin, and phenolic resins and halogen-containing epoxy compounds such as shrimp chlorohydrin.
上記第１の短繊維−ゴム複合体の製造において、これら
エポキシ化合物は、通常、溶液とされ、短繊維をかかる
溶液に浸漬することによって処理する。この後、必要に
応じて、短繊維を熱処理する。In the production of the first short fiber-rubber composite, these epoxy compounds are usually made into a solution, and the short fibers are treated by immersing them in such a solution. After this, the staple fibers are heat treated, if necessary.
この熱処理は、用いる繊維の種類にもよるが、繊維に付
着させたエポキシ化合物を反応定着させるに足る温度に
て行なえばよく、通常、１６０〜２５０℃にて数分間処
理すればよい。This heat treatment may be carried out at a temperature sufficient to react and fix the epoxy compound attached to the fibers, although it depends on the type of fiber used, and is usually carried out at 160 to 250° C. for several minutes.
エポキシ化合物で処理した繊維は、次いで、シランカツ
ブリング剤にて処理する。The fibers treated with the epoxy compound are then treated with a silane cobbling agent.
本発明において用いるシランカップリング剤は、有機官
能基と加水分解基とを有するシランカツブリング剤であ
って、特に、限定されるものではないが、例えば、ビニ
ルトリクロロシラン、ビニルトリス（β−メトキシエト
キシ）シラン、ビニルトリエトキシシラン、Ｔ−メタク
リ口キシブ口ビルトリメトキシシラン、β−（３．４−
エポキシシク口ヘキシル）エチルトリメトキシシラン、
γ一グリシドキシブロビルトリメトキシシラン、Ｎβ一
（アミノエチル）一γ−アミノブロピルトリメトキシシ
ラン、Ｔ−アミノプ口ビルトリエトキシシラン、γ−メ
ルカブトブ口ピルトリメトキシシラン等を挙げることが
できる。The silane coupling agent used in the present invention is a silane coupling agent having an organic functional group and a hydrolyzable group, and examples thereof include, but are not limited to, vinyl trichlorosilane, vinyl tris (β-methoxyethoxy ) silane, vinyltriethoxysilane, T-methacrylate trimethoxysilane, β-(3.4-
epoxysilane, ethyltrimethoxysilane,
Examples include γ-glycidoxybrobyltrimethoxysilane, Nβ-(aminoethyl)-γ-aminopropyltrimethoxysilane, T-aminobyltriethoxysilane, γ-merkabutobyltrimethoxysilane, and the like. .
特に、本発明においては、ゴム組成物の架橋剤とシラン
カツブリング剤の有機官能基との反応性を考慮して、イ
オウ加硫系及び金属架橋系では、γ−メルカブトブ口ピ
ルトリメトキシシランが好ましく用いられ、パーオキサ
イド架橋系では、ビニルトリエトキシシランやＴ−メタ
クリ口キシブ口ビルトリメトキシシランが好まし《用い
られる。In particular, in the present invention, in consideration of the reactivity between the crosslinking agent of the rubber composition and the organic functional group of the silane coupling agent, in the sulfur vulcanization system and the metal crosslinking system, γ-mercaptobutyltrimethoxysilane is used. In the peroxide crosslinking system, vinyltriethoxysilane and T-methacrylate trimethoxysilane are preferably used.
本発明による第１の短繊維−ゴム複合体は、短繊維を予
め分子内にエポキシ基を２以上有するエポキシ化合物に
て処理し、次いで、シランカツブリング剤にて処理し、
これをゴム組成物中に分散させ、ゴムを加硫することに
よって得ることができる。In the first short fiber-rubber composite according to the present invention, short fibers are treated in advance with an epoxy compound having two or more epoxy groups in the molecule, and then treated with a silane cobbling agent,
It can be obtained by dispersing this in a rubber composition and vulcanizing the rubber.
短繊維をシランカップリング剤にて処理するには、通常
、シランカップリング剤は、濃度数％の溶液とされ、こ
れに短繊維を浸漬し、乾燥させる。To treat short fibers with a silane coupling agent, the silane coupling agent is usually prepared as a solution with a concentration of several percent, and the short fibers are immersed in this solution and dried.
この後、必要に応じて、短繊維を１００゜Ｃ前後の温度
にて数分乃至数十分加熱処理してもよい。Thereafter, if necessary, the short fibers may be heat-treated at a temperature of around 100°C for several minutes to several tens of minutes.
このように、本発明によれば、短繊維を希薄なシランカ
ップリング剤溶液で処理するので、ゴム組成物中の添加
分散に際しても、相互に付着凝集しない。As described above, according to the present invention, since short fibers are treated with a dilute silane coupling agent solution, they do not adhere to each other and agglomerate even when added and dispersed in a rubber composition.
本発明による第１の短繊維−ゴム複合体において、短繊
維の配合量は、複合体の用途や、要求される特性にもよ
るが、通常、ゴム１００重量部に対して、短繊維３〜５
０重量部の範囲である。ゴム１００重量部に対して、短
繊維の配合量が３重量部よりも少ないときは、短繊維に
よる補強効果が乏しく、５０重量部を越えるときは、得
られる配合物のムーニー粘度が高くなって、加工性に問
題を生じる。In the first short fiber-rubber composite according to the present invention, the amount of short fibers to be blended depends on the use of the composite and the required properties, but usually 3 to 3 to 10 parts of short fibers are added to 100 parts by weight of rubber. 5
It is in the range of 0 parts by weight. When the blending amount of short fibers is less than 3 parts by weight per 100 parts by weight of rubber, the reinforcing effect of the short fibers is poor, and when it exceeds 50 parts by weight, the resulting compound has a high Mooney viscosity. , which causes problems in processability.
本発明による第２の短繊維−ゴム複合体は、予め分子内
にエポキシ基を２以上有するエポキシ化合物にて処理し
た短繊維とシランヵップリング剤とがゴム組成物中に混
入されてなることを特徴とする。The second short fiber-rubber composite according to the present invention is obtained by mixing short fibers that have been previously treated with an epoxy compound having two or more epoxy groups in the molecule and a silane coupling agent into a rubber composition. Features.
この第２の複合体の製造においては、短繊維のエポキシ
化合物による処理及びかかる短繊維のゴム組成物中への
配合量は、前述したと同じであるが、シランカップリン
グ剤は、通常、ゴム１００重量部について、０．１〜６
重量部が配合される。In the production of this second composite, the treatment of short fibers with an epoxy compound and the blending amount of such short fibers into the rubber composition are the same as described above, but the silane coupling agent is usually added to the rubber composition. For 100 parts by weight, 0.1-6
Parts by weight are blended.
シランカップリング剤の配合量がゴム１００重量部につ
いて、Ｏ． １重量部よりも少ないときは、短繊維をゴ
ムに十分に接着させることができず、他方、６ｆｆｉ量
部を越えるときは、ゴム種にもよるが、得られるゴム配
合物のスコーチタイムが短くなり、加工に支障をきたす
ことがある。The blending amount of the silane coupling agent is O. If it is less than 1 part by weight, the short fibers cannot be sufficiently adhered to the rubber, while if it exceeds 6 parts by weight, the scorch time of the resulting rubber compound will be short, depending on the type of rubber. This may cause processing problems.
第２の複合体を得るには、ゴムとシランヵップリング剤
とを必要に応じてその他の配合剤と共に例えばバンバリ
ーミキサーにて混練した後、これにエポキシ化合物にて
処理した短繊維を混合してもよく、或いはゴム及び所要
の配合剤を予め混練し、これにエポキシ化合物にて処理
した短繊維とシランカップリング剤とを加え、混練して
もよい。To obtain the second composite, the rubber and the silane coupling agent are kneaded together with other compounding agents as necessary, for example, in a Banbury mixer, and then short fibers treated with an epoxy compound are mixed therein. Alternatively, rubber and necessary compounding agents may be kneaded in advance, and short fibers treated with an epoxy compound and a silane coupling agent may be added thereto and kneaded.
後者の方法がより好ましい。The latter method is more preferred.
本発明による第３の短繊維−ゴム複合体は、予め分子内
にイソシアネート基を２以上有するインシアネート化合
物にて処理し、次いで、アミノ基を有するシランカ・ン
プリング剤にて処理した短繊維がゴム組成物中に分散さ
れてなることを特徴とする。The third short fiber-rubber composite according to the present invention is produced by treating the short fibers in advance with an incyanate compound having two or more isocyanate groups in the molecule and then with a silanka/sampling agent having an amino group. It is characterized by being dispersed in a composition.
本発明において用いる分子内に２以上のインシアネート
基を有するイソシアナート化合物は、特に、限定される
ものではないが、好ましい具体例として、例えば、トリ
レンジイソシアネート、ｍ〜フエニレンジイソシアネー
ト、ジフェニルメタンジイソシアネート、．ヘキサメチ
レンジイソシアネート、ポリメチレンボリフエニルイソ
シアネート、トリフエニルメタンジイソシアネート等の
ポリイソシアナートを挙げることができる。The isocyanate compound having two or more inocyanate groups in the molecule used in the present invention is not particularly limited, but preferred specific examples include, for example, tolylene diisocyanate, m-phenylene diisocyanate, diphenylmethane diisocyanate, ．． Examples include polyisocyanates such as hexamethylene diisocyanate, polymethyleneborifhenyl isocyanate, and triphenylmethane diisocyanate.
更に、これらのポリイソシアナートとトリメチロールプ
ロパン、ペンタエリスリトール等の分子内に２以上の活
性水素を有する化合物とをイソシアネート基／水酸基モ
ル比が１よりも大きい条件にて反応させて得られる分子
鎖末端がイソシアネ−ト基であるウレタンプレポリマー
や、或いは前記ポリイソシアナートを例えばフェノール
、チオフェノール、クレゾール、レゾルシノール等のフ
ェノール類、Ｌ−ブタノール、ｔ−ペンタノール等の第
３級アルコール、ジフエニルアミン、キシリジン等の芳
香族第２級アミン、フタル酸イミド等のイミド類、カブ
ロラクタム、バレロラクタム等のラクタム類、アセトキ
シム、メチルエチルケトキシム、シクロヘキサノンオキ
シム等のオキシム類又は亜硝酸ナトリウム等の所謂ブロ
ック化剤にてブロック化したブロック化ポリイソシアナ
ート等を挙げることができる。Furthermore, molecular chains obtained by reacting these polyisocyanates with a compound having two or more active hydrogens in the molecule, such as trimethylolpropane or pentaerythritol, under conditions where the isocyanate group/hydroxyl group molar ratio is greater than 1. A urethane prepolymer whose terminal end is an isocyanate group, or the polyisocyanate, for example, phenols such as phenol, thiophenol, cresol, and resorcinol, tertiary alcohols such as L-butanol and t-pentanol, diphenylamine, With aromatic secondary amines such as xylidine, imides such as phthalic acid imide, lactams such as cabrolactam and valerolactam, oximes such as acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime, or so-called blocking agents such as sodium nitrite. Blocked polyisocyanates and the like can be mentioned.
本発明による第３の短繊維−ゴム複合体は、短繊維を予
めかかるイソシアネート化合物にて処理し、次いで、ア
ミノ基を有するシランカップリング剤にて処理し、これ
をゴム組成物中に分散させ、ゴムを加硫することによっ
て得ることができる。The third short fiber-rubber composite according to the present invention is obtained by treating short fibers in advance with such an isocyanate compound, then treating with a silane coupling agent having an amino group, and dispersing this in a rubber composition. , can be obtained by vulcanizing rubber.
短繊維をイソシアネート化合物にて処理するには、イソ
シアネート化合物は、通常、溶液とされ、短繊維をかか
る溶液に浸漬することによって処理する。この後、必要
に応じて、繊維を熱処理する。To treat short fibers with an isocyanate compound, the isocyanate compound is usually made into a solution, and the short fibers are treated by immersing the short fibers in such a solution. After this, the fibers are heat treated, if necessary.
この熱処理は、用いる繊維の種類にもよるが、繊維に付
着させたポリイソシアナート化合物を反応定着させるに
足る温度にて行なえばよく、通常、１６０〜２５０℃に
て数分間処理すればよい。This heat treatment may be carried out at a temperature sufficient to react and fix the polyisocyanate compound attached to the fibers, although it depends on the type of fiber used, and is usually carried out at 160 to 250° C. for several minutes.
前記アミノ基を有するシランカツブリング剤としては、
例えば、γ−アミノブロピルトリエトキシシラン、Ｎ一
β（アミノエチル）γ−アミノプロビルトリメトキシシ
ラン、ビス（β−ヒドロキシエチル）Ｔ−アミノブロビ
ルトリエトキシシラン、Ｎ− （１−リメトキシシリル
プ口ビル）ジエチレントリアミン、Ｎ−（トリメトキシ
シリルプロビル）尿素、カルポエトキシエチルアミノブ
ロビルトリエトキシシラン、フエニルアミノプロビルト
リメトキシシラン、アミノフエニルトリメトキシシラン
、Ｎ−（ジメトキシメチルシリルブロビル）エチレンジ
アミン等を挙げることができる。As the silane coupling agent having an amino group,
For example, γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, bis(β-hydroxyethyl)T-aminobrobyltriethoxysilane, N-(1-rimethoxysilane) diethylenetriamine, N-(trimethoxysilylprobyl) urea, carpoethoxyethylaminobrobyltriethoxysilane, phenylaminopropyltrimethoxysilane, aminophenyltrimethoxysilane, N-(dimethoxymethylsilyl) Brobyl) ethylenediamine, etc. can be mentioned.
しかし、このようなアミノ基を有するシランカツブリン
グ剤と共に、他のシランカツブリング剤を併用すること
は許される。However, it is permissible to use other silane coupling agents together with such a silane coupling agent having an amino group.
かかるシランカップリング剤による短繊維の処理も、前
述したと同様にして行なえばよい。Treatment of short fibers with such a silane coupling agent may be carried out in the same manner as described above.
このようにして、イソシアネート化合物及びシランカツ
ブリング剤にて処理した短繊維をゴム組成物に添加分散
させ、ゴムを加硫することによって、本発明による短繊
維−ゴム複合体を得ることができる。In this manner, the short fibers treated with an isocyanate compound and a silane cobbling agent are added and dispersed in a rubber composition, and the rubber is vulcanized to obtain the short fiber-rubber composite according to the present invention.
本発明による第４の短繊維−ゴム複合体は、予め分子内
にイソシアネート基を２以上有するイソシアネート化合
物にて処理した短繊維と前述したようなアミノ基を有す
るシランカップリング剤とがゴム組成物中に混入されて
なることを特徴とする。The fourth short fiber-rubber composite according to the present invention is a rubber composition in which short fibers have been treated in advance with an isocyanate compound having two or more isocyanate groups in the molecule and a silane coupling agent having an amino group as described above. It is characterized by being mixed in.
この第４の複合体の製造においては、短繊維のイソシア
ネート化合物による処理及びかかる短繊維のゴム組成物
中への配合量は、前述したと同じであるが、アミノ基を
有するシランカップリング剤は、前述したと同じ理由に
よって、通常、ゴムｌＯＯ重量部について、０． １〜
６重量部が配合される。In the production of this fourth composite, the treatment of short fibers with an isocyanate compound and the amount of such short fibers incorporated into the rubber composition are the same as described above, but the silane coupling agent having an amino group is , for the same reasons as mentioned above, usually 0.00 parts by weight of rubber. 1~
6 parts by weight is blended.
第４の複合体を得るには、前述したと同様に、ゴムとシ
ランカップリング剤とを必要に応じてその他の配合剤と
共に例えばバンバリーミキサーにて混練した後、これに
イソシアネート化合物にて処理した短繊維を混合しても
よく、或いはゴム及び所要の配合剤を予め混練し、これ
にイソシアネート化合物にて処理した短繊維とシランカ
ップリング剤とを加え、混練してもよい。後者の方法が
より好ましい。To obtain the fourth composite, as described above, the rubber and the silane coupling agent were kneaded together with other compounding agents as necessary using, for example, a Banbury mixer, and then treated with an isocyanate compound. The short fibers may be mixed, or the rubber and necessary compounding agents may be kneaded in advance, and the short fibers treated with an isocyanate compound and a silane coupling agent may be added thereto and kneaded. The latter method is more preferred.
本発明による短繊維−ゴム複合体において、短繊維とし
ては、例えば、綿、人絹、ポリビニルアルコール繊維、
脂肪族及び芳香族ポリアミド繊維、ポリエステル繊維、
炭素繊維、ガラス繊維等を挙げることができるが、特に
制限されるものではなく、従来よりゴムとの接着に用い
られるすべての繊維を含む。In the short fiber-rubber composite according to the present invention, the short fibers include, for example, cotton, human silk, polyvinyl alcohol fiber,
aliphatic and aromatic polyamide fibers, polyester fibers,
Carbon fibers, glass fibers, etc. can be mentioned, but the fibers are not particularly limited, and include all fibers conventionally used for bonding with rubber.
また、本発明による短繊維−ゴム複合体において、ゴム
としては、天然ゴム、クロロプレンゴム、スチレンープ
タジエンゴム、ニトリルゴム、クロロスルホン化ポリエ
チレンゴム、水素化二トリルゴム、フッ素ゴム等が好適
に用いられる。これらゴムには、ゴム配合物として知ら
れる種々の充填剤、老化防止剤、可塑剤、架橋剤、加硫
促進剤、加工助剤等の適宜量が配合されていてもよい。Further, in the short fiber-rubber composite according to the present invention, natural rubber, chloroprene rubber, styrene-butadiene rubber, nitrile rubber, chlorosulfonated polyethylene rubber, hydrogenated nitrile rubber, fluororubber, etc. are preferably used as the rubber. It will be done. These rubbers may contain appropriate amounts of various fillers, anti-aging agents, plasticizers, crosslinking agents, vulcanization accelerators, processing aids, etc. known as rubber compounds.
ゴムの加硫は、それぞれのゴムについて知られている通
常の方法及び条件によればよい。Vulcanization of the rubber may be carried out by conventional methods and conditions known for each rubber.
発贋勿力未
以上のように、本発明の第１の短繊維−ゴム複合体にお
いては、分子内にエポキシ基を２以上有するエポキシ化
合物にて短繊維を処理し、次いで、シランカツブリング
剤にて処理した後、これをゴム配合物に加え、分散させ
、ゴムを加硫させるので、短繊維は凝集せず、ゴム組成
物中に均一に分散されており、かくして、破壊強度や疲
労特性にすぐれる短繊維−ゴム複合体を得ることができ
る。As described above, in the first short fiber-rubber composite of the present invention, the short fibers are treated with an epoxy compound having two or more epoxy groups in the molecule, and then a silane cutting agent is used. After treatment, it is added to the rubber compound, dispersed, and the rubber is vulcanized, so the short fibers do not aggregate and are uniformly dispersed in the rubber composition, thus improving fracture strength and fatigue properties. A short fiber-rubber composite with excellent properties can be obtained.
同様に、第２の短繊維−ゴム複合体においても、短繊維
は凝集せず、ゴム組成物中に均一に分散されており、マ
トリックスゴムとよく接着している．しかも、その製造
が容易である。Similarly, in the second short fiber-rubber composite, the short fibers do not aggregate, are uniformly dispersed in the rubber composition, and are well adhered to the matrix rubber. Moreover, it is easy to manufacture.
本発明の第３の短繊維−ゴム複合体においては、分子内
にイソシアネート基を２以上有するイソシアネート化合
物にて短繊維を処理し、次いで、アミノ基を有するシラ
ンカップリング剤にて処理した後、これをゴム配合物に
加え、分散させ、ゴムを加硫させるので、短繊維は凝集
することなく、ゴム組成物中に均一に分散されており、
か《して、破壊強度や疲労特性にすぐれる短繊維−ゴム
複合体を得ることができる。In the third short fiber-rubber composite of the present invention, the short fibers are treated with an isocyanate compound having two or more isocyanate groups in the molecule, and then treated with a silane coupling agent having an amino group. This is added to the rubber compound, dispersed, and the rubber is vulcanized, so the short fibers are uniformly dispersed in the rubber composition without agglomeration.
In this way, a short fiber-rubber composite with excellent fracture strength and fatigue properties can be obtained.
同様に、第４の短繊維−ゴム複合体においても、短繊維
は凝集せずに、ゴム組成物中に均一に分散されており、
マトリックスゴムとよく接着している。しかも、その製
造が容易である。Similarly, in the fourth short fiber-rubber composite, the short fibers do not aggregate and are uniformly dispersed in the rubber composition,
Adheres well to matrix rubber. Moreover, it is easy to manufacture.
叉施貫
以下に実施例を挙げて本発明を説明するが、本発明はこ
れら実施例により何ら限定されるものではない。EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples in any way.
実施例ｌ
芳香族ボリアミド短繊維（長さ３ｍＩ１、強度４ｇ／ｄ
）１０重量部を第１表に示す処理液Ａ（エポキシ化合物
溶液）に浸漬した後、２ ０ ０ ”Ｃで１分間、熱処
理して、上記短繊維に処理液Ａを付着させた。Example 1 Aromatic polyamide short fiber (length 3 mI1, strength 4 g/d
) 10 parts by weight were immersed in treatment liquid A (epoxy compound solution) shown in Table 1, and then heat treated at 200''C for 1 minute to adhere treatment liquid A to the short fibers.
第１表
（注）ｌ）重量部
２）ナガセ化成工業■製ポリグリセロールボリグリシジ
ルエーテル
３）四国化成■製イミダゾール化合物
４）化成アップジョン■製ポリイソシアネート化合物
この後、上記短繊維を第２表に処理液ａ（シランカップ
リング剤溶液）に浸漬し、１１０℃で１０分間、熱処理
して、短繊維にシランカップリング剤を付着させた。Table 1 (Note) l) Parts by weight 2) Polyglycerol polyglycidyl ether manufactured by Nagase Chemical Industry ■ 3) Imidazole compound manufactured by Shikoku Kasei ■ 4) Polyisocyanate compound manufactured by Kasei Upjoon ■ After this, the above short fibers were added to Table 2. The short fibers were immersed in treatment liquid a (silane coupling agent solution) and heat-treated at 110° C. for 10 minutes to adhere the silane coupling agent to the short fibers.
次いで、このように処理した芳香族ポリアミド短繊維を
下記のゴム組成物（組成は重量部）クロロプレンゴム
１００部ＳＦＲカーボン
５０オイル ２
０ステアリン酸 ｌ酸化マグ
ネシウム ６老化防止剤
３亜鉛華
５加硫促進剤
０．５に加え、バンバリーミキサーにて混練し、ロール
でシートとした後、これを１５０℃で２０分間、加硫し
た．得られた短繊維−ゴム複合体加硫物の物性を第３表
に示す。Next, the aromatic polyamide short fibers treated in this way were mixed with the following rubber composition (composition is parts by weight) chloroprene rubber.
100 parts SFR carbon
50 oil 2
0 Stearic acid l Magnesium oxide 6 Anti-aging agent
3 Zinc white
5 Vulcanization accelerator
0.5 and kneaded in a Banbury mixer and formed into a sheet with a roll, which was then vulcanized at 150°C for 20 minutes. Table 3 shows the physical properties of the obtained short fiber-rubber composite vulcanizate.
比較例１
実施例ｌにおいて、短繊維を処理液ａにて処理しなかっ
た以外は、実施例１と同様にして、短繊維−ゴム複合体
加硫物を得た。その物性を第３表に示す。Comparative Example 1 A vulcanized short fiber-rubber composite was obtained in the same manner as in Example 1, except that the short fibers were not treated with treatment liquid a in Example 1. Its physical properties are shown in Table 3.
比較例２
実施例Ｉにおいて、短繊維を処理液Ａで処理することな
く、処理液ａのみで処理した以外は、実施例ｌと同様に
して、短繊維−ゴム複合体加硫物の物性を得た。その物
性を第３表に示す。Comparative Example 2 In Example I, the physical properties of the short fiber-rubber composite vulcanizate were determined in the same manner as in Example I, except that the short fibers were not treated with treatment liquid A and were treated only with treatment liquid a. Obtained. Its physical properties are shown in Table 3.
実施例２
実施例１と同じ芳香族ポリアミド短繊維１０重量部を第
１表に示す処理液Ａ（エポキシ化合物溶液）に浸漬した
後、２００゜Ｃで１分間、熱処理して、上記短繊維に処
理液Ａを付着させた。Example 2 10 parts by weight of the same aromatic polyamide short fibers as in Example 1 were immersed in treatment solution A (epoxy compound solution) shown in Table 1, and then heat treated at 200°C for 1 minute to form the short fibers. Treatment liquid A was applied.
実施例１と同じクロロプレンゴム組成物に上記短繊維と
γ−メルカブトブ口ビルトリメトキシシラン２重量部を
加え、バンバリーミキサーにて混練し、ロールでシート
とした後、これを１５０゜Ｃで２０分間、加硫した。得
られた短繊維−ゴム複合体加硫物の物性を第３表に示す
。The above short fibers and 2 parts by weight of γ-merkabutobyltrimethoxysilane were added to the same chloroprene rubber composition as in Example 1, kneaded in a Banbury mixer, formed into a sheet with a roll, and then heated at 150°C for 20 minutes. , vulcanized. Table 3 shows the physical properties of the obtained short fiber-rubber composite vulcanizate.
実施例２において、短繊維に何らの接着処理をも施さな
かった以外は、実施例２と同様にして、短繊維−ゴム複
合体を得た。その物性を第３表に示す。A short fiber-rubber composite was obtained in the same manner as in Example 2, except that the short fibers were not subjected to any adhesive treatment. Its physical properties are shown in Table 3.
実施例３
実施例１と同じ芳香族ポリアミド短繊維１０重量部を第
１表に示す処理液Ｂ（イソシアネート化合物溶液）に浸
漬した後、２３０゜Ｃで１分間、熱処理して、上記短繊
維に処理液Ｂを付着させた。Example 3 10 parts by weight of the same aromatic polyamide short fibers as in Example 1 were immersed in treatment solution B (isocyanate compound solution) shown in Table 1, and then heat treated at 230°C for 1 minute to form the short fibers. Treatment liquid B was applied.
この後、上記短繊維を第２表に処理液ｂ（シランカツブ
リング剤溶液）に浸漬し、１１０゜Ｃで１０分間、熱処
理して、短繊維にシランカツブリング剤を付着させた。Thereafter, the short fibers were immersed in treatment solution b (silane cobbling agent solution) shown in Table 2, and heat treated at 110° C. for 10 minutes to adhere the silane cobbling agent to the short fibers.
次いで、このように処理した芳香族ボリアミド短繊維を
実施例１と同じゴム組成物に加え、バンバリーミキサー
にて混練し、ロールでシートとした後、これを１５０゜
Ｃで２０分間、加硫した。得られた短繊維−ゴム複合体
加硫物の物性を第３表に示す。Next, the aromatic polyamide short fibers treated in this way were added to the same rubber composition as in Example 1, kneaded in a Banbury mixer, formed into a sheet with a roll, and then vulcanized at 150° C. for 20 minutes. . Table 3 shows the physical properties of the obtained short fiber-rubber composite vulcanizate.
比較例４
実施例３において、短繊維を処理液Ｂで処理した後、処
理液ｂに代えて、処理液ａを用いた以外は、実施例３と
同様にして、短繊維−ゴム複合体を得た。その物性を第
３表に示す。Comparative Example 4 A short fiber-rubber composite was produced in the same manner as in Example 3, except that after treating the short fibers with treatment liquid B, treatment liquid a was used instead of treatment liquid b. Obtained. Its physical properties are shown in Table 3.
実施例４
実施例ｌと同じ芳香族ボリアミド短繊維１０重量部を第
１表に示す処理液Ｂ（イソシアネート化合物溶液）に浸
漬した後、２３０℃で１分間、熱処理して、上記短繊維
に処理液Ｂを付着させた。Example 4 10 parts by weight of the same aromatic polyamide short fibers as in Example 1 were immersed in the treatment solution B (isocyanate compound solution) shown in Table 1, and then heat treated at 230° C. for 1 minute to give the short fibers. Liquid B was applied.
実施例１と同じクロロブレンゴム組成物に上記短繊維と
γ−アミノブロピルトリエトキシシラン２重量部及びＴ
−メルカプトプロビルトリエトキシシラン２重量部を加
え、バンバリーミキサーにて混練し、ロールでシートと
した後、これを１５０゜Ｃで２０分間、加硫した。得ら
れた短繊維−ゴム複合体加硫物の物性を第３表に示す。The above short fibers, 2 parts by weight of γ-aminopropyltriethoxysilane, and T
- 2 parts by weight of mercaptopropyltriethoxysilane were added, kneaded in a Banbury mixer, formed into a sheet with a roll, and then vulcanized at 150°C for 20 minutes. Table 3 shows the physical properties of the obtained short fiber-rubber composite vulcanizate.
比較例５
実施例ｌと同じ芳香族ポリアミド短繊維１０重量部を第
１表に示す処理液Ａ（エポキシ化合物溶液）に浸漬した
後、２００″Ｃで１分間、熱処理して、上記短繊維に処
理液Ｂを付着させた。Comparative Example 5 10 parts by weight of the same aromatic polyamide short fibers as in Example 1 were immersed in treatment solution A (epoxy compound solution) shown in Table 1, and then heat treated at 200"C for 1 minute to form the short fibers. Treatment liquid B was applied.
この後、上記短繊維を第２表に示す処理液Ｃ（ＲＦＬ液
）に浸漬し、１ ５ ０ ”Ｃで２分間、熱処理して、
短繊維にＲＦＬ液を付着させた。After that, the short fibers were immersed in treatment liquid C (RFL liquid) shown in Table 2, and heat-treated at 150''C for 2 minutes.
RFL liquid was applied to the short fibers.
次いで、このように処理した芳香族ポリアミド短繊維を
実施例ｌと同じゴム組成物に加え、バンバリーミキサー
にて混練し、ロールでシートとした後、これを１５０℃
で２０分間、加硫した。得られた短繊維−ゴム複合体加
硫物の物性を第３表に示す。Next, the aromatic polyamide short fibers treated in this way were added to the same rubber composition as in Example 1, kneaded in a Banbury mixer, formed into a sheet with a roll, and heated at 150°C.
Vulcanization was carried out for 20 minutes. Table 3 shows the physical properties of the obtained short fiber-rubber composite vulcanizate.
Claims (4)
化合物にて処理し、次いで、シランカップリング剤にて
処理した短繊維がゴム組成物中に分散されてなることを
特徴とする短繊維−ゴム複合体。(1) A short fiber characterized in that the short fiber has been previously treated with an epoxy compound having two or more epoxy groups in its molecule and then treated with a silane coupling agent and dispersed in a rubber composition. Rubber composite.
化合物にて処理した短繊維とシランカップリング剤とが
ゴム組成物中に混入されてなることを特徴とする短繊維
−ゴム複合体。(2) A short fiber-rubber composite characterized in that short fibers previously treated with an epoxy compound having two or more epoxy groups in the molecule and a silane coupling agent are mixed into a rubber composition.
ソシアネート化合物にて処理し、次いで、アミノ基を有
するシランカップリング剤にて処理した短繊維がゴム組
成物中に分散されてなることを特徴とする短繊維−ゴム
複合体。(3) It is characterized by being made by dispersing short fibers in a rubber composition that have been previously treated with an isocyanate compound having two or more isocyanate groups in the molecule and then treated with a silane coupling agent having an amino group. short fiber-rubber composite.
ソシアネート化合物にて処理した短繊維とアミノ基を有
するシランカップリング剤とがゴム組成物中に混入され
てなることを特徴とする短繊維−ゴム複合体。(4) A short fiber-rubber characterized in that the short fiber has been previously treated with an isocyanate compound having two or more isocyanate groups in its molecule and a silane coupling agent having an amino group is mixed into a rubber composition. complex.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10989689A JPH02292338A (en) | 1989-04-29 | 1989-04-29 | Short fiber-rubber composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10989689A JPH02292338A (en) | 1989-04-29 | 1989-04-29 | Short fiber-rubber composite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02292338A true JPH02292338A (en) | 1990-12-03 |
Family
ID=14521908
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10989689A Pending JPH02292338A (en) | 1989-04-29 | 1989-04-29 | Short fiber-rubber composite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02292338A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017066183A (en) * | 2015-09-28 | 2017-04-06 | 日立金属株式会社 | Chloroprene rubber composition and manufacturing method therefor, wire and cable and manufacturing method therefor, crosslinking method and storing method of chloroprene rubber composition |
-
1989
- 1989-04-29 JP JP10989689A patent/JPH02292338A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017066183A (en) * | 2015-09-28 | 2017-04-06 | 日立金属株式会社 | Chloroprene rubber composition and manufacturing method therefor, wire and cable and manufacturing method therefor, crosslinking method and storing method of chloroprene rubber composition |
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