JP2005089679A - Treating liquid for rubber/fiber bonding and method for producing fiber material for rubber-reinforcement - Google Patents
Treating liquid for rubber/fiber bonding and method for producing fiber material for rubber-reinforcement Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 48
- 229920001971 elastomer Polymers 0.000 title claims abstract description 37
- 239000005060 rubber Substances 0.000 title claims abstract description 36
- 239000007788 liquid Substances 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000002657 fibrous material Substances 0.000 title claims description 5
- 229920000126 latex Polymers 0.000 claims abstract description 28
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 21
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 21
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920001577 copolymer Polymers 0.000 claims abstract description 5
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 4
- 125000003277 amino group Chemical group 0.000 claims abstract description 4
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 4
- 239000004814 polyurethane Substances 0.000 claims abstract description 4
- 229920002635 polyurethane Polymers 0.000 claims abstract description 4
- 230000002787 reinforcement Effects 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 abstract description 5
- 150000002513 isocyanates Chemical class 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 description 21
- 239000007787 solid Substances 0.000 description 18
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- 238000000034 method Methods 0.000 description 7
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- -1 aromatic secondary amines Chemical class 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
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- 239000004760 aramid Substances 0.000 description 4
- 229920003235 aromatic polyamide Polymers 0.000 description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 229920001897 terpolymer Polymers 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000012783 reinforcing fiber Substances 0.000 description 3
- 229960001755 resorcinol Drugs 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- 239000012209 synthetic fiber Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 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 2
- 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 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
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- 239000002981 blocking agent Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004132 cross linking Methods 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
- 239000000839 emulsion Substances 0.000 description 2
- 150000004820 halides Chemical group 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-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
- 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
- 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
- 239000004593 Epoxy Substances 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- JCOJVKFKIOBIRH-UHFFFAOYSA-N buta-1,3-diene;pyridine;styrene Chemical compound C=CC=C.C1=CC=NC=C1.C=CC1=CC=CC=C1 JCOJVKFKIOBIRH-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 229930003836 cresol Natural products 0.000 description 1
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- 150000001993 dienes Chemical class 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 229920006173 natural rubber latex Polymers 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000005543 phthalimide group Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 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
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Abstract
Description
本発明は、ゴム・繊維接着用の処理液及びそれを用いたゴム補強用繊維材料の製造方法に関し、さらに詳しくは、タイヤ、ホース、ベルト等のゴム・繊維複合体に好適に用いられるゴム・繊維接着用の処理液及びそれを用いたゴム補強用繊維の製造方法に関する。 The present invention relates to a rubber / fiber bonding treatment liquid and a method for producing a rubber reinforcing fiber material using the same, and more specifically, a rubber / fiber composite suitably used for rubber / fiber composites such as tires, hoses, and belts. The present invention relates to a fiber bonding treatment liquid and a method for producing a rubber reinforcing fiber using the same.
繊維は高強度、高ヤング率等の優れた物理的特性を有しており、その特性活かし補強用繊維を用いたゴム構造体は、タイヤ、ホース、ベルト等の用途に幅広く用いられている。そしてゴム構造体と、それを補強するための繊維を接着するゴム・繊維用接着剤組成物としては、レゾルシン・ホルマリン・ゴムラテックスを主成分とするいわゆるＲＦＬ系接着剤が、広く一般的に用いられている（例えば、特許文献１、特許文献２など）。 Fibers have excellent physical properties such as high strength and high Young's modulus, and rubber structures using reinforcing fibers taking advantage of these properties are widely used in applications such as tires, hoses, and belts. As a rubber / fiber adhesive composition for adhering a rubber structure and a fiber for reinforcing it, a so-called RFL adhesive mainly composed of resorcin, formalin, and rubber latex is widely used. (For example, Patent Document 1 and Patent Document 2).
しかし、ＲＦＬ系接着剤は、経時的に縮合状態が変化するとともに、接着性や工程通過性が初期の性能から低下する事が知られている。このため、接着剤のポットライフが限られるとともに、製品の性能を一定に維持することが困難であるという問題を有する。 However, it is known that the RFL adhesive changes in the condensation state with time, and the adhesiveness and process passability deteriorate from the initial performance. For this reason, the pot life of the adhesive is limited, and it is difficult to keep the performance of the product constant.
本発明の目的は、接着性能の経時による低下の少ないゴム・繊維接着用の処理液を提供することにある。 An object of the present invention is to provide a treatment liquid for rubber / fiber bonding in which a decrease in bonding performance with time is small.
本発明のゴム・繊維接着用の処理液は、ブロックポリイソシアネート、ゴムラテックス及びイソシアネート反応性の熱可塑性エラストマーを含むことを特徴とする。さらには、該熱可塑性エラストマーが、ハードセグメントにフェノール基、ヒドロキシル基、アミノ基のいずれか一つの基を有することや、ポリブタジエンとポリウレタンとの共重合物であることが好ましい。 The treatment liquid for adhering rubber / fiber according to the present invention is characterized by containing a block polyisocyanate, a rubber latex, and an isocyanate-reactive thermoplastic elastomer. Furthermore, it is preferable that the thermoplastic elastomer has any one of a phenol group, a hydroxyl group, and an amino group in the hard segment, or a copolymer of polybutadiene and polyurethane.
また、本発明のゴム補強用繊維材料の製造方法は、上記の本発明のゴム・繊維接着用の処理液を用いる方法である。 Moreover, the manufacturing method of the fiber material for rubber reinforcement of the present invention is a method using the treatment liquid for bonding rubber / fiber of the present invention.
本発明によれば、接着性能の経時による低下の少ないゴム・繊維接着用の処理液を提供することが出来る。 ADVANTAGE OF THE INVENTION According to this invention, the processing liquid for rubber | gum and fiber adhesion | attachment with little deterioration with time of adhesion performance can be provided.
本発明のゴム・繊維接着用の処理液は、ブロックポリイソシアネート、ゴムラテックス及びイソシアネート反応性の熱可塑性エラストマーを含むものである。 The rubber / fiber bonding treatment liquid of the present invention contains block polyisocyanate, rubber latex, and isocyanate-reactive thermoplastic elastomer.
ここで、本発明に用いるブロックポリイソシアネート化合物とは、ポリイソシアネート化合物とブロック化剤との付加反応生成物であり、加熱によりブロック成分が遊離して活性なポリイソシアネート化合物を生ぜしめるものである。このとき末端のイソシアネート基は３個以上であることが好ましい。ポリイソシアネート化合物としては、トリレンジイソシアネート、メタフェ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、トリス（ヘキサメチレンジイソシアネート）、ポリメチレンポリフェニルイソシアネート、トリフェニルメタントリイソシアネート等のポリイソシアネート、あるいはこれらのポリイソシアネートと活性水素原子を２個以上有する化合物、例えばトリメチロールプロパン、ペンタエリスリトール等とをイソシアネート基（−ＮＣＯ）とヒドロキシル基（−ＯＨ）との比が１を越えるモル比で反応させて得られる末端イソシアネート基含有のポリアルキレングリコールアダクトポリイソシアネート、ポリメチレンポリフェニルイソシアネートの如きポリイソシアネートが優れた性能を発現するので好ましい。ブロック化剤としては、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、ジフェニルアミン、キシリジン等の芳香族第二級アミン類、フタル酸イミド類、カプロラクタム、バレロラクタム等のラクタム類、アセトキシム、メチルエチルケトオキシム、シクロヘキサノンオキシム等のオキシム類及び酸性亜硫酸ソーダ等が挙げられる。 Here, the block polyisocyanate compound used in the present invention is an addition reaction product of a polyisocyanate compound and a blocking agent, and the block component is released by heating to produce an active polyisocyanate compound. In this case, the number of terminal isocyanate groups is preferably 3 or more. Examples of polyisocyanate compounds include tolylene diisocyanate, metaphenylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, tris (hexamethylene diisocyanate), polymethylene polyphenyl isocyanate, triphenylmethane triisocyanate, and other polyisocyanates. Terminal isocyanate obtained by reacting a compound having two or more active hydrogen atoms, such as trimethylolpropane, pentaerythritol, etc., at a molar ratio of isocyanate group (—NCO) to hydroxyl group (—OH) exceeding 1. Group-containing polyalkylene glycol adduct polyisocyanate, polyisocyanate such as polymethylene polyphenyl isocyanate It preferred because it exhibits excellent performance. Examples of the blocking agent include phenols such as phenol, thiophenol, cresol and resorcinol, aromatic secondary amines such as diphenylamine and xylidine, lactams such as phthalimides, caprolactam and valerolactam, acetoxime, methyl ethyl keto Examples include oximes such as oxime and cyclohexanone oxime, and acidic sodium sulfite.
また、本発明に使用するゴムラテックスとしては、例えば、天然ゴムラテックス、スチレン・ブタジエン・コポリマーラテックス、ビニルピリジン・スチレン・ブタジエンターポリマーラテックス、ニトリルゴムラテックス、クロロブレンゴムラテックス、エチレン・プロピレン・ジエンモノマーラテックス等があり、これらを単独、又は、併用して使用することが出来る。なかでも、ビニルピリジン・スチレン・ブタジエンターポリマーラテックスを単独、又は、他のものと併用使用するものが好ましい。併用使用の場合には、該ビニルピリジン・スチレン・ブタジエンターポリマーラテックスを全ラテックス重量の１／３量以上使用した場合が優れた性能のものが得られる。 Examples of rubber latex used in the present invention include natural rubber latex, styrene / butadiene copolymer latex, vinylpyridine / styrene / butadiene terpolymer latex, nitrile rubber latex, chlorobrene rubber latex, ethylene / propylene / diene monomer. There are latex and the like, and these can be used alone or in combination. Of these, vinyl pyridine / styrene / butadiene terpolymer latex is preferably used alone or in combination with another. When used in combination, excellent performance is obtained when the vinylpyridine / styrene / butadiene terpolymer latex is used in an amount of 1/3 or more of the total latex weight.
本発明で用いられるイソシアネート反応性の熱可塑性エラストマーとしては、イソシアネートに反応する基を有するものであれば良く、好ましくはエラストマーのハードセグメントにフェノール基、ヒドロキシル基、アミノ基のいずれか一つの基を有するものが好ましい。さらには、熱可塑性エラストマーが、ポリブタジエンとポリウレタンとの共重合物であることが好ましい。 The isocyanate-reactive thermoplastic elastomer used in the present invention is not particularly limited as long as it has a group that reacts with isocyanate. Preferably, any one group of a phenol group, a hydroxyl group, and an amino group is added to the hard segment of the elastomer. What has is preferable. Furthermore, it is preferable that the thermoplastic elastomer is a copolymer of polybutadiene and polyurethane.
また、熱可塑性エラストマーとゴムラテックスとの比は２：１〜１：２であることが、また熱可塑性エラストマーとブロックポリイソシアネートの比は１００：１５〜１００：１００であることが好ましい。ブロックポリイソシアネートの含有率が少なすぎると、繊維表面に対する化学的な親和性が不十分となり、接着力が不足する傾向にある。逆に多すぎると接着剤層が硬くなり、コード強力が発現しなくなると共に、含浸ディップならびに加工工程中での接着剤層脱離などの問題が起こる傾向にある。また熱可塑性エラストマーとゴムラテックスの比率が少なすぎると繊維を処理した場合に、被処理繊維が硬くなって耐疲労性が低下しやすくなる傾向にある。また、被着体等のゴムとの共加硫が不十分となり接着性が低くなるおそれがある。逆に、熱可塑性エラストマーとゴムラテックスの比率が多すぎると接着剤皮膜として充分な強度を得ることが出来ないため、満足な接着力やゴム付着率が得られないおそれがある。 The ratio of the thermoplastic elastomer to the rubber latex is preferably 2: 1 to 1: 2, and the ratio of the thermoplastic elastomer to the block polyisocyanate is preferably 100: 15 to 100: 100. When the content of the block polyisocyanate is too small, the chemical affinity for the fiber surface is insufficient and the adhesive force tends to be insufficient. On the other hand, if the amount is too large, the adhesive layer becomes hard and the cord strength does not develop, and there is a tendency that problems such as impregnation dipping and removal of the adhesive layer during the processing process occur. On the other hand, if the ratio of the thermoplastic elastomer and the rubber latex is too small, the fiber to be treated tends to become hard and the fatigue resistance tends to decrease when the fiber is treated. In addition, co-vulcanization with a rubber such as an adherend may be insufficient and the adhesiveness may be lowered. On the other hand, if the ratio of the thermoplastic elastomer and the rubber latex is too large, sufficient strength as an adhesive film cannot be obtained, so that there is a possibility that satisfactory adhesive force and rubber adhesion rate cannot be obtained.
このような本発明のゴム・繊維接着用の処理液は、総固形分濃度が１〜３０重量％の範囲であることが好ましく、さらに好ましくは、５〜２０重量％の範囲である。処理液の濃度が低すぎると接着剤の付着量低下を招き、接着性が低下し、逆に、後処理剤の濃度が高すぎると固形分付着量が多くなりすぎるため繊維が硬くなって耐疲労性が低下する傾向にある。 Such a treatment liquid for rubber / fiber bonding of the present invention preferably has a total solid content in the range of 1 to 30% by weight, more preferably in the range of 5 to 20% by weight. If the concentration of the treatment liquid is too low, the adhesion amount of the adhesive will be reduced and the adhesiveness will be reduced. Conversely, if the concentration of the post-treatment agent is too high, the amount of solid content will be too large and the fibers will become hard and resistant. There is a tendency for fatigue to decrease.
本発明の処理液は経時的に安定で、接着性や工程通過性も調合初期から一定であるために、それらを用いた製品の性能も一定に保つことが出来る。 Since the treatment liquid of the present invention is stable over time and the adhesiveness and process passability are constant from the beginning of the preparation, the performance of products using them can be kept constant.
またもう一つの本発明のゴム補強用繊維材料の製造方法は、前記の本発明のゴム・繊維接着用の処理液を用いる製造方法である。 Another manufacturing method of the fiber material for reinforcing rubber according to the present invention is a manufacturing method using the treatment liquid for bonding rubber / fiber according to the present invention.
ここで用いられる繊維としては、特に制限は無いがゴムの補強用繊維としては合成繊維が好適に用いられる。そのような合成繊維の好ましい例としては、ポリエステル繊維、ポリアミド繊維、芳香族ポリアミド繊維などが挙げられるが、特にポリエステル繊維、あるいは芳香族ポリアミド繊維において有効である。ポリエステル繊維としては、特に、テレフタル酸、又は、ナフタレンジカルボン酸を主たる酸成分とし、エチレングリコール、１，３−プロパンジオール又は、テトラメチレングリコールを主たるグリコール成分とするポリエステルからなる繊維であることが好ましい。芳香族ポリアミド繊維としては、ポリパラアミノベンズアミド、ポリパラフェニレンテレフタラミド、ポリパラアミノベンズヒドラジドテレフタルアミド、ポリテレフタル酸ヒドラジド、ポリメタフェニレンイソフタラミド等、もしくはこれらの共重合体からなるいわゆるアラミド繊維であることが好ましく、特に強力が高いパラ型アラミド繊維に有効に用いられる。これら合成繊維のデニール、フィラメント数、断面形状等には制限は無く、ヤーン、コード、不織布、織編物等種々の繊維集合形態を含むものである。 Although there is no restriction | limiting in particular as a fiber used here, A synthetic fiber is used suitably as a fiber for rubber reinforcement. Preferable examples of such synthetic fibers include polyester fibers, polyamide fibers, aromatic polyamide fibers and the like, and are particularly effective for polyester fibers or aromatic polyamide fibers. The polyester fiber is particularly preferably a fiber made of polyester having terephthalic acid or naphthalenedicarboxylic acid as the main acid component and ethylene glycol, 1,3-propanediol or tetramethylene glycol as the main glycol component. . As the aromatic polyamide fiber, polyparaaminobenzamide, polyparaphenylene terephthalamide, polyparaaminobenzhydrazide terephthalamide, polyterephthalic acid hydrazide, polymetaphenylene isophthalamide, or a so-called aramid fiber made of a copolymer thereof is used. It is preferable to be used effectively for para-aramid fibers having particularly high strength. There are no restrictions on the denier, filament number, cross-sectional shape, and the like of these synthetic fibers, and various fiber aggregate forms such as yarns, cords, nonwoven fabrics, and woven and knitted fabrics are included.
また本発明の製造方法に用いられる繊維はあらかじめ接着前処理を行っているものであることが好ましい。この前処理としては、通常ゴム・繊維接着に用いられているエポキシ処理でも良いが、さらには繊維を、多価アルコール、ブロックポリイソシアネート、およびゴムラテックスを含む前処理剤で処理を行うことが好ましい。ここで用いられるブロックポリイソシアネート及びゴムラテックスとしては、前処理剤で用いた前述の物を使用することが出来る。 Moreover, it is preferable that the fiber used for the manufacturing method of this invention has performed the adhesion | attachment pre-processing previously. The pretreatment may be an epoxy treatment usually used for rubber / fiber bonding, but it is preferable to further treat the fiber with a pretreatment agent containing polyhydric alcohol, block polyisocyanate, and rubber latex. . As the block polyisocyanate and rubber latex used here, the above-mentioned materials used in the pretreatment agent can be used.
したがって本発明の最も好ましい態様は、繊維を多価アルコール、ブロックポリイソシアネート、ゴムラテックスを含む前処理剤により処理し、さらに、ブロックポリイソシアネート、ゴムラテックス及びイソシアネート反応性の熱可塑性エラストマーを含む前述したゴム・繊維接着用の処理液で処理する方法である。 Accordingly, the most preferred embodiment of the present invention has been described above in which the fiber is treated with a pretreatment agent comprising polyhydric alcohol, block polyisocyanate, rubber latex, and further comprising block polyisocyanate, rubber latex and isocyanate reactive thermoplastic elastomer. This is a method of treating with a treatment liquid for rubber / fiber bonding.
ここで多価アルコールとは、複数のＯＨ基を有する脂肪族炭化水素を主鎖としたアルコールであり、さらには水溶性を上げるためにポリエチレンオキサイド、ポリプロピレンオキサイド等を導入していることも好ましい。またＯＨ基の数も３個以上である、３官能以上のアルコールであることが好ましい。さらには使用する多価アルコールとしては１０官能以下、好ましくは４〜６官能であることが好ましく、脂肪族部分に水酸基を有する化合物であることが最も好ましい。脂肪族の水酸基ではなく、フェノール性水酸基では、反応性の違いから有効な架橋構造を形成することが出来ず、接着力の向上も見込めない。本発明で用いられる多価アルコールは、熱処理によりブロックポリイソシアネートと反応して高次の架橋構造を形成し、接着剤の凝集構造を強固にする働きが有る。ここで、多価アルコールの官能基数が多すぎると、均一な架橋構造を作りにくくなる傾向にあり、官能基数が少なすぎると、有効な架橋密度を得がたくなり、接着力の向上に有効に働きにくい傾向にある。また多価アルコールの水酸基価としては５００〜１５００であることが好ましい。 Here, the polyhydric alcohol is an alcohol having an aliphatic hydrocarbon having a plurality of OH groups as a main chain, and it is also preferable to introduce polyethylene oxide, polypropylene oxide or the like in order to increase water solubility. Further, it is preferably a trifunctional or higher functional alcohol having 3 or more OH groups. Furthermore, the polyhydric alcohol used is preferably 10 or less functional groups, preferably 4 to 6 functional groups, and most preferably a compound having a hydroxyl group in the aliphatic portion. With a phenolic hydroxyl group instead of an aliphatic hydroxyl group, an effective cross-linked structure cannot be formed due to the difference in reactivity, and an improvement in adhesive strength cannot be expected. The polyhydric alcohol used in the present invention has a function of reacting with the block polyisocyanate by heat treatment to form a high-order cross-linked structure and strengthening the aggregated structure of the adhesive. Here, if the number of functional groups of the polyhydric alcohol is too large, it tends to be difficult to form a uniform cross-linked structure. If the number of functional groups is too small, it is difficult to obtain an effective cross-linking density, which is effective for improving the adhesive force. It tends to be hard to work. Moreover, it is preferable that it is 500-1500 as a hydroxyl value of a polyhydric alcohol.
このような多価アルコールを具体的に列挙すると、グリセリン、ポリグリセリン、ペンタエリスリトール、ジペンタエリスリトール、ソルビトール、トリヒドロキシメチルプロパン、ならびにこれらの重合物、ポリエチレンオキサイド付加物、ポリプロピレン付加物等が挙げられる。中でも、ジペンタエリスリトールの６エチレンオキサイド付加物であることが好ましい。 Specific examples of such polyhydric alcohols include glycerin, polyglycerin, pentaerythritol, dipentaerythritol, sorbitol, trihydroxymethylpropane, and their polymers, polyethylene oxide adducts, polypropylene adducts, and the like. . Among these, a 6-ethylene oxide adduct of dipentaerythritol is preferable.
多価アルコールは、ブロックポリイソシアネート１００重量部に対し、０．１重量部以上１０重量部以下、さらには１重量部以上５重量部以下で用いることが好ましい。添加量が上記範囲外の場合、有効な架橋密度が得にくい傾向にあり、接着力の向上が低下する傾向にある。 The polyhydric alcohol is preferably used in an amount of 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the blocked polyisocyanate. When the addition amount is out of the above range, it tends to be difficult to obtain an effective crosslinking density, and the improvement in adhesive strength tends to decrease.
さらにこの前処理剤には、ビニルハライド基を用いて重合した化合物を添加することも好ましい。このような、該ビニルハライド基を用いた化合物は通常水分散体、乳化物あるいは溶液として用いられる。 Furthermore, it is also preferable to add a compound polymerized using a vinyl halide group to this pretreatment agent. Such a compound using the vinyl halide group is usually used as an aqueous dispersion, an emulsion or a solution.
このような多価アルコール、ブロックポリイソシアネート、ゴムラテックスを含む前処理剤の総固形分濃度は、１〜３０重量％、好ましくは１．５〜２０重量％、さらに好ましくは、２〜１５重量％の範囲であることが好ましい。該総固形分濃度が低すぎると接着剤表面張力が増加し、繊維表面に対する均一付着性が低下すると共に、固形分付着量が低下することにより接着性が低下し、また、一方、該処理剤濃度が高すぎると生産コスト的に不利になるだけでなく、固形分付着量が多くなりすぎるため硬くなり耐疲労性が低下しやすいので好ましくない。また、該前処理剤の組成物を水分散物として用いる際の分散剤、すなわち、界面活性剤の適当な量は、前処理剤の全固形分に対し、１５重量％以下であり、好ましくは、１０重量％以下で用いるものがよい。該界面活性剤の量が、１５重量％を超えると接着性が若干低下する傾向にある。 The total solid concentration of the pretreatment agent containing such polyhydric alcohol, block polyisocyanate and rubber latex is 1 to 30% by weight, preferably 1.5 to 20% by weight, more preferably 2 to 15% by weight. It is preferable that it is the range of these. When the total solid content concentration is too low, the adhesive surface tension increases, the uniform adhesion to the fiber surface decreases, and the adhesion decreases due to the decrease in the solid content, while the treatment agent If the concentration is too high, it is not only disadvantageous in terms of production cost, but it is not preferable because the solid content adheres too much and becomes hard and fatigue resistance tends to decrease. Further, an appropriate amount of the dispersant when using the pretreatment composition as an aqueous dispersion, that is, an appropriate amount of the surfactant is 15% by weight or less based on the total solid content of the pretreatment agent, preferably Those used at 10% by weight or less are preferable. When the amount of the surfactant exceeds 15% by weight, the adhesiveness tends to be slightly lowered.
繊維に対する前処理剤の固形分付着量は、０．１〜１０重量％の範囲で使用することが好ましく、さらには０．３〜７重量％の範囲、最も好ましくは、０．５〜３重量％の範囲で付着せしめたものがよい。該繊維に対する固形分付着量を制御するためには、圧接ローラーによる絞り、スクレバー等によるかき落とし、空気吹きつけによる吹き飛ばし、吸引、ビーターによる叩き等の手段を採用してもよい。また付着量を上げるため、もしくは均一性を確保するために複数回付着せしめてもよい。 The solid content of the pretreatment agent on the fiber is preferably used in the range of 0.1 to 10% by weight, more preferably in the range of 0.3 to 7% by weight, most preferably 0.5 to 3% by weight. It is good that it is adhered in the range of%. In order to control the amount of solid content attached to the fibers, means such as squeezing by a pressure roller, scraping by a scrubber, blowing by air blowing, suction, hitting by a beater, etc. may be employed. Moreover, you may make it adhere several times in order to raise the adhesion amount or to ensure uniformity.
以下、実施例により本発明をさらに詳細に説明する。なお、実施例における特性の測定は、下記の測定法によりおこなった。 Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the measurement of the characteristic in an Example was performed with the following measuring method.
（１）コード剥離接着力
処理コードとゴムとの接着力を示すものである。天然ゴムを主成分とするカーカス配合の未加硫ゴムシート表層近くに７本のコードを埋め、１５０℃の温度で、３０分間、５０ｋｇ／ｃｍ２のプレス圧力（初期値）、又は、１８０℃の温度で４０分間、５０ｋｇ／ｃｍ２のプレス圧力（耐熱値）で加硫し、次いで、両端のコードを残し３本のコードをゴムシート面に対し９０度の方向へ２００ｍｍ／分の速度で剥離するのに要した力をＮ／３本で示したものである。
(1) Cord peeling adhesive strength This shows the adhesive strength between the treated cord and rubber. 7 cords are buried near the surface layer of the uncured rubber sheet containing natural rubber as a main component and carcass is mixed, and the press pressure (initial value) of 50 kg / cm 2 for 30 minutes at a temperature of 150 ° C. or 180 ° C. For 40 minutes at a temperature of 50 kg / cm 2 at a pressing pressure (heat resistance), and then the three cords are left at both ends, and the three cords are oriented at 90 ° with respect to the rubber sheet surface at a speed of 200 mm / min. The force required for peeling is indicated by N / 3.
［実施例１］
３官能ブロックポリイソシアネート（明成化学工業製、ＮＢＰ２１１）、多価アルコール(ジペンタエリスリトールの６エチレンオキサイド付加物)、VPラテックス、塩化ビニルラテックス(日信化学工業製 ビニブラン６０９)の固体成分を１００：１．５：５０：５０で混合し、全体の固体成分濃度を１０％とし、前処理剤用の処理液（１）とした。
[Example 1]
Solid components of trifunctional block polyisocyanate (manufactured by Meisei Chemical Industry Co., Ltd., NBP211), polyhydric alcohol (dipentaerythritol 6-ethylene oxide adduct), VP latex, vinyl chloride latex (Nishin Chemical Industry Co., Ltd., vinyl 609) The mixture was mixed at 1.5: 50: 50, and the total solid component concentration was set to 10% to obtain a treatment liquid (1) for a pretreatment agent.
後処理剤として、熱可塑性エラストマー（第一工業製薬製、Ｆ２００８Ｄ）、ブロックイソシアネート（明成化学工業製、ＤＭ６０１１）、VPラテックスを固体成分比で５０：１５：５０で混合し、全体の固体成分濃度を２０％とした処理液（２）を作成した。また実際に繊維コードを処理する時間に、調液直後、４８時間後、１４日後となる処理液（２−１）、（２−２）、（２−３）をそれぞれ用意した。 As a post-treatment agent, thermoplastic elastomer (Daiichi Kogyo Seiyaku, F2008D), blocked isocyanate (Meisei Chemical Industries, DM6011) and VP latex were mixed at a solid component ratio of 50:15:50, and the total solid component concentration A treatment liquid (2) was prepared with 20%. In addition, treatment liquids (2-1), (2-2), and (2-3) were prepared immediately after preparation, 48 hours later, and 14 days after the fiber cord was actually processed.
一方、固有粘度が０．９５のポリエチレンテレフタレートからなる１６７０ｄｔｅｘ／３８４フィラメントのマルチフィラメント糸を使用し、該マルチフィラメント糸に４０Ｔ／１０cmで下撚りを施し、これを２本合わせて４０Ｔ／ｃｍで上撚りを施して３３４０ｄｔｅｘ／７６８フィラメントのコードを得た。 On the other hand, a 1670 dtex / 384 filament multifilament yarn made of polyethylene terephthalate having an intrinsic viscosity of 0.95 is used, and the multifilament yarn is twisted at 40 T / 10 cm. A cord of 3340 dtex / 768 filament was obtained by twisting.
該コードをコンビュートリーター処理機（ＣＡリッツラー株式会社製、タイヤコード処理機）を用いて、前記の処理液（１）に浸漬した後、１３０℃の温度で２分間乾燥し、引き続き、２４０℃の温度で１分間の熱処理を行い、続いて、処理液（２−１）〜（２−３）に浸漬した後に、１７０℃の温度で２分間乾燥し、引続いて、２４０℃の温度で１分間の熱処理を行った。得られたタイヤコードには、処理剤の固形分として、前処理剤が２．０重量％、後処理剤が２．２重量％付着していた。得られた処理コードを天然ゴムを主成分とするカーカス配合の未加硫ゴム中に埋め込み、１５０℃の温度で３０分間、及び、１８０℃の温度で６０分間、加硫し前記の方法により評価した。その結果を表１に示す。 The cord was immersed in the treatment liquid (1) using a contributor processing machine (tire code processing machine manufactured by CA Ritzler Co., Ltd.), then dried at a temperature of 130 ° C. for 2 minutes, and subsequently 240 ° C. Heat treatment at a temperature of 1 minute, followed by immersion in treatment liquids (2-1) to (2-3), followed by drying at a temperature of 170 ° C. for 2 minutes, and subsequently at a temperature of 240 ° C. Heat treatment was performed for 1 minute. The resulting tire cord had 2.0% by weight of the pretreatment agent and 2.2% by weight of the posttreatment agent as the solid content of the treatment agent. The obtained treated cord was embedded in an unvulcanized rubber containing carcass containing natural rubber as a main component, vulcanized at a temperature of 150 ° C. for 30 minutes and at a temperature of 180 ° C. for 60 minutes, and evaluated by the above method. did. The results are shown in Table 1.
［実施例２］
前処理剤として、ソルビトールポリグリシジルエーテル(ナガセケムテック製、ＥＸ６１１)３．０gを水３７４gに溶解した後に、３２％εカプロラクタムブロックドジフエニルメタンジイソシアネート分散液を３１．３g、４０．５％ビニルピリジンスチレンブタジエンターポリマーゴムラテックス（日本ゼオン製、Ｎｉｐｏｌ ２５１８ＦＳ）を６１．７g、５０％ＰＶＣラテックス (日信化学工業製 ビニブラン６０９)２９．６gを順次添加し、総固形分量１０．０重量％とした配合液を得て、前処理用の処理液（３）とした。
[Example 2]
As a pretreatment agent, 3.0 g of sorbitol polyglycidyl ether (manufactured by Nagase Chemtech, EX611) was dissolved in 374 g of water, and then 31.3 g of a 4% caprolactam blocked diphenylmethane diisocyanate dispersion was obtained. 61.7 g of pyridine styrene butadiene terpolymer rubber latex (manufactured by Nippon Zeon, Nipol 2518FS) and 29.6 g of 50% PVC latex (Vinyl Blanc 609, manufactured by Nissin Chemical Industry) were sequentially added to obtain a total solid content of 10.0% by weight. The obtained liquid mixture was obtained and used as a pretreatment liquid (3).
処理液（１）の代わりに処理液（３）を用いた以外は実施例１と同様の処理を行い、その結果を表１に併せて示した。 The same treatment as in Example 1 was performed except that the treatment liquid (3) was used instead of the treatment liquid (1), and the results are also shown in Table 1.
［比較例１］
後処理剤として、レゾルシン／ホルマリン（Ｒ／Ｆ）のモル比が１／０．６、固形分濃度が６５重量％である初期縮合物をアルカリ条件下で溶解し９重量％の水溶液とする。これをビニルピリジン・スチレン・ブタジエンターボリマーラテックス、４０％水乳化液、１８０重量部に対し、１０９重量部を添加する。この液にホルマリン、５重量部、３３重量％のメチルエチルケトオキシムブロックドフェニルメタシジイソシアネート分散体を２３重量部添加し、４８時間熟成した固形分濃度：１８重量％の配合液を得て、後処理剤用の処理液（４）とした。また実際に繊維コードを処理する時間に、調液直後、４８時間後、１４日後となる処理液（４−１）、（４−２）、（４−３）をそれぞれ用意した。
[Comparative Example 1]
As a post-treatment agent, an initial condensate having a resorcin / formalin (R / F) molar ratio of 1 / 0.6 and a solid content concentration of 65% by weight is dissolved under alkaline conditions to obtain a 9% by weight aqueous solution. 109 parts by weight are added to 180 parts by weight of vinylpyridine / styrene / butadiene turbolimer latex, 40% aqueous emulsion. To this solution, 23 parts by weight of formalin, 5 parts by weight, 33% by weight of methyl ethyl ketoxime blocked phenylmetasidiisocyanate dispersion was added, and a blended liquid having a solid content concentration of 18% by weight was obtained after aging for 48 hours. Treatment liquid for agent (4) was obtained. In addition, treatment liquids (4-1), (4-2), and (4-3) were prepared immediately after preparation, 48 hours, and 14 days after the fiber cord was actually processed.
処理液（２）の代わりに処理液（４−１）〜（４−３）を用い、得られたタイヤコードには、処理剤の固形分として、前処理剤が１．０重量％、後処理剤が１．７重量％付着させた以外は実施例１と同様の処理を行い、その結果を表１に併せて示した。 The treatment liquids (4-1) to (4-3) were used in place of the treatment liquid (2), and the resulting tire cord had a pretreatment agent of 1.0% by weight as the solid content of the treatment agent. The same treatment as in Example 1 was performed except that the treatment agent was attached by 1.7% by weight. The results are also shown in Table 1.
［比較例２］
前処理剤として処理液（１）の代わりに処理液（３）を用いた以外は比較例１と同様の処理を行い、その結果を表１に併せて示した。
[Comparative Example 2]
The same treatment as in Comparative Example 1 was performed except that the treatment liquid (3) was used instead of the treatment liquid (1) as a pretreatment agent, and the results are also shown in Table 1.
このような本発明のゴム・繊維接着用の処理液は、接着剤の経時による性能の変化が少なく安定した接着力を示すものである。さらに本発明の製造方法によって得られたゴム補強用繊維材料は、安定した接着力を示すものであり、この繊維を用いたタイヤ、ベルト及びホース等の繊維補強ゴム構造物は強度や耐久性に優れた製品となる。 Such a treatment liquid for rubber / fiber bonding of the present invention exhibits a stable adhesive force with little change in performance of the adhesive over time. Furthermore, the fiber material for rubber reinforcement obtained by the production method of the present invention exhibits a stable adhesive force, and the fiber reinforced rubber structures such as tires, belts and hoses using this fiber are strong and durable. An excellent product.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007277732A (en) * | 2006-04-03 | 2007-10-25 | Teijin Fibers Ltd | Method for producing rubber-reinforcing fiber |
| CN107236494A (en) * | 2017-07-17 | 2017-10-10 | 山东奥固特化工有限公司 | A kind of organic fiber cord dip adhesive composition and preparation method thereof |
| US11939437B2 (en) | 2018-12-20 | 2024-03-26 | Teijin Frontier Co., Ltd. | Method for producing fiber for reinforcing rubber |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007277732A (en) * | 2006-04-03 | 2007-10-25 | Teijin Fibers Ltd | Method for producing rubber-reinforcing fiber |
| CN107236494A (en) * | 2017-07-17 | 2017-10-10 | 山东奥固特化工有限公司 | A kind of organic fiber cord dip adhesive composition and preparation method thereof |
| CN107236494B (en) * | 2017-07-17 | 2019-01-29 | 山东奥固特化工科技有限公司 | A kind of organic fiber cord dip adhesive composition and preparation method thereof |
| US11939437B2 (en) | 2018-12-20 | 2024-03-26 | Teijin Frontier Co., Ltd. | Method for producing fiber for reinforcing rubber |
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