JP2920314B2 - Method for bonding hydrogenated nitrile rubber composition to fiber material and fiber reinforced hydrogenated nitrile rubber belt - Google Patents
Method for bonding hydrogenated nitrile rubber composition to fiber material and fiber reinforced hydrogenated nitrile rubber beltInfo
- Publication number
- JP2920314B2 JP2920314B2 JP2142131A JP14213190A JP2920314B2 JP 2920314 B2 JP2920314 B2 JP 2920314B2 JP 2142131 A JP2142131 A JP 2142131A JP 14213190 A JP14213190 A JP 14213190A JP 2920314 B2 JP2920314 B2 JP 2920314B2
- Authority
- JP
- Japan
- Prior art keywords
- nitrile rubber
- hydrogenated nitrile
- rubber composition
- fiber
- fiber material
- 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.)
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- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、水素化ニトリルゴム組成物と繊維材料との
接着方法および前記方法によって製造された繊維強化水
素化ニトリルゴムベルトに関する。Description: TECHNICAL FIELD The present invention relates to a method for bonding a hydrogenated nitrile rubber composition to a fiber material and a fiber reinforced hydrogenated nitrile rubber belt produced by the method.
従来の技術 水素化ニトリルゴムは、ニトリルゴムのブタジエンユ
ニットを水素化した高飽和ゴムであり、ニトリル基によ
る耐油性ならびに水素化に起因する耐熱性を合わせ持つ
エラストマーである。近年、この水素化ニトリルゴムに
エチレン性不飽和カルボン酸金属塩を配合した水素化ニ
トリルゴム組成物（ZSC 登録商標、日本ゼオン製）が上
市され、その優れた高強度、耐熱性が注目され、各方
面、各用途への展開が進んでいる。2. Description of the Related Art Hydrogenated nitrile rubber is a highly saturated rubber obtained by hydrogenating a butadiene unit of a nitrile rubber, and is an elastomer having both oil resistance due to a nitrile group and heat resistance due to hydrogenation. In recent years, a hydrogenated nitrile rubber composition (ZSC registered trademark, manufactured by Zeon Corporation) in which an ethylenically unsaturated carboxylic acid metal salt is blended with this hydrogenated nitrile rubber has been marketed, and its excellent high strength and heat resistance have attracted attention. Development in various fields and applications is progressing.
ところで、ホース、伝動ベルト、コンベアベルト、な
どのゴム製品、特にゴムベルトは、通常ゴム組成物が繊
維材料によって強化されている。この強化されたゴムベ
ルトは、ゴム組成物と繊維材料との強固な接着が要求さ
れる。前記水素化ニトリルゴム組成物を、このようなゴ
ム製品に適用した場合も同様に繊維材料との強力な接着
力が必要であるが、従来から用いられているレゾルシン
−ホルマリン−ラテックス法（以下RFL法と略称する）
では、ゴム破壊に至るまでの接着力は得ることはできな
い。By the way, rubber products such as hoses, transmission belts, conveyor belts and the like, particularly rubber belts, are usually reinforced with a rubber composition by a fiber material. This reinforced rubber belt requires strong adhesion between the rubber composition and the fiber material. When the above-mentioned hydrogenated nitrile rubber composition is applied to such a rubber product, a strong adhesive force with a fiber material is similarly required. However, the resorcinol-formalin-latex method (hereinafter referred to as RFL) has been conventionally used. Abbreviated as law)
Then, it is not possible to obtain the adhesive strength up to the destruction of rubber.
発明が解決しようとする課題 したがって、本発明の目的は、上記技術的課題を解決
し、水素化ニトリルゴム組成物と繊維材料とを強固に接
着する方法およびこの方法によって製造された繊維強化
水素化ニトリルゴムベルトを提供することである。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above technical problems, to provide a method for firmly bonding a hydrogenated nitrile rubber composition to a fiber material, and a fiber reinforced hydrogenation produced by this method. It is to provide a nitrile rubber belt.
課題を解決するための手段 本発明者らは鋭意研究を進めた結果、繊維材料を予め
エポキシ基を含有する化合物と硬化剤とで処理し、この
繊維材料と、エチレン性不飽和カルボン酸金属塩と有機
過酸化物を含む水素化ニトリルゴム組成物とを密着架橋
することによって、強固な接着が得られることを見いだ
し本発明に至った。Means for Solving the Problems As a result of intensive studies, the present inventors have previously treated a fiber material with a compound containing an epoxy group and a curing agent, and obtained the fiber material and an ethylenically unsaturated carboxylic acid metal salt. The present inventors have found that strong adhesion can be obtained by tightly cross-linking a hydrogenated nitrile rubber composition containing an organic peroxide with a hydrogenated nitrile rubber composition, and have accomplished the present invention.
すなわち本発明は、繊維材料にエポキシ基含有化合物
と硬化剤とを含む処理液を含浸、加熱した後、有機過酸
化物およびエチレン性不飽和カルボン酸の金属塩を配合
した水素化ニトリルゴム組成物と密着加熱して、両者の
間を架橋することを特徴とする水素化ニトリルゴム組成
物と繊維材料との接着方法およびこの方法によって製造
された繊維強化水素化ニトリルゴムベルトである。That is, the present invention relates to a hydrogenated nitrile rubber composition in which a fiber material is impregnated with a treatment liquid containing an epoxy group-containing compound and a curing agent, heated, and then mixed with an organic peroxide and a metal salt of an ethylenically unsaturated carboxylic acid. And a method for bonding a hydrogenated nitrile rubber composition and a fiber material, characterized in that the two are cross-linked by heating in close contact with each other, and a fiber-reinforced hydrogenated nitrile rubber belt produced by this method.
本発明において、エポキシ基含有化合物とは、多価ア
ルコール、ポリアルキレングリコール、フェノール類、
フェノー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である通常のエポキシ
樹脂またはエポキシ基含有シランカップリング剤などで
あり、これらの一種以上が使用される。In the present invention, the epoxy group-containing compound is a polyhydric alcohol, a polyalkylene glycol, a phenol,
It is an ordinary epoxy resin or an epoxy group-containing silane coupling agent which is a reaction product of a phenol resin and a halogen-containing epoxy compound such as epichlorohydrin, and one or more of these are used.
本発明において、これらエポキシ基含有化合物は通常
溶液とされ、アミン類、有機酸または無水物などの硬化
剤とともに用いられる。また繊維材料は、この溶液に浸
漬した後、加熱処理される。この加熱処理は用いる繊維
材料、エポキシ基含有化合物の種類にもよるが、通常10
0℃〜240℃にて数分間行えばよい。なお、前記硬化剤量
ならびに加熱処理により処理後の残存エポキシ基量が少
なくなりすぎると強固な接着力は発現しなくなるため、
充分注意する必要がある。In the present invention, these epoxy group-containing compounds are usually made into a solution, and used together with a curing agent such as an amine, an organic acid or an anhydride. The fiber material is subjected to a heat treatment after being immersed in this solution. Although this heat treatment depends on the type of the fiber material and the epoxy group-containing compound to be used, it is usually 10 hours.
It may be performed at 0 ° C. to 240 ° C. for several minutes. Note that if the amount of the curing agent and the amount of residual epoxy groups after the treatment by the heat treatment become too small, a strong adhesive force will not be developed,
Care must be taken.
本発明において、水素化ニトリルゴムは特に限定され
るものではないが、その耐熱性を発現させるため、水素
添加率が80％以上のものが好適に用いられる。In the present invention, the hydrogenated nitrile rubber is not particularly limited, but those having a hydrogenation rate of 80% or more are preferably used in order to exhibit the heat resistance.
本発明において、有機過酸化物とは、通常ゴムの過酸
化物架橋に用いられるものであればよく、特に限定され
ない。たとえばジクミルパーオキサイド、ジ−ｔ−ブチ
ルパーオキサイド、ｔ−ブチルクミルパーオキサイド、
ベンゾイルパーオキサイド、2,5−ジメチル−2,5−ジ
（ｔ−ブチルパーオキシ）ヘキシン−３、2,5−ジメチ
ル−2,5−ジ（ベンゾイルパーオキシ）ヘキサン、2,5−
ジメチル−2,5−モノ（ｔ−ブチルパーオキシ）−ヘキ
サンなどが挙げられる。これらの有機過酸化物は１種以
上使用され、通常ゴム組成物100重量部に対して0.2〜10
重量部の範囲で使用されるが、要求される物性値に応じ
て適宜最適量を決定することができる。In the present invention, the organic peroxide is not particularly limited as long as it is usually used for peroxide crosslinking of rubber. For example, dicumyl peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide,
Benzoyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-
Dimethyl-2,5-mono (t-butylperoxy) -hexane and the like. One or more of these organic peroxides are used, and usually 0.2 to 10 parts by weight per 100 parts by weight of the rubber composition.
Although used in the range of parts by weight, the optimum amount can be appropriately determined according to the required physical property values.
本発明で使用されるエチレン性不飽和カルボン酸の金
属塩は（メタ）アクリル酸、クロトン酸、３−ブテン酸
などの不飽和モノカルボン酸；マレイン酸、フマル酸、
イタコン酸などの不飽和ジカルボン酸；マレイン酸モノ
メチル、マレイン酸モノエチル、イタコン酸モノエチル
などの不飽和ジカルボン酸のモノエステル、前記以外の
不飽和多価カルボン酸および少なくとも１個のフリーの
カルボキシル基を残した不飽和多価カルボン酸のエステ
ルの少なくとも１種の金属塩である。金属塩を構成する
金属としては上記のカルボン酸と塩を形成するものであ
れば特に制限されないが、亜鉛、マグネシウム、カルシ
ウムおよびアルミニウムが特に適している。The metal salt of the ethylenically unsaturated carboxylic acid used in the present invention includes unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, and 3-butenoic acid; maleic acid, fumaric acid,
Unsaturated dicarboxylic acids such as itaconic acid; monoesters of unsaturated dicarboxylic acids such as monomethyl maleate, monoethyl maleate and monoethyl itaconate, other unsaturated polycarboxylic acids and at least one free carboxyl group And at least one metal salt of an ester of an unsaturated polycarboxylic acid. The metal constituting the metal salt is not particularly limited as long as it forms a salt with the above carboxylic acid, but zinc, magnesium, calcium and aluminum are particularly suitable.
これらのエチレン性不飽和カルボン酸の金属塩は該金
属塩として使用してもよく、また、本発明の組成物製造
時にゴム組成物中で前記のエチレン性不飽和カルボン酸
と前記金属の酸化物、水酸化物あるいは炭酸塩とを反応
させてゴム組成物中でエチレン性不飽和カルボン酸の金
属塩を生成させる方法によってもよい。該金属塩の使用
量は特に制限されないが、ゴム組成物100重量部当り３
〜100重量部の範囲が好ましい。３重量部未満および100
重量部を越えると強度特性の改良効果は少ない。好まし
くは５〜60重量部である。These metal salts of the ethylenically unsaturated carboxylic acid may be used as the metal salt, and the above-mentioned ethylenically unsaturated carboxylic acid and the oxide of the metal may be used in the rubber composition during the production of the composition of the present invention. , A hydroxide or a carbonate to form a metal salt of an ethylenically unsaturated carboxylic acid in the rubber composition. The amount of the metal salt used is not particularly limited, but may be 3 to 100 parts by weight of the rubber composition.
A range of 100100 parts by weight is preferred. Less than 3 parts by weight and 100
Exceeding the parts by weight has little effect on improving the strength characteristics. Preferably it is 5 to 60 parts by weight.
上記エチレン性不飽和カルボン酸金属塩は、水素化ニ
トリルゴム組成物に配合混練して使用してもよく、ま
た、市販されているエチレン性不飽和カルボン酸金属塩
配合水素化ニトリルゴム組成物、たとえばZSC（登録商
標、日本ゼオン製）を用いてもよい。The metal salt of an ethylenically unsaturated carboxylic acid may be used by compounding and kneading with a hydrogenated nitrile rubber composition, or a commercially available hydrogenated nitrile rubber composition containing a metal salt of an ethylenically unsaturated carboxylic acid, For example, ZSC (registered trademark, manufactured by Zeon Corporation) may be used.
本発明のゴム組成物においては、上記の各成分ととも
にカーボングラック、シリカ等の補強剤、炭カル、タル
クなどの充填剤、トリアリルイソシアヌレート、トリメ
チロールプロパン等の架橋助剤、可塑剤、安定剤、加工
助剤、着色剤等の通常ゴム工業で使用される種々の薬剤
が使用目的に応じて適宜配合される。In the rubber composition of the present invention, a carbon black, a reinforcing agent such as silica, a filler such as carbon talc, talc, a cross-linking aid such as triallyl isocyanurate and trimethylolpropane, a plasticizer, Various agents commonly used in the rubber industry, such as agents, processing aids, and coloring agents, are appropriately compounded according to the purpose of use.
本発明において、繊維材料としては、代表的には、
綿、人絹、ポリビニルアルコール繊維、脂肪族および芳
香族ポリアミド繊維、ポリエステル繊維、炭素繊維、ガ
ラス繊維等を挙げることができるが、特に制限されるも
のではなく、従来よりゴムとの接着に用いられるすべて
の繊維を含む。これらの繊維材料は、ステープル、フィ
ラメント、コード状、ロープ状、帆布などの形態で使用
し、前記したようにエポキシ基含有化合物と硬化剤とを
含む処理液を含浸させる前に、繊維との接着力を増すた
めにイソシアネート処理などの処理を行ってもよい。In the present invention, as the fiber material, typically,
Cotton, human silk, polyvinyl alcohol fiber, aliphatic and aromatic polyamide fiber, polyester fiber, carbon fiber, glass fiber and the like can be mentioned, but are not particularly limited, and are conventionally used for bonding with rubber. Including all fibers. These fiber materials are used in the form of staples, filaments, cords, ropes, canvas, and the like, and before being impregnated with the treatment liquid containing the epoxy group-containing compound and the curing agent, as described above, the fibers are bonded to the fibers. A treatment such as an isocyanate treatment may be performed to increase the power.
このように処理した繊維材料と水素化ニトリルゴム組
成物とを密着架橋することによって、かかる水素化ニト
リルゴム組成物と繊維材料との間に、強力な接着を達成
することができ、高強度の繊維材料と耐油性、耐熱性に
優れた水素化ニトリルゴム組成物から構成された繊維強
化水素化ニトリルゴムが得られる。しかし、本発明にお
いて架橋接着の条件は特に限定されるものではなく、有
機過酸化物の分解温度に応じて行えばよい。By tightly cross-linking the fiber material thus treated and the hydrogenated nitrile rubber composition, strong adhesion can be achieved between the hydrogenated nitrile rubber composition and the fiber material, and high strength A fiber-reinforced hydrogenated nitrile rubber composed of a fiber material and a hydrogenated nitrile rubber composition having excellent oil resistance and heat resistance is obtained. However, in the present invention, the conditions for cross-linking and adhesion are not particularly limited, and may be performed according to the decomposition temperature of the organic peroxide.
以下に実施例をあげて本発明を説明する。 Hereinafter, the present invention will be described with reference to examples.
実施例 第１回処理として、1000d/2×５のポリエステル繊維
コードならびに1500d/2×３のアラミド繊維コードを第
１表に示す処理液Ａに浸漬し、235℃で１分間熱処理し
た。その後、第２回処理として、これらのコードを第２
表に示す処理液ＢもしくはＣに再び浸漬し、200℃で１
分間熱処理した。その後、第３回処理として、処理液Ｂ
で処理したもののうち半数を第２表に示す処理液Ｄに浸
漬、風乾後、110℃で１分間熱処理した。以上の処理繊
維コードを第３表に示す組成の未加硫ゴムシート上に平
行にすきまなくしきつめた後、170℃で30分間架橋し、
接着物を得た。この１インチ巾について、コードとゴム
間の180℃剥離接着力（剥離速度100mm/分）を測定し
た。この結果を第６表に示す。Example As a first treatment, a polyester fiber cord of 1000 d / 2 × 5 and an aramid fiber cord of 1500 d / 2 × 3 were immersed in the treatment liquid A shown in Table 1 and heat-treated at 235 ° C. for 1 minute. Then, as a second process, these codes are
Immerse again in treatment solution B or C shown in the table,
Heat treated for minutes. Thereafter, as a third process, the processing solution B
Half of those treated in the above was immersed in treatment solution D shown in Table 2, air-dried, and then heat-treated at 110 ° C. for 1 minute. After tightly tightening the above treated fiber cords in parallel on an unvulcanized rubber sheet having the composition shown in Table 3, crosslinking was performed at 170 ° C. for 30 minutes.
An adhesive was obtained. For this one inch width, the 180 ° C. peel adhesion between the cord and the rubber (peeling speed 100 mm / min) was measured. The results are shown in Table 6.
比較例 第１回処理として、実施例と同様に1000d/2×５のポ
リエステル繊維コードならびに1500d/2×３のアラミド
繊維コードを第１表に示す処理液Ａに浸漬し、235℃で
１分間熱処理をした。その後、第２回処理としてこれら
のコードを第５表に示すRFL（RFの組成は第４表に示
す）に浸漬した後、220℃で１分間熱処理をした。その
後実施例と同様に第３表に示す組成の未加硫ゴムシート
と密着架橋させ、同様の接着評価を行った。結果を第６
表にあわせて示す。Comparative Example As a first treatment, a polyester fiber cord of 1000 d / 2 × 5 and an aramid fiber cord of 1500 d / 2 × 3 were immersed in the treatment liquid A shown in Table 1 in the same manner as in the example, and were heated at 235 ° C. for 1 minute. Heat treatment was performed. Then, as a second treatment, these codes were immersed in RFL shown in Table 5 (RF composition is shown in Table 4), and then heat-treated at 220 ° C. for 1 minute. Thereafter, it was intimately crosslinked with an unvulcanized rubber sheet having the composition shown in Table 3 in the same manner as in the examples, and the same adhesion was evaluated. Result 6
It is shown along with the table.
第６表から明らかなように、本発明の方法によれば、
比較例1,2に示す従来のRFL法による接着とは異なり、強
固な接着力を得ることができる。As is apparent from Table 6, according to the method of the present invention,
Unlike the conventional RFL method shown in Comparative Examples 1 and 2, a strong adhesive force can be obtained.
発明の効果 以上のように本発明によれば、繊維材料と水素化ニト
リルゴム組成物との間に、強固な架橋ができ、繊維材料
と水素化ニトリルゴム組成物とが強固に接着される。こ
れによって高強度の繊維材料と耐油性、耐熱性に優れた
水素化ニトリルゴム組成物とから構成された繊維強化ゴ
ムが得られる。この繊維強化ゴムは、動力伝動用ベルト
やコンベヤベルトなどのゴムベルトに好適に用いられ
る。 Advantageous Effects of the Invention As described above, according to the present invention, strong cross-linking can be performed between the fiber material and the hydrogenated nitrile rubber composition, and the fiber material and the hydrogenated nitrile rubber composition are firmly bonded. As a result, a fiber-reinforced rubber composed of a high-strength fiber material and a hydrogenated nitrile rubber composition having excellent oil resistance and heat resistance can be obtained. This fiber reinforced rubber is suitably used for rubber belts such as power transmission belts and conveyor belts.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｄ０６Ｍ 13/196 Ｄ０６Ｍ 13/196 15/55 15/55 15/693 15/693 // Ｃ０８Ｌ 9/02 Ｃ０８Ｌ 9/02 Ｄ０６Ｍ 15/55 15/693 13/10 (58)調査した分野(Int.Cl.6，ＤＢ名) C09J 5/02,5/06 C08J 5/06,5/12 D06M 15/55,15/693,13/196 C08L 9/02 B29B 15/08 - 15/14 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI D06M 13/196 D06M 13/196 15/55 15/55 15/693 15/693 // C08L 9/02 C08L 9/02 D06M 15 / 55 15/693 13/10 (58) Field surveyed (Int.Cl. 6 , DB name) C09J 5 / 02,5 / 06 C08J 5 / 06,5 / 12 D06M 15 / 55,15 / 693,13 / 196 C08L 9/02 B29B 15/08-15/14
Claims (5)
剤とを含む処理液を含浸、加熱する工程と、 有機過酸化物およびエチレン性不飽和カルボン酸の金属
塩を配合した水素化ニトリルゴム組成物と前記エポキシ
含有化合物を接着した繊維材料とを密着加熱して、繊維
材料と水素化ニトリルゴム組成物との間を架橋する工程
とを含むことを特徴とするニトリルゴム組成物と繊維材
料との接着方法。1. A step of impregnating a fiber material with a treatment liquid containing an epoxy group-containing compound and a curing agent and heating, and a hydrogenated nitrile rubber containing an organic peroxide and a metal salt of an ethylenically unsaturated carboxylic acid. Heating the composition and the fibrous material to which the epoxy-containing compound has been adhered, thereby crosslinking the fibrous material and the hydrogenated nitrile rubber composition. And bonding method.
レン性不飽和モノカルボン酸であることを特徴とする請
求項１記載の水素化ニトリルゴム組成物と繊維材料との
接着方法。2. The method for bonding a hydrogenated nitrile rubber composition to a fiber material according to claim 1, wherein the ethylenically unsaturated carboxylic acid is an ethylenically unsaturated monocarboxylic acid.
の遊離カルボキシル基を有するエチレン性不飽和ポリカ
ルボン酸エステルであることを特徴とする請求項１記載
の水素化ニトリルゴム組成物と繊維材料との接着方法。3. The hydrogenated nitrile rubber composition and fiber according to claim 1, wherein the ethylenically unsaturated carboxylic acid is an ethylenically unsaturated polycarboxylic acid ester having one free carboxyl group. How to bond with material.
ネシウム、カルシウムおよびアルミニウムから成る群の
１種であることを特徴とする請求項１〜３のいずれかに
記載のニトリルゴム組成物と繊維材料との接着方法。4. The nitrile rubber composition according to claim 1, wherein the metal constituting the metal salt is one of a group consisting of zinc, magnesium, calcium and aluminum. Adhesion method with fiber material.
と水素化ニトリルゴム組成物とを接着したことを特徴と
する繊維強化水素化ニトリルゴムベルト。5. A fiber reinforced hydrogenated nitrile rubber belt, wherein a fiber material and a hydrogenated nitrile rubber composition are adhered by the method according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2142131A JP2920314B2 (en) | 1990-05-30 | 1990-05-30 | Method for bonding hydrogenated nitrile rubber composition to fiber material and fiber reinforced hydrogenated nitrile rubber belt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2142131A JP2920314B2 (en) | 1990-05-30 | 1990-05-30 | Method for bonding hydrogenated nitrile rubber composition to fiber material and fiber reinforced hydrogenated nitrile rubber belt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0433976A JPH0433976A (en) | 1992-02-05 |
| JP2920314B2 true JP2920314B2 (en) | 1999-07-19 |
Family
ID=15308095
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2142131A Expired - Fee Related JP2920314B2 (en) | 1990-05-30 | 1990-05-30 | Method for bonding hydrogenated nitrile rubber composition to fiber material and fiber reinforced hydrogenated nitrile rubber belt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2920314B2 (en) |
-
1990
- 1990-05-30 JP JP2142131A patent/JP2920314B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0433976A (en) | 1992-02-05 |
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