JP2006089877A - Method for producing carbon fiber cord for rubber reinforcement and carbon fiber cord for rubber reinforcement - Google Patents
Method for producing carbon fiber cord for rubber reinforcement and carbon fiber cord for rubber reinforcement Download PDFInfo
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Abstract
Description
本発明は、ゴム補強用炭素コードの製造方法、およびゴム補強用炭素繊維コードに関するものであり、詳しくはタイヤ、ベルト、ホースなどの産業資材に好適に使用できるゴム補強用炭素繊維コードの製造方法、およびこれにより得られるゴム補強用炭素繊維コードに関するものである。 TECHNICAL FIELD The present invention relates to a method for producing a rubber cord for reinforcing rubber and a carbon fiber cord for reinforcing rubber, and more specifically, a method for producing a carbon fiber cord for reinforcing rubber that can be suitably used for industrial materials such as tires, belts and hoses. , And a carbon fiber cord for rubber reinforcement obtained thereby.
ゴムが強化繊維により補強されてなる繊維強化ゴム材料は、タイヤ、ベルト、ホースなどの産業資材に、広く活用されている。 Fiber reinforced rubber materials in which rubber is reinforced with reinforcing fibers are widely used in industrial materials such as tires, belts, hoses and the like.
これら繊維強化ゴム材料は、撚りが付与された強化繊維束の表層部分に接着剤が塗布されてなるゴム補強用コードにより、ゴムを主成分とする基材が補強されてなるものである。 These fiber reinforced rubber materials are obtained by reinforcing a base material containing rubber as a main component by a rubber reinforcing cord in which an adhesive is applied to a surface layer portion of a reinforced fiber bundle to which twist is imparted.
このようなゴム補強用コードに要求される特性としては、引張強度、引張弾性率、耐熱性、耐水性、およびゴムとの接着性などが挙げられ、中でも、外力により繰り返し受ける応力変形による破壊を防ぐ観点から、ゴム補強用コードとゴムを主成分とする基材との界面における接着性およびコードの耐疲労性が重要である。 Properties required for such a rubber reinforcing cord include tensile strength, tensile modulus, heat resistance, water resistance, and adhesion to rubber. From the viewpoint of prevention, adhesion at the interface between the rubber reinforcing cord and the base material containing rubber as a main component and fatigue resistance of the cord are important.
炭素繊維束が使用されてなるゴム補強用コードは、引張強度、引張弾性率、耐熱性、耐水性には優れるが、ゴムを主成分とする基材との界面における接着性に劣り、ゴム補強用コードとゴムを主成分とする基材との界面において、剥離が生じ易いことが欠点と言われてきた。また、繊維自体の耐疲労性も、ポリエステル、ナイロンなどの他の繊維対比低く、この点についても改良が求められてきた。 Rubber reinforcing cords using carbon fiber bundles are excellent in tensile strength, tensile elastic modulus, heat resistance, and water resistance, but are poor in adhesion at the interface with rubber-based base materials. It has been said to be a drawback that peeling easily occurs at the interface between the cord for use and the base material mainly composed of rubber. In addition, the fatigue resistance of the fiber itself is low compared to other fibers such as polyester and nylon, and this point has also been demanded for improvement.
かかる問題を解決する試みとして、特許文献１（特開昭６２−１３３１８７号公報）には、ウレタン変性エポキシ樹脂およびアクリレート化合物を炭素繊維に付着さる方法が、また、特許文献２（特開昭６２−１４１１７９号公報）には、柔軟骨格を有するウレタン変性エポキシ樹脂を炭素繊維に付着させる方法がそれぞれ開示されている。 As an attempt to solve such a problem, Patent Document 1 (Japanese Patent Laid-Open No. 62-133187) discloses a method in which a urethane-modified epoxy resin and an acrylate compound are attached to carbon fibers. -141179) discloses a method of attaching a urethane-modified epoxy resin having a flexible skeleton to carbon fibers.
しかしながら、これら手法によっても、繊維強化ゴム材料の各種用途において要求される接着性が不足し、炭素繊維束が使用されてなるゴム補強用コードには、タイヤ、ベルト、ホースなどの用途に問題なく適用できる、充分な接着性を有するものにはなっていなかった。また、耐疲労性も不良であった。 However, even with these methods, the adhesiveness required for various uses of fiber reinforced rubber materials is insufficient, and the rubber reinforcing cord using a carbon fiber bundle has no problem in applications such as tires, belts and hoses. It could not be applied and had sufficient adhesiveness. Moreover, fatigue resistance was also poor.
これらの問題を解決するため、炭素繊維束にポリウレタン樹脂を含む樹脂を含浸させる方法（特許文献３：特開２００２−７１０５７号公報）、炭素繊維単糸の表面をゴム成分を含む接着剤組成物で被覆する方法（特許文献４：特開２００３−１９３３７４号公報）などが開示されている。しかしながら、炭素繊維束にポリウレタン樹脂を含む樹脂を含浸させる方法では、接着自体は大幅に改善されるものの、未だ耐疲労性は不十分であった。また、炭素繊維単糸表面をゴム成分を含む接着剤組成物で被覆する方法では、接着性および耐疲労性は改善されるものの、処理工程においてローラーへのスカム付着が非常に多く、繰り返し停止→ローラー清掃を実施しなければならないため、事実上、工業的に適用可能な技術ではなかった。
本発明は、炭素繊維コードとゴムを主成分とする基材との界面における接着性に優れ、かつ耐疲労性にも優れたゴム補強用炭素繊維を提供することにある。 An object of the present invention is to provide a carbon fiber for reinforcing rubber having excellent adhesion at the interface between a carbon fiber cord and a base material containing rubber as a main component and excellent fatigue resistance.
本発明は、実質的に無撚の炭素繊維束に、ポリウレタンを含む樹脂組成物を含浸した後、該繊維束１本にまたは複数本合糸した繊維束に対し、下記式（１）で示される範囲の撚を加えることを特徴とするゴム補強用炭素繊維コードの製造方法に関する。
２≦ ＴＣ≦ ７ 式 （１）
ただし
ＴＣ＝撚係数＝（１／３０３１）×Ｔ（Ｄ）１／２
Ｔ ：加えられた撚数(回/ｍ)
Ｄ :１本または複数本の炭素繊維束の繊度（ｄｔｅｘ）
また、本発明は、上記の製造方法によって得られるゴム補強用炭素繊維コードに関する。
The present invention shows a fiber bundle obtained by impregnating a substantially untwisted carbon fiber bundle with a polyurethane-containing resin composition and then combining one or a plurality of the fiber bundles with the following formula (1). The present invention relates to a method for producing a rubber-reinforcing carbon fiber cord characterized by adding a twist within a range.
2 ≦ TC ≦ 7 Formula (1)
However, TC = twisting coefficient = (1/3031) × T (D) 1/2
T: Number of twists added (times / m)
D: Fineness (dtex) of one or more carbon fiber bundles
Moreover, this invention relates to the carbon fiber cord for rubber reinforcement obtained by said manufacturing method.
本発明によれば、炭素繊維コードとゴムを主成分とする基材との界面における接着性に優れ、かつ耐疲労性にも優れたゴム補強用炭素繊維コードが得られ、この繊維コードを用いることにより、タイヤ、ベルト、ホースなどの産業資材に好適に使用できる繊維強化ゴム材料を提供することができる。 According to the present invention, a carbon fiber cord for reinforcing rubber having excellent adhesion at the interface between a carbon fiber cord and a base material containing rubber as a main component and excellent in fatigue resistance is obtained, and this fiber cord is used. By this, the fiber reinforced rubber material which can be used conveniently for industrial materials, such as a tire, a belt, and a hose, can be provided.
本発明に用いられる炭素繊維束は、実質的に無撚であることが必要である。
実質的に無撚であることは、ポリウレタンを含む樹脂組成物を含浸した際、炭素繊維束表面のみにではなく、単糸にポリウレタンを含む樹脂組成物が被覆するために必要である。
炭素繊維束の撚数としては、５０ｔ／ｍ以下であることが好ましく、１０ｔ／ｍ以下であることがより好ましい。
The carbon fiber bundle used in the present invention needs to be substantially untwisted.
The fact that the resin composition containing polyurethane is impregnated is necessary for the resin composition containing polyurethane to cover not only the surface of the carbon fiber bundle but also the single fiber when impregnated with the resin composition containing polyurethane.
The twist number of the carbon fiber bundle is preferably 50 t / m or less, and more preferably 10 t / m or less.
本発明に使用される炭素繊維束としては特に限定はされないが、炭素繊維表面の酸素量が多い方がポリウレタンを含む樹脂組成物の炭素繊維に対する濡れ性が向上し、ひいてはゴムに対する炭素繊維の接着性および耐疲労性も向上するため好ましい。
Ｘ線電子分光法により測定された表面酸素濃度をＯ／Ｃとした場合、好ましい酸素量はＯ／Ｃ≧０．０５であり、より好ましくはＯ／Ｃ≧０．１である。
The carbon fiber bundle used in the present invention is not particularly limited. However, when the amount of oxygen on the surface of the carbon fiber is larger, the wettability of the resin composition containing polyurethane to the carbon fiber is improved, and as a result, the adhesion of the carbon fiber to the rubber is increased. This is preferable because it improves the resistance and fatigue resistance.
When the surface oxygen concentration measured by X-ray electron spectroscopy is O / C, a preferable oxygen amount is O / C ≧ 0.05, and more preferably O / C ≧ 0.1.
本発明では、以上の実質的無撚の炭素繊維束にポリウレタンを含む樹脂組成物を含浸させる。
ここで、ポリウレタンを含む樹脂組成物を十分に炭素繊維測に含浸させるためには、炭素繊維束の繊度はあまり大きくない方が好ましい。好ましい炭素繊維束の繊度としては、６，０００ｄｔｅｘ以下であり、さらに好ましくは３，０００ｄｔｅｘ以下、特に好ましくは５００〜２，５００ｄｔｅｘである。
本発明の特長は、上記炭素繊維束にポリウレタン樹脂を含む樹脂組成物を含浸させる点にある。ポリウレタン樹脂組成物は、粘着性は大きくないが、靭性があり、ゴムに対する接着性の良好な樹脂であるため、炭素繊維単糸の表面をゴム成分を含む接着剤組成物で被覆する方法（特開２００３−１９３３７４号公報）のように、工程内ローラー部にスカムが多量に付着することなく、炭素繊維コード物性を向上させることが可能となる。
In the present invention, the substantially non-twisted carbon fiber bundle is impregnated with a resin composition containing polyurethane.
Here, in order to sufficiently impregnate the carbon-fiber measurement with a resin composition containing polyurethane, it is preferable that the fineness of the carbon fiber bundle is not so large. The fineness of the carbon fiber bundle is preferably 6,000 dtex or less, more preferably 3,000 dtex or less, and particularly preferably 500 to 2,500 dtex.
The feature of the present invention is that the carbon fiber bundle is impregnated with a resin composition containing a polyurethane resin. A polyurethane resin composition is a resin that is not very tacky but has toughness and good adhesion to rubber. Therefore, the surface of a carbon fiber single yarn is coated with an adhesive composition containing a rubber component (special feature). As described in Japanese Laid-Open Patent Publication No. 2003-193374, the physical properties of the carbon fiber cord can be improved without a large amount of scum adhering to the in-process roller portion.
本発明においては、ポリウレタンの靭性および接着性が重要であるため、その特性を阻害しない範囲で他の化合物を含むことは何らさしつかえがない。例えば、ポリウレタンにポリエポキシ化合物を含有させた場合には、接着処理後のゴムに対する接着性が向上する。樹脂組成物中のポリウレタンの好ましい含有範囲は５０重量％以上であり、より好ましくは７０重量％以上、さらに好ましくは９０重量％以上である。 In the present invention, since the toughness and adhesiveness of polyurethane are important, there is no doubt that other compounds are included as long as the properties are not impaired. For example, when a polyepoxy compound is contained in polyurethane, adhesion to rubber after the adhesion treatment is improved. A preferable content range of polyurethane in the resin composition is 50% by weight or more, more preferably 70% by weight or more, and further preferably 90% by weight or more.
本発明においては、ゴム補強用コードとゴム基材の界面における接着性（以下、接着性と略記）を向上させる観点から、ポリウレタンは、ポリイソシアネートとポリエーテルポリオールの反応により得られるポリエーテル系ポリウレタンよりも、むしろ、ポリイソシアネートとポリエステルポリオールの反応により得られるポリエステル系ポリウレタンの方が好ましく用いられる。 In the present invention, from the viewpoint of improving the adhesion at the interface between the rubber reinforcing cord and the rubber substrate (hereinafter abbreviated as adhesion), the polyurethane is a polyether-based polyurethane obtained by the reaction of polyisocyanate and polyether polyol. Rather, a polyester polyurethane obtained by the reaction of polyisocyanate and polyester polyol is preferably used.
ここで、ポリイソシアネートの具体例としては、トリ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、イソホロンジイソシアネート、ジシクロヘキシルメタンジイソシアネートなどが挙げられる。 Here, specific examples of the polyisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and the like.
また、ポリエーテルポリオールの具体例としては、ポリプロピレングリコール、ポリテトラメチレングリコールなどが挙げられる。 Specific examples of the polyether polyol include polypropylene glycol and polytetramethylene glycol.
ポリエステルポリオールの具体例としては、多価アルコールとアジピン酸の縮合反応により得られるアジペート系ポリエステルポリオール、多価アルコールを開始剤とし、ε−カプロラクタムの開環重合により得られるラクトン系ポリエステルポリオールなどが挙げられる。 Specific examples of the polyester polyol include an adipate polyester polyol obtained by a condensation reaction of a polyhydric alcohol and adipic acid, a lactone polyester polyol obtained by ring-opening polymerization of ε-caprolactam using a polyhydric alcohol as an initiator, and the like. It is done.
ポリウレタンのガラス転移温度は、０℃以下であるのが良く、好ましくは−２０℃以下、より好ましくは−４０℃以下であるのが良い。ガラス転移温度が０℃を超えると、２５℃付近におけるゴム補強用コードの柔軟性が乏しくなり、タイヤ、ベルトなどの用途に適用できなくなることがある。 The glass transition temperature of the polyurethane may be 0 ° C. or lower, preferably −20 ° C. or lower, more preferably −40 ° C. or lower. When the glass transition temperature exceeds 0 ° C., the flexibility of the rubber reinforcing cord at around 25 ° C. becomes poor and may not be applicable to uses such as tires and belts.
ポリウレタンは、炭素繊維束に対する含浸性の観点から、水などの溶媒に分散させた微粒子または溶液の形態であるのが好ましい。この場合、ポリウレタンの平均粒径は１μｍ以下であるのが良く、好ましくは０．５μｍ以下、より好ましくは０．１μｍ以下であるのが良い。ポリウレタンの粒子径が１μｍを超えた場合には、繊維単糸を十分被覆できず、繊維束内部に未被覆の単糸が残る可能性があり 耐疲労性悪化の原因となるため好ましくない。 The polyurethane is preferably in the form of fine particles or a solution dispersed in a solvent such as water from the viewpoint of impregnation with the carbon fiber bundle. In this case, the average particle diameter of the polyurethane may be 1 μm or less, preferably 0.5 μm or less, more preferably 0.1 μm or less. When the particle diameter of the polyurethane exceeds 1 μm, the fiber single yarn cannot be sufficiently covered, and an uncoated single yarn may remain inside the fiber bundle, which is not preferable because it causes deterioration in fatigue resistance.
本発明において、ポリウレタンを含む樹脂組成物の付着量は、固形分換算で、炭素繊維束１００重量％に対して、５〜４０重量％であるのが良く、好ましくは１０〜３０重量％、より好ましくは１０〜２０重量％であるのが良い。５重量％未満であると、炭素繊維束内における単繊維どうしの擦過により、ゴム補強用コードの耐久性が不足することがあり、一方、４０重量％を超えると、ゴム補強用コードの耐熱性や耐水性が不足することがある。 In the present invention, the amount of the resin composition containing polyurethane is preferably 5 to 40% by weight, more preferably 10 to 30% by weight, based on 100% by weight of the carbon fiber bundle in terms of solid content. Preferably it is 10 to 20% by weight. If it is less than 5% by weight, the durability of the rubber reinforcing cord may be insufficient due to abrasion of the single fibers in the carbon fiber bundle. On the other hand, if it exceeds 40% by weight, the heat resistance of the rubber reinforcing cord And water resistance may be insufficient.
本発明では、炭素繊維束にウレタン樹脂を含む樹脂組成物を含浸した後、１本にまたは複数本合糸した繊維束に対し、下記式（１）で示される範囲の撚を加える。
２≦ ＴＣ≦ ７ 式 （１）
ただし
ＴＣ＝撚係数＝（１／３０３１）×Ｔ（Ｄ）１／２
Ｔ ：加えられた撚数(回/ｍ)
Ｄ :１本または複数本の炭素繊維束の繊度（ｄｔｅｘ）
In the present invention, after impregnating a carbon fiber bundle with a resin composition containing a urethane resin, a twist in a range represented by the following formula (1) is added to one or a plurality of combined fiber bundles.
2 ≦ TC ≦ 7 Formula (1)
However, TC = twisting coefficient = (1/3031) × T (D) 1/2
T: Number of twists added (times / m)
D: Fineness (dtex) of one or more carbon fiber bundles
撚を加える理由は、耐疲労性の向上とコードヤング率の安定化である。
前述の撚係数が２より小さい場合には、該炭素繊維コードの耐疲労性は不十分であり実質的にゴム補強用コードとしては使用できない。一方、前述の撚係数が７より大きい場合には、ヤング率が低い値で安定化してしまい、炭素繊維を使用することの特徴が失われる、また強力の低下も見られる。好ましい撚係数の範囲は３以上６以下である。また、これらの撚を加えられたコードを複数本引きそろえ、さらに上撚を加えることも耐疲労性の向上には好ましく、本発明では否定されない。
The reason for adding twist is to improve fatigue resistance and to stabilize the cord Young's modulus.
When the above-mentioned twist coefficient is smaller than 2, the fatigue resistance of the carbon fiber cord is insufficient and cannot be used as a rubber reinforcing cord. On the other hand, when the above-mentioned twist coefficient is larger than 7, the Young's modulus is stabilized at a low value, the characteristics of using carbon fiber are lost, and the strength is also reduced. The range of a preferable twist coefficient is 3 or more and 6 or less. It is also preferable to improve the fatigue resistance by arranging a plurality of these twisted cords and further adding an upper twist, which is not denied in the present invention.
なお、本発明では、実質的に無撚の炭素繊維束にポリウレタンを含む樹脂組成物を含浸したのち、上記式(１)で表される範囲の撚りを加えるに先立ち、含浸処理した炭素繊維束を乾燥・熱処理することが好ましい。
この乾燥・熱処理条件としては、温度が１１０〜２７０℃、好ましくは１５０〜２２０℃、処理時間が０．５〜１０分、好ましくは１〜３分である。
In the present invention, a substantially untwisted carbon fiber bundle is impregnated with a resin composition containing polyurethane and then impregnated carbon fiber bundle prior to adding a twist in the range represented by the above formula (1). Is preferably dried and heat-treated.
As drying and heat treatment conditions, the temperature is 110 to 270 ° C., preferably 150 to 220 ° C., and the treatment time is 0.5 to 10 minutes, preferably 1 to 3 minutes.
本発明においては、接着性をさらに向上させる観点から、上記の式(１)で表される撚りを加えたのち、レゾルシノール−ホルムアルデヒド樹脂とラテックスの混合物（以下、ＲＦＬ系接着剤と略記）を、コード／ゴム界面の接着剤として用いるのが好ましい。 In the present invention, from the viewpoint of further improving the adhesion, after adding the twist represented by the above formula (1), a mixture of resorcinol-formaldehyde resin and latex (hereinafter abbreviated as RFL adhesive), It is preferably used as an adhesive at the cord / rubber interface.
ＲＦＬ系接着剤は、例えば、水酸化ナトリウムなどのアルカリ性化合物を含む水溶液に、レゾルシノールとホルマリンを加え、室温で数時間静置し、レゾルシノールとホルムアルデヒドを初期縮合させた後、ゴムラテックスを加える方法などにより製造することができる。 The RFL adhesive is, for example, a method in which resorcinol and formalin are added to an aqueous solution containing an alkaline compound such as sodium hydroxide, left at room temperature for several hours, and after initial condensation of resorcinol and formaldehyde, a rubber latex is added. Can be manufactured.
ゴムラテックスの具体例としては、アクリルゴムラテックス、アクリロニトリル−ブタジエンゴムラテックス、イソプレンゴムラテックス、ウレタンゴムラテックス、エチレン−プロピレンゴムラテックス、クロロプレンゴムラテックス、シリコーンゴムラテックス、スチレン−ブタジエンゴムラテックス、天然ゴムラテックス、ビニルピリジン−スチレン−ブタジエンゴムラテックス、ブタジエンゴムラテックスなどが挙げられる。中でも、ビニルピリジン−スチレン−ブタジエンゴムラテックスは、接着性改善に有効である。 Specific examples of the rubber latex include acrylic rubber latex, acrylonitrile-butadiene rubber latex, isoprene rubber latex, urethane rubber latex, ethylene-propylene rubber latex, chloroprene rubber latex, silicone rubber latex, styrene-butadiene rubber latex, natural rubber latex, Examples thereof include vinylpyridine-styrene-butadiene rubber latex, butadiene rubber latex, and the like. Among these, vinylpyridine-styrene-butadiene rubber latex is effective for improving adhesiveness.
また、ＲＦＬ系接着剤は、乾燥前は、水分を含む、いわゆる水系接着剤のため、ゴム補強用コードの耐久性が不足する原因となるボイドの発生を防ぐ観点から、ゴム補強用コードの表面に付着させた後、加熱により水分を乾燥除去しておくのが好ましい。 Further, since the RFL adhesive is a so-called aqueous adhesive that contains moisture before drying, the surface of the rubber reinforcing cord is prevented from the occurrence of voids that cause the durability of the rubber reinforcing cord to be insufficient. After adhering to water, it is preferable to dry and remove moisture by heating.
ここで、乾燥状態におけるＲＦＬ系接着剤の付着量は、炭素繊維束１００重量％に対して、１〜１０重量％であるのが良く、好ましくは２〜９重量％、より好ましくは３〜８重量％であるのが良い。付着量が１重量％未満であると、接着性の改善効果が不足することがあり、一方、１０重量％を超えると、ゴム補強用コードの柔軟性が不足することがある。
また、ゴムとの接着性をさらに向上させるため、エポキシ化合物を含む化合物を付着し、引き続き熱処理した後にＲＦＬを付着することも接着性向上のためには好ましく例示できる。
Here, the adhesion amount of the RFL adhesive in the dry state may be 1 to 10% by weight, preferably 2 to 9% by weight, more preferably 3 to 8% with respect to 100% by weight of the carbon fiber bundle. It is good to be weight%. If the adhesion amount is less than 1% by weight, the effect of improving adhesiveness may be insufficient. On the other hand, if it exceeds 10% by weight, the flexibility of the rubber reinforcing cord may be insufficient.
In order to further improve the adhesiveness to rubber, it is also preferable to attach RFL after adhering a compound containing an epoxy compound and subsequently heat treating it.
以下、本発明を実施例に基づいてさらに詳細に説明するが、実施例はあくまで一例であって、本発明を限定するものではない。 EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, an Example is an example to the last, Comprising: This invention is not limited.
実施例１
実質的に無撚の炭素繊維束（東邦テナックス社製、ベスファイト ＩＭ６００−６Ｋ，２，０５０ｄｔｅｘ）を第一工業製薬社製、水分散型ポリウレタン樹脂スーパーフレックス１０７に浸漬させた後、１３０℃１分熱処理、引き続き２００℃で２分熱処理を実施した。以上の工程は連続工程で実施した。炭素繊維束に対するポリウレタン樹脂の付着量は１０重量％であった。この炭素繊維束１本に撚数３００ｔ／ｍ(下記式で示されるＴＣ=撚係数=４．５)で撚をかけ、撚糸コードを得た。
ＴＣ＝撚係数＝（１／３，０３１）×Ｔ（Ｄ）１／２
Ｔ ：加えられた撚数 (回/ｍ)
Ｄ ：１本または複数本の炭素繊維束の繊度（ｄｔｅｘ）
本撚糸コードに対し、表１で示される組成のＲＦＬ接着剤を付着させた後、１５０℃で１分熱処理を実施、引き続き２２０℃で２分熱処理を実施した。ＲＦＬ接着剤の付着量は、炭素繊維撚糸コード重量（ポリウレタン樹脂重量を含む）に対し、４重量％であった。
Example 1
A substantially untwisted carbon fiber bundle (manufactured by Toho Tenax Co., Ltd., Besfight IM600-6K, 2,050 dtex) was immersed in Daiichi Kogyo Seiyaku Co., Ltd., water-dispersible polyurethane resin Superflex 107, and then 130 ° C 1 A partial heat treatment was subsequently performed at 200 ° C. for 2 minutes. The above process was implemented by the continuous process. The adhesion amount of the polyurethane resin to the carbon fiber bundle was 10% by weight. One carbon fiber bundle was twisted at a twist number of 300 t / m (TC = twisting coefficient = 4.5 shown by the following formula) to obtain a twisted cord.
TC = twisting coefficient = (1 / 3,031) × T (D) 1/2
T: Number of twists added (times / m)
D: Fineness (dtex) of one or more carbon fiber bundles
After the RFL adhesive having the composition shown in Table 1 was attached to the present twisted cord, heat treatment was performed at 150 ° C. for 1 minute, and subsequently, heat treatment was performed at 220 ° C. for 2 minutes. The adhesion amount of the RFL adhesive was 4% by weight with respect to the weight of the carbon fiber twisted cord (including the weight of the polyurethane resin).
＊１）住友化学社製 レゾルシン・ホルマリン反応物
＊２）ＪＳＲ社製 スチレン・ブタジエン・ビニルピリジン３元重合体ラテックス
＊３）明成化学社製 ブロックドイソシアネート
剤調製後 ２４時間以上１週間以内の間に使用
* 1) Resorcin / formalin reaction product manufactured by Sumitomo Chemical Co., Ltd. * 2) Styrene / butadiene / vinylpyridine terpolymer latex manufactured by JSR Co., Ltd. * 3) Blocked isocyanate manufactured by Meisei Chemical Co., Ltd. Used for
《耐疲労性の測定方法》
図１に示すように、炭素繊維コード１の一端に１．５ｋｇの荷重２を取り付け、直径１０ｍｍのローラー３に掛け渡し、他端４をコード長軸方向に振幅３０ｍｍ、速度１２０回/分で振動させることにより、コードを繰り返し屈曲させ、破断するまでの回数を測定した。
実施例１における破断回数は、１０．１万回であった。
<< Measurement method of fatigue resistance >>
As shown in FIG. 1, a 1.5
The number of breaks in Example 1 was 10.11,000.
《接着性の測定方法》
評価用ゴムとして、天然ゴム／スチレン・ブタジエンゴム（重量比）＝６／４ のゴムを使用した。
剥離接着試験として、ゴムシート表層近くに５本のコードを埋め、１５０℃で３０分間、１０ｋｇ／ｃｍ２のプレス圧力で加硫し、５本のコードをゴムシートから２００ｍｍ／ｍｉｎの速度で剥離するのに要した力を、N／５本コードで表示した。
実施例１サンプルの剥離力は、８０N／５本コードであった。
<Measurement method of adhesiveness>
As the rubber for evaluation, a rubber of natural rubber / styrene-butadiene rubber (weight ratio) = 6/4 was used.
As a peel adhesion test, five cords were buried near the surface of the rubber sheet, vulcanized at a pressure of 10 kg / cm 2 for 30 minutes at 150 ° C., and the five cords were peeled from the rubber sheet at a rate of 200 mm / min. The force required to do this is displayed in N / 5 codes.
The peel force of the sample of Example 1 was 80 N / 5 cords.
《スカム量の評価方法》
本実験において使用した炭素繊維束に、所定の剤を含浸→乾燥させる設備に敷設されている金属ローラに付着するスカム量を評価した。運転は３０分間実施した。
実施例1においては、金属ローラーに付着したスカムは見られなかった。
以上の結果を表２に示す。
<Evaluation method of scum amount>
The carbon fiber bundle used in this experiment was evaluated for the amount of scum adhering to a metal roller installed in a facility for impregnating and drying a predetermined agent. The operation was carried out for 30 minutes.
In Example 1, no scum adhering to the metal roller was observed.
The results are shown in Table 2.
比較例１
炭素繊維束にウレタン樹脂を含浸（ｄｉｐ）することなく（ウレタン樹脂含浸工程を省き）炭素繊維束を撚糸３００ｔ／ｍで撚糸した以外は、実施例１と同様に実施した。
測定結果を表２に示す。
Comparative Example 1
The same procedure as in Example 1 was carried out except that the carbon fiber bundle was twisted with 300 t / m of twisted yarn without impregnating (diping) the urethane resin into the carbon fiber bundle (the urethane resin impregnation step was omitted).
The measurement results are shown in Table 2.
実施例２
炭素繊維束を、大日本インキ社製、クリスボンAH−５００（溶剤系ポリウレタン樹脂溶液）をアセトンで希釈した溶液に浸漬した以外は、実施例１と同様に実施した。測定結果を表２に示す。
Example 2
The carbon fiber bundle was carried out in the same manner as in Example 1 except that the carbon fiber bundle was immersed in a solution obtained by diluting Crisbon AH-500 (solvent polyurethane resin solution) manufactured by Dainippon Ink Co., Ltd. with acetone. The measurement results are shown in Table 2.
比較例２
炭素繊維束を３００ｔ／ｍで撚糸した後に、ポリウレタン樹脂を含浸し乾燥した点以外は、実施例１と同様に実施した。測定結果を表２に示す。
Comparative Example 2
The same procedure as in Example 1 was performed, except that the carbon fiber bundle was twisted at 300 t / m, then impregnated with polyurethane resin and dried. The measurement results are shown in Table 2.
比較例３
ポリウレタン樹脂を含浸させる代りに、ＪＳＲ社製、スチレン・ブタジエン・ビニルピリジン３元重合体ラテックス、ＪＳＲ ０６５０を含浸させる点以外は、実施例１と同様に実施した。測定結果を表２に示す。
Comparative Example 3
The same procedure as in Example 1 was performed except that, instead of impregnation with polyurethane resin, impregnation with styrene-butadiene-vinylpyridine terpolymer latex, JSR 0650, manufactured by JSR Corporation. The measurement results are shown in Table 2.
実施例３
ポリウレタン樹脂付着後に撚数２００ｔ/ｍ（上記式で示される撚係数＝３）で撚糸を行った点以外は、実施例１と同様に実施した。測定結果を表３に示す。
Example 3
This was carried out in the same manner as in Example 1 except that the twisted yarn was applied at a twist number of 200 t / m (twist coefficient represented by the above formula = 3) after the polyurethane resin was adhered. Table 3 shows the measurement results.
実施例４
ポリウレタン樹脂付着後に撚数３７０ｔ/ｍ（上記式で示される撚係数＝５．５）で撚糸を行った点以外は、実施例１と同様に実施した。測定結果を表３に示す。
Example 4
This was carried out in the same manner as in Example 1 except that the twisted yarn was applied at a twist number of 370 t / m (twist coefficient represented by the above formula = 5.5) after the polyurethane resin was adhered. Table 3 shows the measurement results.
比較例４
ポリウレタン樹脂付着後に撚数１００ｔ/ｍ（上記式で示される撚係数＝１．５）で撚糸を行った点以外は、実施例１と同様に実施した。測定結果を表３に示す。
Comparative Example 4
This was carried out in the same manner as in Example 1 except that the twisted yarn was applied at a twist number of 100 t / m (twist coefficient shown by the above formula = 1.5) after the polyurethane resin was adhered. Table 3 shows the measurement results.
比較例５
ポリウレタン樹脂付着後に撚数６００ｔ/ｍ（上記式で示される撚係数＝９）での撚糸を試みたが、撚糸時にコードが破断し評価が行えなかった。
Comparative Example 5
After attaching the polyurethane resin, an attempt was made to twist the yarn with a twist number of 600 t / m (twisting coefficient represented by the above formula = 9), but the cord was broken during the twisting and evaluation could not be performed.
実施例１，２と比較例１とを比較することにより、炭素繊維束に応力ウレタン樹脂を含浸させない場合には、耐疲労性が非常に悪いことが分かる。
また、実施例１，２と比較例２とを比較することにより、撚糸後にポリウレタン樹脂を含浸させた場合には、ポリウレタン樹脂含浸無き場合よりも耐疲労性は向上するが、未だ不十分なことが分かる。
実施例１，２と比較例３とを比較することにより、先行技術にあるラテックス処理の場合には、耐疲労性の向上は見られるが、ローラーへのスカム付着量がポリウレタン樹脂含浸対比約１０倍となっており、工程上に問題があることが分かる。
実施例１，３，４と、比較例４，５との比較により、一定レベル以上の耐疲労性を確保するためには特定範囲の撚数は必要であることがわかる。
By comparing Examples 1 and 2 with Comparative Example 1, it can be seen that the fatigue resistance is very poor when the carbon fiber bundle is not impregnated with the stress urethane resin.
Further, by comparing Examples 1 and 2 with Comparative Example 2, when the polyurethane resin is impregnated after twisting, the fatigue resistance is improved as compared with the case without the polyurethane resin impregnation, but it is still insufficient. I understand.
By comparing Examples 1 and 2 with Comparative Example 3, in the case of the latex treatment in the prior art, an improvement in fatigue resistance is seen, but the amount of scum adhering to the roller is about 10 in comparison with the polyurethane resin impregnation. It can be seen that there is a problem in the process.
From comparison between Examples 1, 3, and 4 and Comparative Examples 4 and 5, it can be seen that a specific number of twists is necessary to ensure fatigue resistance of a certain level or more.
本発明は、炭素繊維コードとゴムを主成分とする基材との界面における接着性に優れ、かつ耐疲労性にも優れたゴム補強用炭素繊維コードが得られ、タイヤ、ベルト、ホース、などの繊維強化ゴム材料の用途に好適に使用することができる。 The present invention provides a carbon fiber cord for reinforcing rubber having excellent adhesion at the interface between a carbon fiber cord and a base material containing rubber as a main component and also having excellent fatigue resistance, such as a tire, belt, hose, etc. It can use suitably for the use of the fiber reinforced rubber material of this.
１：炭素繊維コード
２：荷重
３：ローラー
４：炭素繊維コードの他端
1: Carbon fiber cord 2: Load 3: Roller 4: The other end of the carbon fiber cord
Claims (2)
２≦ ＴＣ≦ ７ 式 （１）
ただし
ＴＣ＝撚係数＝（１／３，０３１）×Ｔ（Ｄ）１／２
Ｔ ：加えられた撚数(回/ｍ)
Ｄ :１本または複数本の炭素繊維束の繊度（ｄｔｅｘ） After impregnating a substantially untwisted carbon fiber bundle with a polyurethane-containing resin composition, the fiber bundle obtained by combining one or a plurality of the fiber bundles is twisted within the range represented by the following formula (1). A method for producing a rubber-reinforcing carbon fiber cord comprising adding
2 ≦ TC ≦ 7 Formula (1)
However, TC = twisting coefficient = (1 / 3,031) × T (D) 1/2
T: Number of twists added (times / m)
D: Fineness (dtex) of one or more carbon fiber bundles
A carbon fiber cord for rubber reinforcement obtained by the production method according to claim 1.
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| JP2004277276A JP4402556B2 (en) | 2004-09-24 | 2004-09-24 | Manufacturing method of carbon fiber cord for rubber reinforcement, and carbon fiber cord for rubber reinforcement |
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|---|---|---|---|
| JP2004277276A JP4402556B2 (en) | 2004-09-24 | 2004-09-24 | Manufacturing method of carbon fiber cord for rubber reinforcement, and carbon fiber cord for rubber reinforcement |
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| Publication Number | Publication Date |
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| JP2006089877A true JP2006089877A (en) | 2006-04-06 |
| JP4402556B2 JP4402556B2 (en) | 2010-01-20 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008123066A1 (en) * | 2007-03-23 | 2008-10-16 | Toho Tenax Co., Ltd. | Rubber-reinforcing carbon fiber cord and method for producing the same |
| WO2012169207A1 (en) * | 2011-06-10 | 2012-12-13 | 日本板硝子株式会社 | Reinforcement cord for reinforcing rubber product, and rubber product using same |
| JP2014080513A (en) * | 2012-10-16 | 2014-05-08 | Toray Ind Inc | Water dispersion type polyurethane resin composition, sheet-like material, and method for producing the sheet-like material |
| US9944763B2 (en) | 2009-12-01 | 2018-04-17 | Gates Corporation | Polyurea-urethane cord treatment for power transmission belt and belt |
| US10220545B2 (en) * | 2016-04-30 | 2019-03-05 | Contitech Antriebssysteme Gmbh | Water based urethane as predip for carbon fiber cord |
-
2004
- 2004-09-24 JP JP2004277276A patent/JP4402556B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008123066A1 (en) * | 2007-03-23 | 2008-10-16 | Toho Tenax Co., Ltd. | Rubber-reinforcing carbon fiber cord and method for producing the same |
| US9944763B2 (en) | 2009-12-01 | 2018-04-17 | Gates Corporation | Polyurea-urethane cord treatment for power transmission belt and belt |
| US11111342B2 (en) | 2009-12-01 | 2021-09-07 | Gates Corporation | Polyurea-urethane cord treatment for power transmission belt and belt |
| WO2012169207A1 (en) * | 2011-06-10 | 2012-12-13 | 日本板硝子株式会社 | Reinforcement cord for reinforcing rubber product, and rubber product using same |
| CN103608513A (en) * | 2011-06-10 | 2014-02-26 | 日本板硝子株式会社 | Reinforcement cord for reinforcing rubber product, and rubber product using same |
| JPWO2012169207A1 (en) * | 2011-06-10 | 2015-02-23 | 日本板硝子株式会社 | Reinforcing cord for reinforcing rubber product and rubber product using the same |
| US10041194B2 (en) | 2011-06-10 | 2018-08-07 | Nippon Sheet Glass Company, Limited | Reinforcement cord for reinforcing rubber product, and rubber product using same |
| JP2014080513A (en) * | 2012-10-16 | 2014-05-08 | Toray Ind Inc | Water dispersion type polyurethane resin composition, sheet-like material, and method for producing the sheet-like material |
| US10220545B2 (en) * | 2016-04-30 | 2019-03-05 | Contitech Antriebssysteme Gmbh | Water based urethane as predip for carbon fiber cord |
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| Publication number | Publication date |
|---|---|
| JP4402556B2 (en) | 2010-01-20 |
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