JPH03269177A - Rubber reinforcing fiber - Google Patents
Rubber reinforcing fiberInfo
- Publication number
- JPH03269177A JPH03269177A JP2068447A JP6844790A JPH03269177A JP H03269177 A JPH03269177 A JP H03269177A JP 2068447 A JP2068447 A JP 2068447A JP 6844790 A JP6844790 A JP 6844790A JP H03269177 A JPH03269177 A JP H03269177A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- layer
- liquid
- vulcanizing agent
- latex
- 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
- 229920001971 elastomer Polymers 0.000 title claims abstract description 78
- 239000005060 rubber Substances 0.000 title claims abstract description 78
- 239000012783 reinforcing fiber Substances 0.000 title claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000012948 isocyanate Substances 0.000 claims abstract description 18
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 18
- 239000006229 carbon black Substances 0.000 claims abstract description 17
- 239000011159 matrix material Substances 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 14
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 12
- 150000002367 halogens Chemical class 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 9
- 239000000835 fiber Substances 0.000 claims description 8
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 claims description 6
- 229920000126 latex Polymers 0.000 abstract description 34
- 239000004816 latex Substances 0.000 abstract description 27
- 229920001897 terpolymer Polymers 0.000 abstract description 10
- 238000005452 bending Methods 0.000 abstract description 9
- 229920000459 Nitrile rubber Polymers 0.000 abstract description 7
- 229920002681 hypalon Polymers 0.000 abstract description 7
- QUEICCDHEFTIQD-UHFFFAOYSA-N buta-1,3-diene;2-ethenylpyridine;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=N1 QUEICCDHEFTIQD-UHFFFAOYSA-N 0.000 abstract description 3
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 abstract 1
- 230000007774 longterm Effects 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 61
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 14
- 230000001070 adhesive effect Effects 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000007423 decrease Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 5
- 229960001755 resorcinol Drugs 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- BMFMTNROJASFBW-UHFFFAOYSA-N 2-(furan-2-ylmethylsulfinyl)acetic acid Chemical compound OC(=O)CS(=O)CC1=CC=CO1 BMFMTNROJASFBW-UHFFFAOYSA-N 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 208000037062 Polyps Diseases 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002611 lead compounds Chemical class 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 125000001174 sulfone group Chemical group 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- MKZXROSCOHNKDX-UHFFFAOYSA-N 1,4-dinitrosobenzene Chemical compound O=NC1=CC=C(N=O)C=C1 MKZXROSCOHNKDX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical class COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- UIGULSHPWYAWSA-UHFFFAOYSA-N 3-amino-4-[(2-methylpropan-2-yl)oxy]-4-oxobutanoic acid;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)C(N)CC(O)=O UIGULSHPWYAWSA-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004801 Chlorinated PVC Substances 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-M chlorosulfate Chemical compound [O-]S(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-M 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- YJOMWQQKPKLUBO-UHFFFAOYSA-L lead(2+);phthalate Chemical compound [Pb+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O YJOMWQQKPKLUBO-UHFFFAOYSA-L 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal 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
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- PQCHENNROHVIHO-UHFFFAOYSA-M silver;2-methylprop-2-enoate Chemical compound [Ag+].CC(=C)C([O-])=O PQCHENNROHVIHO-UHFFFAOYSA-M 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明はゴム補強用繊維に関する。[Detailed description of the invention] (Industrial application field) The present invention relates to rubber reinforcing fibers.
（従来の技術）
ゴムベルト、タイヤ等のゴム製品の強度を増大させる為
、ガラス繊維ヤーン等の補強繊維が広く用いられる。(Prior Art) Reinforcing fibers such as glass fiber yarn are widely used to increase the strength of rubber products such as rubber belts and tires.
ゴムベルト等のゴム製品は繰返し屈曲応力を受けるため
屈曲疲労を生して性能か低下し、補強材とゴムマトリク
スの間に剥離か生じ易い。Rubber products such as rubber belts are subjected to repeated bending stress, resulting in bending fatigue, resulting in decreased performance, and peeling between the reinforcing material and the rubber matrix.
このような剥離或は性能の劣化を防止し、充分な補強効
果を得るためには、補強ｍ維とゴムとの馴染み、接着力
を大きくする必要かあり、このため補強繊維表面に処理
剤が塗布される。In order to prevent such peeling or performance deterioration and obtain a sufficient reinforcing effect, it is necessary to increase the compatibility and adhesion between the reinforcing fibers and the rubber. applied.
処理剤としては各種組成のものが提案されている。Various compositions of processing agents have been proposed.
例えばビニルピリジン−スチレン−ツタジエンのターポ
リマーラテックス及びレゾルシンとホルマリンの水溶性
縮合物を併用した処理剤、或はゴムラテックスを添加し
た処理剤等各種処理剤か提案されている（特開昭５５−
１１４５５１号参照）。For example, various processing agents have been proposed, such as a processing agent using a combination of a terpolymer latex of vinylpyridine-styrene-tutadiene and a water-soluble condensate of resorcinol and formalin, or a processing agent containing rubber latex (Japanese Unexamined Patent Application Publication No. 1983-1982).
114551).
又、ポリイソシアネート、ポリニトロソ芳香族化合物、
酸性のハロゲン含堝ポリマーを含む処理液も提案されて
いる（特開昭４９−１４５４６号参照）。Also, polyisocyanates, polynitroso aromatic compounds,
A treatment liquid containing an acidic halogen-containing polymer has also been proposed (see Japanese Patent Laid-Open No. 14546/1983).
ヌ、ゴム補強用ｍ維にレゾルシンホルムアルデヒドの水
溶性縮合物及びゴムラテックスを含む第１液（ＲＦＬ液
）を塗布して該繊維上にレゾルシンホルムアルデヒド縮
合物及びゴムを含む第１層を形成させ、次いてゴムラテ
ックス及びイソシアネートを含むオーバーコート液で処
理し、イソシアネ−１〜及びゴムを含む第２層を形成さ
せることも知られている（特開昭４９−１４５４６号公
報参照）。n) Applying a first liquid (RFL liquid) containing a water-soluble condensate of resorcin formaldehyde and rubber latex to the m-fiber for rubber reinforcement to form a first layer containing the condensate of resorcin formaldehyde and rubber on the fiber; It is also known that the layer is then treated with an overcoat liquid containing rubber latex and isocyanate to form a second layer containing isocyanate-1 and rubber (see JP-A-49-14546).
更に又、ＲＦＬ中に含有せしむべきゴムラテックスとし
てＨ−ＮＢＲラテックスを使用することも提案されてい
る（特開昭６３−２７０８７７号公報参照）。Furthermore, it has also been proposed to use H-NBR latex as the rubber latex to be contained in RFL (see Japanese Patent Laid-Open No. 63-270877).
（発明か解決しようとする課題）
従来のゴム補強繊維用処理液並びにゴム補強用繊維の処
理方法は次のような問題点を４１する。(Problems to be Solved by the Invention) Conventional treatment liquids for rubber reinforcing fibers and methods for treating rubber reinforcing fibers have the following problems.
（１）充分な接着力か得られない。(1) Sufficient adhesive strength cannot be obtained.
（２）充分な屈曲強度を有するゴム製品か得難い。(2) It is difficult to obtain rubber products with sufficient bending strength.
（３）高温て使用すると接着性か低ドする。即ち、耐熱
性か不充分である。(3) Adhesiveness decreases when used at high temperatures. That is, the heat resistance is insufficient.
近時、自動用のエンジン付近の温度り昇に伴い、タイミ
ンクベルト用のゴムとして、クロロスルフォン化ポリエ
チレン、水素化ニトリルゴムのような耐熱性のゴムか使
用されるようになって来たか、このような耐熱性のゴム
は接着性か一般のゴムに比して小さいため上述の欠点は
−・般のゴムに比し大きくなり易く、長距離走行に耐え
るタイミングベルトは得られていない。Recently, with the rise in temperature near automatic engines, heat-resistant rubbers such as chlorosulfonated polyethylene and hydrogenated nitrile rubber have come to be used as rubber for timing belts. Since such heat-resistant rubber has less adhesive properties than ordinary rubber, the above-mentioned drawbacks tend to be greater than ordinary rubber, and a timing belt that can withstand long-distance running has not been obtained.
ＲＦＬ液でゴム補強用ｌａ＃を処理し、次いて、ゴムラ
テックス及びイソシアネートを含むオーバーコート液で
処理することにより、上述の問題点を成る程度解消する
ことはてきるか、この方法は次のような問題点を有する
。Is it possible to solve the above-mentioned problems to some extent by treating the rubber reinforcing LA# with an RFL liquid and then with an overcoat liquid containing rubber latex and isocyanate? It has the following problems.
（１）接着力が時間経過とともに低下する。(1) Adhesive strength decreases over time.
（２）充分な効果をうるためには多量のインシアネ−１
・を使用する必要があり、イソシアネートの量を増大さ
ゼると液の安定性が悪化し、オーバーコート液を使用の
都度少量づつ調合する必要がある。(2) In order to obtain sufficient effects, a large amount of incyane-1 is required.
If the amount of isocyanate is increased, the stability of the solution deteriorates, and it is necessary to prepare a small amount of the overcoat solution each time it is used.
（３）ＲＦＬ層（第１層）とオーバーコート液（第２層
）の間の界面接着性が悪く、第１゜２層間に剥離が生じ
易い。(3) The interfacial adhesion between the RFL layer (first layer) and the overcoat liquid (second layer) is poor, and peeling easily occurs between the first and second layers.
Ｉｆ−ＮＢＲラテックスを含むＲＦＬ液を使用する方法
は、マトリクスゴムがＨ−ＮＢＲの場合特に有効な方法
であるが、この方法も次のような難点を有する。Although the method of using an RFL liquid containing If-NBR latex is particularly effective when the matrix rubber is H-NBR, this method also has the following drawbacks.
即ち、ＲＦＬ液中に含有せしむべきゴムラテックスとし
ては水性エマルジョンを使用する必要がある。Ｈ−ＮＢ
Ｒを含む水性エマルジョンの製造は技術的には回旋であ
るが、その製造工程が複雑であるためコストが大幅に上
昇する。That is, it is necessary to use an aqueous emulsion as the rubber latex to be contained in the RFL liquid. H-NB
Although the production of an aqueous emulsion containing R is technically a convoluted process, the production process is complicated, which significantly increases the cost.
本発明は、上述の従来技術の問題点を解消し、繰返し屈
曲応力を受けるような高温の条ヂ↑ドで使用していても
、時間の経過とともに接着力が低下することなく、耐熱
性も大きく、Ｌ２かも製造コストも低いゴム補強用繊維
を提供することを［１的としている。The present invention solves the above-mentioned problems of the conventional technology, and even when used in high-temperature steel strips that are subjected to repeated bending stress, the adhesive strength does not decrease over time and the heat resistance is maintained. Our first objective is to provide rubber reinforcing fibers that are large, have low L2, and have low manufacturing costs.
（課題を解決するための手段）
上記目的を達成するために本発明においては、マトリク
スゴムを補強するためのゴム補強用ＮｈＨとして、該繊
維上に形成されたレゾルシンホルトアルデヒドの水溶性
縮合物及びゴムを含む第１層の上に、第１層と親和性を
有する第２層を、第２層の上に更にマトリクスゴムと同
質のゴムを含む第３層を形成させたｕｈ維を使用する。(Means for Solving the Problems) In order to achieve the above object, the present invention uses a water-soluble condensate of resorcinformaldehyde formed on the fibers as a rubber reinforcing NhH for reinforcing the matrix rubber. UH fibers are used in which a second layer having affinity with the first layer is formed on the first layer containing rubber, and a third layer containing the same rubber as the matrix rubber is further formed on the second layer. .
本発明の好ましい態様において、／＼ロゲン含イ］ポリ
マー、イソシアネート、加硫剤を含む第２層、或はハロ
ゲン含有ポリマー、イソシアネート、加硫剤、カーボン
ブラック、又はシリカ等の不活性微粉末を含む第２層を
使用し、又マトリクスゴムと同質のゴム、加硫剤、カー
ボンブラック又はシリカ等の不活性微粉末を含む第３層
を形成させた補強用繊維を使用する。In a preferred embodiment of the present invention, the second layer contains a halogen-containing polymer, an isocyanate, a vulcanizing agent, or a halogen-containing polymer, an isocyanate, a vulcanizing agent, carbon black, or an inert fine powder such as silica. A reinforcing fiber is used to form a second layer containing rubber of the same quality as the matrix rubber, a vulcanizing agent, and a third layer containing inert fine powder such as carbon black or silica.
次に、本発明を更に具体的に説明する。Next, the present invention will be explained in more detail.
本発明においては、ゴム補強用繊維上に、レゾルシンホ
ルムアルデヒド縮合物及びゴムラテックスを含む液（Ｒ
ＦＬ液）を塗布することにより第１層を形成させる。In the present invention, a liquid (R
The first layer is formed by applying FL liquid).
レゾルシンホルムアルデヒドの水溶性縮合物（以下単に
縮合物という）としては、レゾルシンとホルムアルデヒ
ドを水酸化アルカリ、アンモニア、アミンなどのアルカ
リ性触媒の存在下で反応させて得られるレゾルシンとホ
ルムアルデヒドのオキシメチル基に富んだ水溶性の初期
の付加縮合物（レゾール）が好適に使用できる。特にレ
ゾルシンとホルムアルデヒドをモル比で１ ： ０．３
〜２．５の割合で反応させたものが好ましい。A water-soluble condensate of resorcin formaldehyde (hereinafter simply referred to as a condensate) is a resorcin and formaldehyde rich in oxymethyl groups obtained by reacting resorcin and formaldehyde in the presence of an alkaline catalyst such as an alkali hydroxide, ammonia, or an amine. Water-soluble initial addition condensates (resols) can be preferably used. In particular, the molar ratio of resorcinol and formaldehyde is 1:0.3.
It is preferable to react at a ratio of 2.5 to 2.5.
ＲＦＬ液（第１液）において使用されるゴムラテックス
としては、ゴム補強用繊維用処理剤として使用される比
較的低重合度のラテックスが好適に使用でき、限定はな
いが、特にブタジェン系ラテックス、ビニルピリジン−
スチレン−ブタジェンのターポリマーラテックスＣ以下
ターポリマーラテックスという）就中、ターポリマーラ
テックスが好ましい。As the rubber latex used in the RFL liquid (first liquid), a latex with a relatively low degree of polymerization used as a treatment agent for rubber reinforcing fibers can be suitably used, and there are no limitations, but in particular, butadiene latex, vinyl pyridine
Styrene-butadiene terpolymer latex C (hereinafter referred to as terpolymer latex) Among these, terpolymer latex is preferred.
ターポリマーラテックスとしては、ビニルピリジン、ス
チレン、ブタジェンの重量割合が１０〜２０：１０〜２
０ ： ６０〜８０のものが特に適当であり、Ｐｙｒａ
ｔｅｘ （商品名、住友ノーガタック社製） 、 ０
８５０ （商品名、日本合成ゴム製） 、 Ｎ１ｐｏ１
２５１８ＦＳ （商品名、日本ゼオン製）等が好適に使
用できる。The terpolymer latex has a weight ratio of vinylpyridine, styrene, and butadiene of 10 to 20:10 to 2.
0: 60 to 80 is particularly suitable, and Pyra
tex (product name, manufactured by Sumitomo Naugatuck), 0
850 (product name, made by Japan Synthetic Rubber), N1po1
2518FS (trade name, manufactured by Nippon Zeon) etc. can be suitably used.
又ブタジェン系ラテックスとしては、ブタジェンラテッ
クス、ブタジェン−スチレンの共重合体ラテックス、ブ
タジェン−ニトリルの共重合体ラテックス等が適当であ
り、０７００ （商品名、日本合成ゴム製） 、 Ｎ１
ｐｏｌ ＬＸＩＩＩ、Ｎ１ｐｏｌ １５Ｂ２ （商品名
、日本ゼオン製）等が好適に使用できる。As the butadiene latex, butadiene latex, butadiene-styrene copolymer latex, butadiene-nitrile copolymer latex, etc. are suitable, such as 0700 (trade name, manufactured by Japan Synthetic Rubber Co., Ltd.) and N1.
pol LXIII, N1pol 15B2 (trade name, manufactured by Nippon Zeon), etc. can be suitably used.
上記ターポリマーラテックス、ブタジェン系ラテックス
は単独で使用することもできるが、両者を併用し且つ以
下述べるクロロスル２オン化ポリエチレン（ＣＳＭ）ラ
テックスと混合して用いるのが好ましい。Although the above-mentioned terpolymer latex and butadiene latex can be used alone, it is preferable to use both in combination and in a mixture with chlorosulfate polyethylene (CSM) latex described below.
Ｃ３Ｍラテックスとしては、塩素含有量２０〜４０ｗｔ
％、好ましくは２５〜３５ｗｔ％、スルフォン基中のＳ
含有量は０．５〜２．Ｏｗｔ％、好ましくは１．１〜１
．４ ｗｔ％のものが適当であり、生ゴムのムーニー粘
度が３０〜９５のものが好適に使用できる。C3M latex has a chlorine content of 20 to 40 wt.
%, preferably 25-35 wt%, S in the sulfone group
The content is 0.5-2. Owt%, preferably 1.1-1
．． 4 wt% is suitable, and raw rubber having a Mooney viscosity of 30 to 95 can be suitably used.
なお、Ｃ３Ｍラテックスの一部（５０ｗｔ％以下、好ま
しくは２５ｗｔ％以下）をクロロブレン（ＣＲ）又は水
素化ニトリルゴム（Ｈ−ＮＢＲ）のラテックスで置換す
ることもできる。Note that a part of the C3M latex (50 wt% or less, preferably 25 wt% or less) can also be replaced with a latex of chlorobrene (CR) or hydrogenated nitrile rubber (H-NBR).
上述の各成分を含むゴム補強繊維処理用液第１液中のタ
ーポリマーラテックス、又はブタジェン系ラテックス、
Ｃ３Ｍラテックス、縮合物の濃度は夫々ｌＯ〜３０ｗｔ
％、３〜２５ｗｔ％、０．５〜６ｗｔ％、好ましくは１
５〜２５ｗｔ％、５〜１５ｖｔ％、１〜３ｗｔ％、２〜
６ｗｔ％としてこれらの合計量は１０〜５０ｗｔ％、好
ましくは２０〜４゜ｗｔ％とし、又補強繊維に対する第
１液の付与量は固型分としてｍｔａ重量の１２〜２５ｗ
ｔ％、好ましくは１６〜２２ｗｔ％とするのが適当であ
る。Terpolymer latex or butadiene latex in the first liquid for rubber reinforcing fiber treatment containing each of the above-mentioned components,
The concentration of C3M latex and condensate is 10~30wt, respectively.
%, 3-25 wt%, 0.5-6 wt%, preferably 1
5-25wt%, 5-15vt%, 1-3wt%, 2-
6 wt%, the total amount of these is 10 to 50 wt%, preferably 20 to 4 wt%, and the amount of the first liquid applied to the reinforcing fibers is 12 to 25 w of mta weight as solid content.
t%, preferably 16 to 22 wt%.
なお、第１液中には、必要に応じラテックスの安定剤、
老化防止剤等を添加することも出来る。The first liquid may contain a latex stabilizer, if necessary.
It is also possible to add anti-aging agents and the like.
本発明において使用する補強繊維に特に限定はないが、
ガラス繊維を用いるのか実際的である。Although there are no particular limitations on the reinforcing fibers used in the present invention,
Is it practical to use glass fiber?
例えば、太さ９弘のガラス繊維に集束剤を付与して２０
０本程度集束したガラスｍ維か好適に使用できる。For example, if a sizing agent is added to glass fiber with a thickness of 9 hiro,
Glass m-fibers bundled with about 0 fibers can be suitably used.
このような補強繊維を３本引揃え、これに第１液を１２
〜２５ｗｔ％、望ましくは１６〜２２ｗｔ％常法に従い
塗布する。Arrange three such reinforcing fibers and add 12 ml of the first liquid to them.
~25 wt%, preferably 16 to 22 wt%, according to a conventional method.
第１液を付与乾燥させて後、第２液を常法に従い塗布す
る。第１液の乾燥は２００〜３５０ ’Ｃで行うのが望
ましい。After the first liquid is applied and dried, the second liquid is applied according to a conventional method. It is desirable to dry the first liquid at 200 to 350'C.
本発明においては、このようにして形成された第１層の
上に、第１層と親和性を有する第２層を形成させる。In the present invention, a second layer having affinity with the first layer is formed on the first layer thus formed.
第２層は以下述べるような第２液を塗布することによっ
て好適に形成することができる。The second layer can be suitably formed by applying a second liquid as described below.
第２液の塗布量は補強繊維に対し、０．５〜５ｗｔ％、
望ましくは１〜４ｗｔ％とするのが適当である。第２液
を塗布した後、好ましくは１００〜２００℃において乾
繰する。The amount of the second liquid applied is 0.5 to 5 wt% based on the reinforcing fibers.
A suitable content is desirably 1 to 4 wt%. After applying the second liquid, it is preferably dried at 100 to 200°C.
なお、１−述の第１液を塗布した補強繊維に２．５４ｃ
ｍ（１インチ）当り０．５〜４．０程度のＳ、又はＺ撚
り（Ｆ撚り）をう−えたものを更に２〜１３本程度引揃
えて２．５４ｃ−当り０．５〜３．０程度の、下撚りと
逆方向の撚り（上撚り）を与えてヤーンとし、これに第
２液を塗布するのが望ましい。In addition, 2.54c was applied to the reinforcing fibers coated with the first liquid described in
A further 2 to 13 strands of S or Z twist (F twist) of about 0.5 to 4.0 per m (1 inch) are arranged to give a 0.5 to 3.0 per 2.54 cm (1 inch). It is desirable to give the yarn a twist of about 0 in the opposite direction to the first twist (first twist), and then apply the second liquid to the yarn.
第２液としては、公知のオーバーコート液も使用しうる
か、ハロゲン含有ポリマー、イソシアネート及び加硫剤
、好ましくはハロゲン含有ポリマー、イソシアネート、
加硫剤、カーボンブラック、シリカ等の不活性微粉末を
含む液特に以下述べる液か好適に用いられる。As the second liquid, a known overcoat liquid may be used, or a halogen-containing polymer, an isocyanate, and a vulcanizing agent, preferably a halogen-containing polymer, an isocyanate,
Liquids containing inert fine powders such as vulcanizing agents, carbon black, and silica are preferably used, especially the liquids described below.
ハロゲン含有ポリマーとじては塩素化ゴム、クロロブレ
ン、塩素化ポリエチレン、塩素化エチレン−プロピレン
共重合体、塩素化ポリ塩化ビニル、クロロスルフォン化
ポリエチレン等か使用できるか、クロロスルフォン化ポ
リエチレンが特に好適な結果を今゛、える。Regarding the halogen-containing polymer, chlorinated rubber, chlorobrene, chlorinated polyethylene, chlorinated ethylene-propylene copolymer, chlorinated polyvinyl chloride, chlorosulfonated polyethylene, etc. can be used, but chlorosulfonated polyethylene is particularly suitable. I can get it now.
クロロスルフォン化ポリエチレン（Ｃ５Ｍ）ラテックス
としては、塩素含有量２０〜４０ｗｔ％、好ましくは２
５〜３５ｗｔ％、スルフォン基中のＳ含有量は０．５〜
２．Ｏｗｔ％、好ましくは１．１〜１，４ｗｔ％のもの
か適当てあり、生ゴムのムーニー粘度か３０〜９５のも
のか好適に使用できる。The chlorosulfonated polyethylene (C5M) latex has a chlorine content of 20 to 40 wt%, preferably 2
5-35 wt%, S content in sulfone group is 0.5-35 wt%
2. Owt%, preferably 1.1 to 1.4 wt%, can be suitably used, and raw rubber Mooney viscosity of 30 to 95 can be suitably used.
又、第２液中のハロゲン含有ポリマーの閂は、固型分と
して１〜１０ｗｔ％、好ましくは２・〜５ａｔ％とする
のが適当である。この量かあまり少ないと、その効果が
充分てはなく、この量かあまり多いと接着力が低下する
。Further, the solid content of the halogen-containing polymer bar in the second liquid is suitably 1 to 10 wt%, preferably 2 to 5 at%. If this amount is too small, the effect will not be sufficient, and if this amount is too large, the adhesive force will decrease.
第２液中には、イソシアネートを添加する。Isocyanate is added to the second liquid.
イソシアネートの呈〜は、０．５〜・２．Ｏｗｔ％、好
ましくは１〜１．５ ｗｔ％とするのが適当てあり、接
着性を向上させることかできる。The isocyanate value is 0.5 to 2. Owt%, preferably 1 to 1.5 wt%, is suitable and can improve adhesiveness.
イソシアネートの量は、従来技術の約５０％程度で充分
であり、イソシアネートを過剰に用いた場合に生ずる屈
曲疲労性、並びに耐熱性の悪化か生ずることもなく、又
オーバーコーＩ・液の安定性か増大する。The amount of isocyanate is sufficient to be about 50% of the conventional technology, and there is no deterioration in bending fatigue or heat resistance that would occur if too much isocyanate is used, and the stability of overcoat I/liquid is improved. or increase.
第２液中のイソシアネートとハロゲン含有ポリマーの合
計量の重量％は、３〜１５ｗｔ％、好ましくは５〜ｌｏ
ｗｔ％とするのか適当てあり、この１度があまり大きい
と液の粘度が大となり、ムラか出来易くなり、この濃度
かあまり小さいと付着量が減少し、充分な効果か得られ
なくなる。The weight percent of the total amount of isocyanate and halogen-containing polymer in the second liquid is from 3 to 15 wt%, preferably from 5 to 10% by weight.
It is up to you whether it is wt% or not; if this 1 degree is too large, the viscosity of the liquid will be high and unevenness will easily occur, and if this concentration is too small, the amount of adhesion will decrease and a sufficient effect will not be obtained.
更にヌ、第２液中には加硫剤を含有せしめることにより
、更に接着性を向上させ、−層好適な結果をうることか
できる。Furthermore, by incorporating a vulcanizing agent into the second liquid, it is possible to further improve the adhesion and obtain favorable results.
加硫剤としてはポリニトロソ芳香族化合ｅＪＡ（例えば
ｐ−ジニトロソベンゼン）、テトラクロロベンゾキノン
、ポリｐ−ジニトロソベンゼン。Examples of the vulcanizing agent include polynitroso aromatic compound eJA (for example, p-dinitrosobenzene), tetrachlorobenzoquinone, and polyp-dinitrosobenzene.
ｐ、ｐ −ジベンゾイル、ベンゾキノンジオキシム、ｐ
−ベンゾキノンオキシムが例示されるが、テトラクロロ
ベンゾキノン、ポリｐ−ジニトロソベンゼン、Ｐ、Ｐ′
−ジベンゾイルベンゾキノンジオキシム、Ｐ−ベンゾキ
ノンジオキシムが特に好ましい。p, p-dibenzoyl, benzoquinone dioxime, p
Examples include -benzoquinone oxime, such as tetrachlorobenzoquinone, polyp-dinitrosobenzene, P, P'
-dibenzoylbenzoquinone dioxime and P-benzoquinone dioxime are particularly preferred.
第２液中の加硫剤の量は０．３〜３ｗｔ％、望ましくは
０．６〜２．５ ａｔ％程度とするのか適当でありこの
量かあまり少ないと効果か充分でなく、第１層と第２層
との間に剥離か生じ易くなる。The amount of the vulcanizing agent in the second liquid is approximately 0.3 to 3 wt%, preferably 0.6 to 2.5 at%. Peeling is likely to occur between the layer and the second layer.
第２液中には更に、リサージ、マレイン酸鉛、フタル酸
鉛のような鉛化合物を加λることもてき、耐水性を向上
させる効果を有する。A lead compound such as litharge, lead maleate, or lead phthalate may be further added to the second liquid, which has the effect of improving water resistance.
第２液中の鉛化合物の華は１）、５−１５ｗｔ％、好ま
しくは１〜３ｗｔ％とするのか適当である。The content of lead compounds in the second liquid is 1) 5-15 wt%, preferably 1-3 wt%.
更に、第２液中に加硫助剤としてメタクリル酸塩又はア
クリル酸塩を添加することにより一層良好な結果をうろ
ことかてきる。Furthermore, even better results can be obtained by adding methacrylate or acrylate as a vulcanization aid to the second liquid.
メタクリル酸塩、アクリル酸塩としてはメタクリル酸鉛
、メタクリル酸亜鉛、メタクリル酸アルミニウム、メタ
クリル酸銀及び、アクリル酸の同様な金属塩を好適に用
いることかできる。As the methacrylate and acrylate, lead methacrylate, zinc methacrylate, aluminum methacrylate, silver methacrylate, and similar metal salts of acrylic acid can be suitably used.
第２液中に懸濁せしむべきメタクリル酸塩又はアクリル
酸塩の量は３〜（］、００１ ｗｔ％、望ましくは１．
５〜０．０５ ｗｔ％とするのが適当である。The amount of methacrylate or acrylate to be suspended in the second liquid is between 3 and 001 wt%, preferably 1.001 wt%.
A suitable content is 5 to 0.05 wt%.
カーボンブラック又はシソ力、チタン等の不活性微粉末
としては粒径１ｏ〜２００ｍμ、望まし〈は２０〜１０
０ ｍ ｇのものが好適に使用てきる。カーボンブラッ
ク、シリカ等の不活性微粉末は予めゴム中に混練してお
くのか実際的である。Inert fine powder of carbon black, titanium, etc. has a particle size of 1 to 200 mμ, preferably 20 to 10 mμ.
0 mg can be suitably used. It is practical to knead inert fine powders such as carbon black and silica into the rubber in advance.
カーボンブラック又はシリカ等の不活性微粉末の量はゴ
ムに対し１０〜５０ｗｔ％、望ましくは２０〜４０ｗｔ
％とするのが適当である。The amount of inert fine powder such as carbon black or silica is 10 to 50 wt%, preferably 20 to 40 wt% based on the rubber.
% is appropriate.
カーボンブラック、又はシリカ等の不活性微粉末を添加
することにより第２層の強度を増大させることかできる
。The strength of the second layer can be increased by adding carbon black or an inert fine powder such as silica.
なお、第２液の塗布量は補強繊維に対し、固型分として
０．５〜５ｗｔ％、望ましくは２〜４ｗｔ％とするのか
適当である。The amount of the second liquid to be applied is suitably 0.5 to 5 wt%, preferably 2 to 4 wt%, based on the solid content of the reinforcing fibers.
本発明においては、このように形成した第２層を乾燥し
た後、その上にマトリクスゴムと同質のゴムを含む第３
層を形成させる。In the present invention, after drying the second layer formed in this way, a third layer containing rubber of the same quality as the matrix rubber is formed on top of the second layer.
Form a layer.
ゴムとしては、クロロスルレフオン化ポリエチン、ニト
リルゴム、水素化ニトリルゴム（Ｈ−ＮＢＲ）、エチレ
ン−プロピレンゴム（Ｅ Ｐ ＤＭ）か例示される。Examples of the rubber include chlorosulfurionated polyethine, nitrile rubber, hydrogenated nitrile rubber (H-NBR), and ethylene-propylene rubber (EPDM).
第３層の形成は、以下述べる第３液の塗布により好適に
行なうことができる。以下第３液について説明する。The third layer can be suitably formed by applying the third liquid as described below. The third liquid will be explained below.
第３液としてはマトリクスゴムと同質、好ましくは同一
のゴムの有機溶媒溶液を用いるのが適当である。As the third liquid, it is appropriate to use an organic solvent solution of the same, preferably the same rubber as the matrix rubber.
有機溶媒としては、トルエン、ＭＥＫ、キシレン、トリ
クロルエタン、トリクロルエチレン等ヲ好適に用いるこ
とができる。又濃度は３〜２０ｗｔ％、望ましくは５〜
１５ｗｔ％とするのが好ましい。As the organic solvent, toluene, MEK, xylene, trichloroethane, trichloroethylene, etc. can be suitably used. The concentration is 3 to 20 wt%, preferably 5 to 20 wt%.
The content is preferably 15 wt%.
第３液中には、更にカーボンブラック、又はシリカ等の
不活性微粉末、加硫剤を含有せしめるのが望ましい。It is desirable that the third liquid further contains carbon black, inert fine powder such as silica, and a vulcanizing agent.
カーボンブラック、シリカ、チタン等の不活性微粉末は
、粒径１０〜２００ ｍ ４、望ましくは２０〜１００
ｍｇのものを用い、第３液中に懸濁させる。カーボンブ
ラック、シリカ等の不活性微粉末の量はゴムに対し１０
〜５０ｗｔ％、望ましくは２０〜４０ｗｔ％とするのが
適当であり、又予めゴム中に混練しておくのが実際的で
ある。これらを添加することにより、第３層の強度を増
大させることができる。Inert fine powder such as carbon black, silica, titanium, etc. has a particle size of 10 to 200 m4, preferably 20 to 100 m4.
mg is used and suspended in the third liquid. The amount of inert fine powder such as carbon black and silica is 10% relative to rubber.
It is appropriate to set the amount to 50 wt%, preferably 20 to 40 wt%, and it is practical to knead it into the rubber in advance. By adding these, the strength of the third layer can be increased.
加硫剤としては、第２液において述べた加硫剤又はイオ
ウ、ジクミールパーオキサイド等の過酸化物を好適に使
用することができ、又第２液において述べた加硫助剤を
併用することもでき、−層良好な結果をうることができ
る。As the vulcanizing agent, the vulcanizing agents mentioned in the second liquid or peroxides such as sulfur and dicumyl peroxide can be suitably used, and the vulcanizing aids mentioned in the second liquid are used together. It is also possible to obtain good results.
なお、加硫剤及び加硫助剤の量は、夫々ゴムに対し０．
５〜１５ｗｔ％、０．１〜１．５ ａｔ％、望ましくは
１〜１０ｗｔ％、０．２〜１ ｗｔ％とし、又第３液の
塗布量は補強繊維に対し、固型分として０，５〜５ｗｔ
％、望ましくは１〜４ｗｔ％とするのが適当である。Note that the amounts of the vulcanizing agent and vulcanizing aid are 0.0% relative to the rubber, respectively.
5 to 15 wt%, 0.1 to 1.5 at%, preferably 1 to 10 wt%, 0.2 to 1 wt%, and the amount of the third liquid applied is 0. 5~5wt
%, preferably 1 to 4 wt%.
（作 用）
マトリクスゴムを補強するためのゴム補強用繊維上に形
成されたレゾルシンホルムアルデヒドの水溶性縮合物及
びゴムを含む第１層の上に、第１暦と親和性を有する第
２層を、第２層の上に更にマトリクスゴムと同質のゴム
を含む第３層を、形成させることにより、マトリクスゴ
ムと補強繊維の接着力を増大させ、ゴムと補強繊維との
接着力か、繰返し応力を受けるような条件下で使用した
場合においても、時間の経過とともに低下するのを防止
し、補強繊維、第１層、第２層、第３層、マトリクスゴ
ムとの界面接着力を増大させて剥離を防止する。(Function) On the first layer containing rubber and a water-soluble condensate of resorcin formaldehyde formed on rubber reinforcing fibers for reinforcing the matrix rubber, a second layer having affinity with the first layer is formed. By forming a third layer containing rubber of the same quality as the matrix rubber on the second layer, the adhesive force between the matrix rubber and the reinforcing fibers is increased, and the adhesive force between the rubber and the reinforcing fibers or the repeated stress is increased. It prevents deterioration over time and increases the interfacial adhesive strength between the reinforcing fibers, the first layer, the second layer, the third layer, and the matrix rubber, even when used under conditions that are subject to high temperatures. Prevents peeling.
又ハロゲン含有ポリマー、イソシアネート、加硫剤を含
む第２層を用いることにより、イソシアネートの使用量
を減少させ、イソシアネートを過剰に用いた場合の屈曲
疲労性並びに耐熱性の悪化を防止する。Further, by using a second layer containing a halogen-containing polymer, an isocyanate, and a vulcanizing agent, the amount of isocyanate used can be reduced, and deterioration of flex fatigue resistance and heat resistance that would occur if too much isocyanate is used can be prevented.
又、第２液自身の経時変化による性能低下を防止する。Further, performance deterioration due to aging of the second liquid itself is prevented.
更に又、第２層にカーボンブラック、シリカ等の不活性
微粉末を含有させ、第３層に加硫剤、カーボンブラック
、シリカ等の不活性微粉末を含有させることにより、本
発明の効果を一層増大させる。Furthermore, the effects of the present invention can be obtained by containing an inert fine powder such as carbon black or silica in the second layer, and by containing a vulcanizing agent, inert fine powder such as carbon black or silica in the third layer. Increase it further.
（実施例）
ビニルピリジン、スチレン及びブタジェンを１５：１５
ニア０の割合て含有するビニルピリジン−スチレン−ブ
タジェンのターポリマーラテックス（Ｐｙｒａｔｅｘ
、商品名、住友ノーガタック社製、ターポリマーの含有
量４１ｗｔ％）６５重量部、ブタジェンラテックス（０
７００、商品名、日本合成ゴム製、ブタジェンの含有量
５７ｗｔ％）８重量部、レゾルシンとホルムアルデヒド
の付加縮合物（レゾール）を２０ｗｔ％含む水溶液を１
５重量部、水１２重量部の混合物に、更に老化防止剤と
して鉱油の乳化物（鉱油の含有量５５ｗｔ％）１重量部
、アンモニア水（濃度１８ｗｔ％）を１重量部加えて第
１液（ＲＦＬ液）を得た。(Example) Vinylpyridine, styrene and butadiene at 15:15
Vinylpyridine-styrene-butadiene terpolymer latex (Pyratex
, trade name, manufactured by Sumitomo Naugatac, terpolymer content 41 wt%) 65 parts by weight, butadiene latex (0
700, trade name, Japan Synthetic Rubber Co., Ltd., butadiene content: 57 wt%) 8 parts by weight, 1 aqueous solution containing 20 wt% of an addition condensate (resol) of resorcinol and formaldehyde.
To a mixture of 5 parts by weight and 12 parts by weight of water, 1 part by weight of mineral oil emulsion (mineral oil content 55 wt%) and 1 part by weight of aqueous ammonia (concentration 18 wt%) as antioxidants were added to prepare the first liquid ( RFL liquid) was obtained.
メタクリル酸亜鉛０．８重量部、クロロスルフォン化ポ
リエチレン（へイバロン４０、商品名、昭和電エデュボ
ン社製）６重量部、ポリイソシアネー）−（ＭＲ−２０
０、商品名、日本ポリウレタン社製）１．１重量部、ｐ
、ｐ −ジベンゾイルベンゾキノンジオキシム（加硫
剤）１．５重量部、トルエンを加えて、濃度１０ｗｔ％
の第２液を得た。0.8 parts by weight of zinc methacrylate, 6 parts by weight of chlorosulfonated polyethylene (Heibalon 40, trade name, manufactured by Showa Den Edubon Co., Ltd.), polyisocyanate (MR-20)
0, trade name, manufactured by Nippon Polyurethane Co., Ltd.) 1.1 parts by weight, p
, 1.5 parts by weight of p-dibenzoylbenzoquinone dioxime (vulcanizing agent) and toluene were added to give a concentration of 10 wt%.
A second liquid was obtained.
エチレン−プロピレンゴムのトルエン溶液（濃度７．５
ｗｔ％）に、粒径５０ｍＩＬのカーボンブラックをゴ
ムに対し５０ｗｔ％懸濁させ、更にイオウを１、Ｏｗｔ
％加えて第３液を得た。Toluene solution of ethylene-propylene rubber (concentration 7.5
wt%), carbon black with a particle size of 50 ml was suspended at 50 wt% in the rubber, and sulfur was further added to 1 Owt%.
% was added to obtain a third solution.
第１液を、９ｐのガラス繊維を２００本集束してなるガ
ラス繊維束３本を引揃え、常法に従って付与した（固型
分１７ｗｔ％）。２５０℃で１分間乾燥後、このガラス
繊維束に２．５４ ｃｍ当り４．０回のＺ撚り（下撚り
）を与え、更にこの下撚りを与えた繊維束を１３本引揃
えて２．５４ ｃｍ当り２．１回のＳ撚り（上撚り）を
施したものに第２液を固型分として２％付与した後、１
４０°Ｃて１分間乾燥し、更に第３液を固型分として２
ｗｔ％付与し、１４０℃で１分間加熱、乾燥したものを
、補強繊維として使用し、試験片を作成した。The first liquid was applied to three glass fiber bundles made of 200 9p glass fibers in a conventional manner (solid content: 17 wt%). After drying at 250°C for 1 minute, this glass fiber bundle was given 4.0 Z twists (pre-twist) per 2.54 cm, and 13 fiber bundles to which this pre-twist had been given were pulled together to give a 2.54 cm After applying 2% of the second liquid as a solid content to the S twist (ply twist) of 2.1 times per cm,
Dry at 40°C for 1 minute, and then add the third liquid as a solid to 2.
wt%, heated and dried at 140° C. for 1 minute, and used as reinforcing fibers to prepare test pieces.
ゴムの種類
エチレン−プロピレンゴム１００重量部に対しカーボン
ブラック５０重量部、ステアリン酸５重量部、老化防止
剤２．５重量部、加硫剤１重量部、加硫促進剤１．５重
量部、可塑剤５重量部を配合したもの。Type of rubber: 100 parts by weight of ethylene-propylene rubber: 50 parts by weight of carbon black, 5 parts by weight of stearic acid, 2.5 parts by weight of anti-aging agent, 1 part by weight of vulcanizing agent, 1.5 parts by weight of vulcanization accelerator, Contains 5 parts by weight of plasticizer.
試験片の作成
上記組成を有するゴムを使用し、次のような試験片を作
成した。Preparation of test piece The following test piece was prepared using rubber having the above composition.
試験片１
厚み１麿朧、輻１０■■、長さ５００■のゴムシートの
間に上記補強繊維を１本挟んでプレスし、１６０°Ｃて
、３０分間加硫。Test piece 1 One of the above-mentioned reinforcing fibers was sandwiched between rubber sheets with a thickness of 1 mm, a width of 10 mm, and a length of 500 mm, pressed, and vulcanized at 160°C for 30 minutes.
試験片２
厚み３ ｍｍ、輻２５．４ ａｍ 、長さ１００ｍｍの
ゴムシートの間に上記補強繊維を隙間なく並べ、プレス
して、１６０℃て２０分間加硫。Test piece 2 The reinforcing fibers were arranged without gaps between rubber sheets with a thickness of 3 mm, a diameter of 25.4 am, and a length of 100 mm, pressed, and vulcanized at 160° C. for 20 minutes.
この試験片ｌを用い、室温で屈曲疲労試験機を使用し、
破断化の屈曲回数を測定した。Using this test piece l, a bending fatigue tester was used at room temperature,
The number of bends at breakage was measured.
この試験片２をオートグラフを用い、５０■■／１ｎの
引張り速度で剥離し、接着力を測定した。This test piece 2 was peeled off using an autograph at a tensile speed of 50 mm/1 n, and the adhesive strength was measured.
上記テストの結果を別表に示す。The results of the above tests are shown in the attached table.
（比較例）
上記実施例の第１液、第２液のみを使用し第３液を使用
することなく同一の実験を行った（比較例１）。(Comparative Example) The same experiment was conducted using only the first and second liquids of the above example but without using the third liquid (Comparative Example 1).
又実施例の第１液で処理し、第２液、第３液による処理
を全く行わなかった場合についても同様な実験を行った
（比較例２）。A similar experiment was also conducted in the case where the first liquid of the example was used and the second and third liquids were not used at all (Comparative Example 2).
これらの実験の結果を別表に示す。The results of these experiments are shown in the attached table.
別 表
（発明の効果）
繰返し屈曲強度を与える条件下て長時間使用した場合で
も接着強度の低下は小さく、マトリクスゴムとしてクロ
ロスルフォン化ポリエチレン、水素化ニトリルゴム等を
使用した場合でも大きな接着力を有し、屈曲疲労性か大
幅に向上する。Attached Table (Effects of the Invention) Even when used for a long time under conditions that provide repeated bending strength, the decrease in adhesive strength is small, and even when chlorosulfonated polyethylene, hydrogenated nitrile rubber, etc. are used as the matrix rubber, high adhesive strength is maintained. This greatly improves bending fatigue resistance.
Claims (4)
において、該繊維上に形成されたレゾルシンホルムアル
デヒドの水溶性縮合物及びゴムを含む第１層の上に、第
１層と親和性を有する第２層を、第２層の上に更にマト
リクスゴムと同質のゴムを含む第３層を形成させたゴム
補強用繊維。(1) In a rubber reinforcing fiber for reinforcing matrix rubber, a first layer containing a water-soluble condensate of resorcin formaldehyde and rubber formed on the fiber, and having an affinity with the first layer, is formed on the first layer. A rubber reinforcing fiber comprising two layers, and a third layer containing the same rubber as the matrix rubber formed on the second layer.
、加硫剤を含む請求項１記載のゴム補強用繊維。(2) The rubber reinforcing fiber according to claim 1, wherein the second layer contains a halogen-containing polymer, an isocyanate, and a vulcanizing agent.
、加硫剤、カーボンブラック又はシリカ等の不活性微粉
末を含む請求項１記載のゴム補強用繊維。(3) The rubber reinforcing fiber according to claim 1, wherein the second layer contains a halogen-containing polymer, an isocyanate, a vulcanizing agent, carbon black, or an inert fine powder such as silica.
カーボンブラック又はシリカ等の不活性微粉末を含む請
求項１、２又は３記載のゴム補強用繊維。(4) The third layer is a rubber of the same quality as the matrix rubber, a vulcanizing agent,
The rubber reinforcing fiber according to claim 1, 2 or 3, containing an inert fine powder such as carbon black or silica.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2068447A JPH03269177A (en) | 1990-03-20 | 1990-03-20 | Rubber reinforcing fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2068447A JPH03269177A (en) | 1990-03-20 | 1990-03-20 | Rubber reinforcing fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03269177A true JPH03269177A (en) | 1991-11-29 |
| JPH0571710B2 JPH0571710B2 (en) | 1993-10-07 |
Family
ID=13373970
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2068447A Granted JPH03269177A (en) | 1990-03-20 | 1990-03-20 | Rubber reinforcing fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03269177A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002309484A (en) * | 2001-04-18 | 2002-10-23 | Nippon Sheet Glass Co Ltd | Treating agent, rubber-reinforcing cord, and rubber product |
| US6929857B2 (en) | 2001-03-12 | 2005-08-16 | Honda Giken Kogyo Kabushiki Kaisha | Fiber for reinforcing rubber products |
| WO2008146708A1 (en) * | 2007-05-25 | 2008-12-04 | Nippon Sheet Glass Company, Limited | Rubber reinforcing member and rubber product utilizing the same |
| US7814741B2 (en) | 2005-12-13 | 2010-10-19 | Ocv Intellectual Capital, Llc | Glass fiber for reinforcing rubber products and method for producing it |
| US20150369336A1 (en) * | 2013-01-30 | 2015-12-24 | Nippon Sheet Glass Company, Limited | Carbon fiber cord for reinforcing rubber product and rubber product using the same |
-
1990
- 1990-03-20 JP JP2068447A patent/JPH03269177A/en active Granted
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6929857B2 (en) | 2001-03-12 | 2005-08-16 | Honda Giken Kogyo Kabushiki Kaisha | Fiber for reinforcing rubber products |
| JP2002309484A (en) * | 2001-04-18 | 2002-10-23 | Nippon Sheet Glass Co Ltd | Treating agent, rubber-reinforcing cord, and rubber product |
| WO2002086226A1 (en) * | 2001-04-18 | 2002-10-31 | Nippon Sheet Glass Co., Ltd. | Treating agent, cord for rubber reinforcement, and rubber product |
| KR100842338B1 (en) * | 2001-04-18 | 2008-06-30 | 닛폰 이타가라스 가부시키가이샤 | Treating agent, cord for rubber reinforcement, and rubber product |
| JP4520069B2 (en) * | 2001-04-18 | 2010-08-04 | 日本板硝子株式会社 | Treatment agent, rubber reinforcing cord and rubber product |
| US7814741B2 (en) | 2005-12-13 | 2010-10-19 | Ocv Intellectual Capital, Llc | Glass fiber for reinforcing rubber products and method for producing it |
| WO2008146708A1 (en) * | 2007-05-25 | 2008-12-04 | Nippon Sheet Glass Company, Limited | Rubber reinforcing member and rubber product utilizing the same |
| JP5290967B2 (en) * | 2007-05-25 | 2013-09-18 | 日本板硝子株式会社 | Rubber reinforcing member and rubber product using the same |
| US8962129B2 (en) | 2007-05-25 | 2015-02-24 | Nippon Sheet Glass Company, Limited | Rubber-reinforcing member and rubber product utilizing the same |
| US20150369336A1 (en) * | 2013-01-30 | 2015-12-24 | Nippon Sheet Glass Company, Limited | Carbon fiber cord for reinforcing rubber product and rubber product using the same |
| US9752649B2 (en) * | 2013-01-30 | 2017-09-05 | Nippon Sheet Glass Company, Limited | Carbon fiber cord for reinforcing rubber product and rubber product using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0571710B2 (en) | 1993-10-07 |
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