JPH04202332A - Bonding of fiber to rubber formulation - Google Patents
Bonding of fiber to rubber formulationInfo
- Publication number
- JPH04202332A JPH04202332A JP2334372A JP33437290A JPH04202332A JP H04202332 A JPH04202332 A JP H04202332A JP 2334372 A JP2334372 A JP 2334372A JP 33437290 A JP33437290 A JP 33437290A JP H04202332 A JPH04202332 A JP H04202332A
- Authority
- JP
- Japan
- Prior art keywords
- fibers
- rubber
- bonding
- fiber
- urethane prepolymer
- 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
- 239000000835 fiber Substances 0.000 title claims abstract description 58
- 238000010058 rubber compounding Methods 0.000 title abstract 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003822 epoxy resin Substances 0.000 claims abstract description 18
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 18
- 229920000768 polyamine Polymers 0.000 claims abstract description 15
- 229920000126 latex Polymers 0.000 claims abstract description 14
- 125000003277 amino group Chemical group 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 30
- 229920001971 elastomer Polymers 0.000 claims description 30
- 239000005060 rubber Substances 0.000 claims description 30
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 7
- 150000001412 amines Chemical class 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 230000000717 retained effect Effects 0.000 abstract 1
- 239000000853 adhesive Substances 0.000 description 14
- 230000001070 adhesive effect Effects 0.000 description 14
- 239000002131 composite material Substances 0.000 description 11
- 229960001755 resorcinol Drugs 0.000 description 9
- -1 tires Substances 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 4
- 229920001084 poly(chloroprene) Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000004760 aramid Substances 0.000 description 3
- 229920003235 aromatic polyamide Polymers 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 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
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-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
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 1
- SOKFWRPORPTXSA-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)-2-methylpropyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)CC1=CC=C(O)C=C1 SOKFWRPORPTXSA-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 229940072049 amyl acetate Drugs 0.000 description 1
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 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
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 239000004761 kevlar Substances 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
- 239000000463 material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920006174 synthetic rubber latex Polymers 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-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
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Reinforced Plastic Materials (AREA)
- Tyre Moulding (AREA)
Abstract
Description
【発明の詳細な説明】
童呈上少剋里圀団
本発明は、繊維とゴム配合物との接着方法に関し、詳し
くは、繊維の強力を保持しつつ、繊維とゴム配合物との
間に強固な接着を達成することができる繊維とゴム配合
物との接着方法に関する。[Detailed Description of the Invention] The present invention relates to a method of adhering fibers and rubber compounds, and more specifically, it relates to a method of adhering fibers and rubber compounds, and more specifically, to bonding between fibers and rubber compounds while maintaining the strength of the fibers. The present invention relates to a method of adhering fibers and rubber compounds that can achieve strong adhesion.
従来■及歪
一般に、タイヤ、ゴム・ホース、伝動ヘルド、コンヘヤ
ヘルト等の工業用ゴム製品は、ゴムに繊維材料を接着し
て補強されてなる接着複合体である。従来、このように
、繊維とゴム配合物とを接着するには、通常、レゾルシ
ン・ホルマリン・ゴムラテックス混合液（以下、ＲＦＬ
液という。）にて繊維を処理する方法が知られている。BACKGROUND OF THE INVENTION In general, industrial rubber products such as tires, rubber hoses, power transmission healds, conveyor healds, etc. are adhesive composites made by bonding and reinforcing fiber materials to rubber. Conventionally, in order to bond fibers and rubber compounds in this way, a resorcinol/formalin/rubber latex mixture (hereinafter referred to as RFL) is usually used.
It's called liquid. ) is known.
しかし、この方法によれば、多くの場合、繊維とゴム配
合物との間に得られる接着力は不十分である。However, this method often provides insufficient adhesion between the fibers and the rubber compound.
そこで、従来、かかる問題を解決するために、繊維をＲ
ＦＬ処理する前に、エポキシ樹脂で処理する方法が提案
されている。エポキシ樹脂による前処理は、接着性にす
ぐれる接着複合体を与えるものの、耐衝撃性に劣る。そ
こで、例えば、特開昭５８−５２４３号公報には、繊維
をエポキシ化合物と液状ゴムとを含む溶液にて処理した
後、ＲＦＬ液にて処理する方法が記載されている。また
、特開昭５８−１２４６３１号公報には、ウレタン変性
エポキシ樹脂にて繊維を処理した後、ＲＦＬ液にて処理
する方法が提案されている。Therefore, conventionally, in order to solve this problem, fibers were
A method of treating with epoxy resin before FL treatment has been proposed. Pretreatment with epoxy resin provides a bonded composite with good adhesion but poor impact resistance. For example, JP-A-58-5243 describes a method in which fibers are treated with a solution containing an epoxy compound and liquid rubber and then treated with an RFL liquid. Further, Japanese Patent Application Laid-Open No. 124631/1983 proposes a method in which fibers are treated with a urethane-modified epoxy resin and then treated with an RFL liquid.
これらの方法によれば、接着力及び可撓性にすぐれる接
着複合体を得ることができるが、繊維の強力が低下する
傾向がみられる。このような繊維の強力の低下は、接着
複合体の耐久性を低めるので、実用上、重要な問題であ
る。According to these methods, adhesive composites with excellent adhesive strength and flexibility can be obtained, but the strength of the fibers tends to decrease. Such a decrease in the strength of the fibers is an important problem in practice because it reduces the durability of the adhesive composite.
■が７′シようとするｉ
本発明は、従来の繊維とゴム配合物の接着における上記
したような問題を解決するためになされたものであって
、繊維の強力を保持しつつ、繊維とゴム配合物との間に
強固な接着を達成することができる繊維とゴム配合物と
の接着方法を擾供することを目的とする。The present invention was made in order to solve the above-mentioned problems in the conventional adhesion of fibers and rubber compounds. It is an object of the present invention to provide a method for adhering fibers and rubber compounds that can achieve strong adhesion to the rubber compound.
エ 占をゞするための
本発明による繊維とゴム配合物との接着方法は、エポキ
シ樹脂とブロック化ウレタンプレポリマーと分子内に１
つ以上のアミノ基を有するポリアミンとを含む処理溶液
で繊維を処理し、次いで、レゾルシン・ホルマリン・ゴ
ムラテックスにて処理した後、繊維を未加硫ゴム配合物
と加硫接着することを特徴とする。D. The method of adhering fibers and rubber compounds according to the present invention for the purpose of bonding is to bond epoxy resin, blocked urethane prepolymer, and
The fibers are treated with a treatment solution containing a polyamine having three or more amino groups, then treated with resorcinol/formalin/rubber latex, and then vulcanized and bonded to an unvulcanized rubber compound. do.
上記エポキシ樹脂は、分子内に少な（とも１つのエポキ
シ基を有する化合物であって、例え′ば、エチレングリ
コール、グリセリン、ノルビトール、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ピ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−ヒドロキシフェニル）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
とエピ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が好ましく用いられる。脂肪族又は
脂環族不飽和化合物の有する二重結合を化酢酸等にて酸
化して得られるエポキシ化合物も好ましく用いられる。The above-mentioned epoxy resin is a compound having one epoxy group in its molecule, such as polyhydric alcohols such as ethylene glycol, glycerin, norbitol, and pentaerythritol, and polyalkylene glycols such as polyethylene glycol. Reaction products with halogen-containing epoxy compounds such as epichlorohydrin, polyhydric phenols such as resorcinol, bis(4-hydroxyphenyl) dimethylethane, phenol/formamide resin, resorcinol/formamide resin, and phenolic resins such as epichlorohydrin. A reaction product with a halogen-containing epoxy compound is preferably used.An epoxy compound obtained by oxidizing the double bond of an aliphatic or alicyclic unsaturated compound with acetic acid or the like is also preferably used.
また、エポキシ基を有する種々のシランカップリング剤
も好ましく用いられる。Moreover, various silane coupling agents having an epoxy group are also preferably used.
上記ブロック化ウレタンプレポリマーは、ウレタンプレ
ポリマーの末端イソシアネート基をブロック化してなる
ものであって、既に知られており、市販品を用いること
ができる。ブロック化ウレタンプレポリマーは、例えば
、よく知られているように、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、
ポリメチレンポリフエニルジイソシアネート等のポリイ
ソシアネートと種々のポリオール類とを反応させてウレ
タンプレポリマーとし、その末端のイソシアネート基を
トリメチロールプロパン、ペンタエリスリトール等のよ
うに分子内に活性水素を２つ以上有する化合物を反応さ
せることによって得ることができる。また、ブロック化
ウレタンプレポリマーは、ウレタンプレポリマーにケト
オキシム類、フェノール類、アミン類等を反応させるこ
とによっても得ることができる。The blocked urethane prepolymer is obtained by blocking the terminal isocyanate groups of a urethane prepolymer, and is already known, and commercially available products can be used. Blocked urethane prepolymers include, for example, tolylene diisocyanate, metaphenylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, as is well known.
A polyisocyanate such as polymethylene polyphenyl diisocyanate is reacted with various polyols to form a urethane prepolymer, and the terminal isocyanate group has two or more active hydrogens in the molecule, such as trimethylolpropane, pentaerythritol, etc. It can be obtained by reacting compounds. Further, the blocked urethane prepolymer can also be obtained by reacting a urethane prepolymer with ketooximes, phenols, amines, etc.
本発明の方法において、処理溶液は、その合計量に基づ
いて、エポキシ樹脂８０〜３０］ｉ１％、ブロック化ウ
レタンプレポリマーを２０〜７０１量％含有する。また
、処理溶液は、エポキシ樹脂とブロック化ウレタンプレ
ポリマーとを合計量にて固形分で１〜２０重量％の範囲
で含有する。In the method of the invention, the treatment solution contains, based on its total amount, 80-30]i1% of epoxy resin and 20-701% by weight of blocked urethane prepolymer. Further, the treatment solution contains an epoxy resin and a blocked urethane prepolymer in a total amount of 1 to 20% by weight in terms of solid content.
更に、本発明による方法においては、処理溶液は、ポリ
アミンを含有する。このポリアミンは分子内にアミノ基
を１つ以上有する単量体化合物であって、本発明におい
ては、ウレタンプレポリマー及びエポキシ樹脂のための
硬化剤として用いられる。通常、エポキシ樹脂とポリウ
レタンとポリアミンを反応させた場合、ポリウレタンと
ポリアミンの反応が圧倒的に速いので、生成する重合体
は、可撓性は上がるが接着強さが低下する。そこで、本
発明によれば、ブロック化ウレタンプレポリマーを用い
ることにより、エポキシ樹脂とポリアミンの反応速度、
ブロック化ウレタンプレポリマーとポリアミンの反応速
度をほぼ同じにし、接着強さを低下させることなく可撓
性を得る。Furthermore, in the method according to the invention, the treatment solution contains a polyamine. This polyamine is a monomeric compound having one or more amino groups in its molecule, and is used as a curing agent for urethane prepolymers and epoxy resins in the present invention. Normally, when an epoxy resin, polyurethane, and polyamine are reacted, the reaction between the polyurethane and the polyamine is overwhelmingly fast, so the resulting polymer has increased flexibility but reduced adhesive strength. Therefore, according to the present invention, by using a blocked urethane prepolymer, the reaction rate between the epoxy resin and the polyamine can be improved.
The reaction rate of blocked urethane prepolymer and polyamine is almost the same, and flexibility is obtained without reducing adhesive strength.
本発明においては、このようなポリアミンとして、例え
ば、ジエチレントリアミン、３，３゛−ジクロロ−４，
４′−ジアミノジフェニルメタン、トリエチレンテトラ
ミン、テトラエチレンペンタミン、３．３”−ジメチル
−４，４゛−ジアミノジシクロヘキシルメタン、ポリア
ミドポリアミン、メンセンジアミン、イソホロンジアミ
ン、メタキシレンジアミン、ジアミノジフェニルメタン
、ジアミノジフェニルスルホン、ジシアンジアミド等を
挙げることができる。In the present invention, such polyamines include, for example, diethylenetriamine, 3,3'-dichloro-4,
4'-diaminodiphenylmethane, triethylenetetramine, tetraethylenepentamine, 3.3"-dimethyl-4,4'-diaminodicyclohexylmethane, polyamide polyamine, menthene diamine, isophorone diamine, metaxylene diamine, diaminodiphenylmethane, diaminodiphenyl Examples include sulfone, dicyandiamide, and the like.
本発明において、かかるポリアミンは、特に限定される
ものではないが、通常、（エポキシ基十イソシアネート
基）／アミンの活性水素当量が０゜５〜１．５の範囲と
なるように含まれる。In the present invention, such a polyamine is usually included so that the active hydrogen equivalent of (epoxy group and isocyanate group)/amine is in the range of 0.5 to 1.5, although it is not particularly limited.
このような処理溶液を形成するための溶剤としては、特
に、限定されるものではないが、通常、ヘンゼン、キシ
レン、トルエン等の芳香族炭化水素、メチルエチルケト
ン、メチルイソブチルケトン等の脂肪族ケトン、酢酸エ
チル、酢酸アミル等のエステル等が好適に用いられる。Solvents for forming such treatment solutions are typically, but not limited to, aromatic hydrocarbons such as Hensen, xylene, toluene, aliphatic ketones such as methyl ethyl ketone, methyl isobutyl ketone, and acetic acid. Esters such as ethyl and amyl acetate are preferably used.
このような処理溶液による繊維の処理は、通常、繊維を
処理溶液に浸漬した後、熱処理することによって行なわ
れる。この熱処理は、繊維に付着させた処理溶液を反応
定着させるに足る温度にて行なえばよく、通常、１６０
〜２５０°Ｃにて数分間処理すればよい。Treatment of fibers with such a treatment solution is usually carried out by immersing the fibers in the treatment solution and then heat-treating the fibers. This heat treatment may be carried out at a temperature sufficient to react and fix the treatment solution attached to the fibers, and is usually carried out at a temperature of 160°C.
It is sufficient to process at ~250°C for several minutes.
次いで、本発明の方法によれば、繊維をＲＦＬ液にて処
理する。ＲＦＬ液は、前述したように、レゾルシン・ホ
ルマリンとゴムラテックスの水性混合物であり、従来よ
り、一般にゴムと繊維との接着において知られているも
のであって、通常、レゾルシンとホルマリンとをレゾル
シン／ホルマリンモル比１／３〜３／１にて塩基性触媒
の存在下に縮合させて得られる初期縮合物をゴムラテッ
クスと混合してなる水性混合物である。レゾルシン／ホ
ルマリンモル比が上記範囲をはずれるときは、接着に必
要な分子量を有する初期縮合物を得ることができない。According to the method of the invention, the fibers are then treated with an RFL liquid. As mentioned above, RFL liquid is an aqueous mixture of resorcin/formalin and rubber latex, and is conventionally known for bonding rubber and fibers. This is an aqueous mixture obtained by mixing an initial condensate obtained by condensing formalin in the presence of a basic catalyst at a molar ratio of 1/3 to 3/1 with rubber latex. When the resorcin/formalin molar ratio is outside the above range, it is not possible to obtain an initial condensate having a molecular weight necessary for adhesion.
上記ゴムラテックスとしては、通常、合成ゴムラテック
スが用いられる。例えば、クロロプレンゴムラテックス
、スチレン−ブタジェン−ビニルピリシンゴムラテック
ス、アクリロニトリループクジエンゴムラテックス、水
素化ニトリルゴムラテックス等が好適に用いられる。As the rubber latex, synthetic rubber latex is usually used. For example, chloroprene rubber latex, styrene-butadiene-vinylpyricine rubber latex, acrylonitrile rubber latex, hydrogenated nitrile rubber latex, etc. are preferably used.
繊維のＲＦＬ液による処理も、繊維に付着させたＲＦＬ
液を繊維に反応定着させるに足る温度にて行なえばよ（
、通常、１００〜２７０ ’Ｃにて数分間処理すればよ
い。Treatment of fibers with RFL liquid also involves the treatment of RFL attached to fibers.
Just do it at a temperature high enough to cause the liquid to react and fix on the fibers (
, usually at 100 to 270'C for several minutes.
以上のように処理した繊維をゴム配合物と密着され、そ
のゴム配合物において知られている通常の処理条件にて
加硫接着することによって、繊維の強力を保持しつつ、
繊維とゴム配合物との間に強固な接着を達成することが
できる。The fibers treated as described above are brought into close contact with a rubber compound and vulcanized and bonded under normal processing conditions known for the rubber compound, thereby maintaining the strength of the fibers.
Strong adhesion can be achieved between the fibers and the rubber compound.
本発明においては、ゴムとしては、例えば、天然ゴム、
ブタジェンゴム、イソプレンゴム、スチレン−ブタジェ
ンゴム、エチレン−プロピレンゴム、ブチルゴム、クロ
ロプレンゴム、アクリロニトリル−ブタジェンゴム、水
素化ニトリルゴム、ウレタンゴム、シリコーンゴム、フ
ッ素ゴム等が用いられる。かかるゴムは、それぞれに応
じて、通常のゴム配合物として知られてる種々の補強性
充填剤、老化防止剤、可塑剤、加硫助剤、加工助剤等の
適宜量を含有してもよい。In the present invention, examples of rubber include natural rubber,
Butadiene rubber, isoprene rubber, styrene-butadiene rubber, ethylene-propylene rubber, butyl rubber, chloroprene rubber, acrylonitrile-butadiene rubber, hydrogenated nitrile rubber, urethane rubber, silicone rubber, fluororubber, etc. are used. Such rubbers may contain appropriate amounts of various reinforcing fillers, anti-aging agents, plasticizers, vulcanization aids, processing aids, etc., which are known as conventional rubber compounds. .
また、繊維としては、代表的には、絹、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、これらに限定されるものではない。In addition, typical examples of fibers include silk, human silk, polyvinyl alcohol fiber, aliphatic and aromatic polyamide fiber,
Examples include polyester fiber, carbon fiber, glass fiber, etc., but are not limited to these.
尖隻炭
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 described below with reference to Examples, but the present invention is not limited to these Examples in any way.
実施例１
第１表に示すように、種々の配合組成の処理溶液を調製
し、これにポリエステル繊維コード（１０００Ｄ／２Ｘ
５）を浸漬した後、２３５°Ｃで１分間熱処理した。Example 1 As shown in Table 1, treatment solutions with various compositions were prepared, and polyester fiber cords (1000D/2X
5), and then heat treated at 235°C for 1 minute.
レゾルシン１７重量部、ホルマリン１５重量部、１０重
量％水酸化ナトリウム水溶液１３重量部及び脱イオン水
を用いてレゾルシン・ホルマリン樹脂液を調製し、この
レゾルシン・ホルマリン樹脂ｉ３０重量部をクロロプレ
ンゴムラテックス３２重量部及び脱イオン水３８重量部
と混合して、ＲＦＬ液を調製した。A resorcinol/formalin resin solution was prepared using 17 parts by weight of resorcin, 15 parts by weight of formalin, 13 parts by weight of a 10% by weight aqueous sodium hydroxide solution, and deionized water, and 30 parts by weight of this resorcin/formalin resin i was mixed with 32 parts by weight of chloroprene rubber latex. An RFL solution was prepared by mixing 1 part with 38 parts by weight of deionized water.
前記繊維コードをこのＲＦＬ液に浸漬し、２００°Ｃで
１分間熱処理した。The fiber cord was immersed in this RFL liquid and heat treated at 200°C for 1 minute.
次いで、クロロプレンゴム１００重量部、酸化マグネシ
ウム４重量部、酸化亜鉛１５重量部、加硫促進剤２重量
部、イオウ０．５重量部、老化防止剤２重量部、カーボ
ンブラック６５重量部及びオイル８重量部なる組成を有
するゴム配合物の未加硫シート上に上記繊維コードを平
行に配列し、１７０°Ｃで３０分間加硫して、接着複合
体を得た。Next, 100 parts by weight of chloroprene rubber, 4 parts by weight of magnesium oxide, 15 parts by weight of zinc oxide, 2 parts by weight of vulcanization accelerator, 0.5 parts by weight of sulfur, 2 parts by weight of anti-aging agent, 65 parts by weight of carbon black, and 8 parts by weight of oil. The above fiber cords were arranged in parallel on an unvulcanized sheet of a rubber compound having a composition of parts by weight, and vulcanized at 170°C for 30 minutes to obtain an adhesive composite.
この接着複合体から輻１インチの試料を裁断し、剥離速
度１００ｍｍ／分にて繊維コードとゴムとの間の１８０
°剥離接着力を測定した。結果を第１図に示す。A 1-inch sample was cut from this adhesive composite, and the 180 mm diameter between the fiber cord and the rubber was cut at a peeling speed of 100 mm/min.
°Peel adhesion was measured. The results are shown in Figure 1.
実施例２
実施例１において、繊維コードとして、芳香族ポリアミ
ド繊維コード（デュポン社製ケブラー繊維からなる１５
００Ｄ／２ｘ３の繊維コード）を用いた以外は、実施例
１と同様にして、接着複合体を得、１８０“剥離接着力
を測定した。結果を第２図に示す。
（登里久四果
１以上のように、本発明の方法によ
れば、エポキシ樹脂とポリアミンと共に、ブロック化ウ
レタンプレポリマーを含む処理溶液で繊維を処理し、次
「いで、レゾルシン・ホルマリン・ゴムラテックス
にて処理した後、繊維を未加硫ゴム配合物と加硫接着す
ることによって、繊維の強力を保持しつつ、繊維とゴム
配合物とが強固に接着された接着複合体を得ることがで
きる。Example 2 In Example 1, the fiber cord was an aromatic polyamide fiber cord (15% made of Kevlar fiber manufactured by DuPont).
An adhesive composite was obtained in the same manner as in Example 1, except that a 00D/2x3 fiber cord was used, and the 180" peel adhesion strength was measured. The results are shown in FIG.
(Kushika Noori
As described above, according to the method of the present invention, fibers are treated with a treatment solution containing a blocked urethane prepolymer together with an epoxy resin and a polyamine, and then treated with a resorcinol-formalin-rubber latex. By vulcanizing and adhering the fibers to an unvulcanized rubber compound, it is possible to obtain an adhesive composite in which the fibers and the rubber compound are firmly bonded while maintaining the strength of the fibers.
ブロック化ウレタンプレポリマーに代えて、通常のウレ
タンプレポリマーを用いるときは、ウレタンプレポリマ
ーとポリアミンとの反応がエポキシ樹脂とポリアミンと
の反応よりも優先して起こるために、得られる接着複合
体において、繊維の強力を避けることができない。When a regular urethane prepolymer is used instead of a blocked urethane prepolymer, the reaction between the urethane prepolymer and the polyamine takes precedence over the reaction between the epoxy resin and the polyamine, so that the resulting adhesive composite is , the strength of the fiber cannot be avoided.
第１図は、処理溶液におけるブロック化ウレタンプレポ
リマーとエポキシ樹脂の重量比と、得られる接着複合体
におけるポリエステル繊維コートの接着力との関係を示
すグラフ、第２図は、処理溶液におけるブロック化ウレ
タンプレポリマーとエポキシ樹脂の重量比と、得られる
接着複合体にむける芳香族ポリアミド繊維コードの接着
力との短係を示すグラフである。
第１図
第２図Figure 1 is a graph showing the relationship between the weight ratio of blocked urethane prepolymer and epoxy resin in the treatment solution and the adhesive strength of the polyester fiber coat in the resulting adhesive composite. 1 is a graph showing the relationship between the weight ratio of urethane prepolymer and epoxy resin and the adhesion strength of an aromatic polyamide fiber cord to the resulting adhesive composite. Figure 1 Figure 2
Claims (2)
と分子内に１つ以上のアミノ基を有するポリアミンとを
含む処理溶液で繊維を処理し、次いで、レゾルシン・ホ
ルマリン・ゴムラテックスにて処理した後、繊維を未加
硫ゴム配合物と加硫接着することを特徴とする繊維とゴ
ム配合物との接着方法。(1) The fibers are treated with a treatment solution containing an epoxy resin, a blocked urethane prepolymer, and a polyamine having one or more amino groups in the molecule, and then treated with resorcinol, formalin, and rubber latex. A method for bonding fibers and a rubber compound, characterized by vulcanizing and adhering the fibers and a rubber compound to an unvulcanized rubber compound.
レポリマーとの合計量に基づいて、エポキシ樹脂を８０
〜３０重量％、ブロック化ウレタンプレポリマーを２０
〜７０重量％含有することを特徴とする請求項第１項記
載の繊維とゴム配合物との接着方法。(2) The treatment solution contains 80% of epoxy resin based on the total amount of epoxy resin and blocked urethane prepolymer.
~30% by weight, 20% blocked urethane prepolymer
The method for adhering fibers and rubber compound according to claim 1, characterized in that the content is 70% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2334372A JP3008373B2 (en) | 1990-11-29 | 1990-11-29 | Bonding method between fiber and rubber compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2334372A JP3008373B2 (en) | 1990-11-29 | 1990-11-29 | Bonding method between fiber and rubber compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04202332A true JPH04202332A (en) | 1992-07-23 |
| JP3008373B2 JP3008373B2 (en) | 2000-02-14 |
Family
ID=18276635
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2334372A Expired - Lifetime JP3008373B2 (en) | 1990-11-29 | 1990-11-29 | Bonding method between fiber and rubber compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3008373B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016145440A (en) * | 2015-01-30 | 2016-08-12 | 三ツ星ベルト株式会社 | Producing method and treatment agent for aramid core wire, and method for producing transmission belt |
-
1990
- 1990-11-29 JP JP2334372A patent/JP3008373B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016145440A (en) * | 2015-01-30 | 2016-08-12 | 三ツ星ベルト株式会社 | Producing method and treatment agent for aramid core wire, and method for producing transmission belt |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3008373B2 (en) | 2000-02-14 |
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