JP2001003273A - Polyester fiber for reinforcing rubber and its production - Google Patents
Polyester fiber for reinforcing rubber and its productionInfo
- Publication number
- JP2001003273A JP2001003273A JP11175210A JP17521099A JP2001003273A JP 2001003273 A JP2001003273 A JP 2001003273A JP 11175210 A JP11175210 A JP 11175210A JP 17521099 A JP17521099 A JP 17521099A JP 2001003273 A JP2001003273 A JP 2001003273A
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- Japan
- Prior art keywords
- rubber
- weight
- fiber
- polyester fiber
- polyethyleneimine
- 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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- Compositions Of Macromolecular Compounds (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ゴムとの接着性が
改善され、強力および耐疲労性にも優れたゴム補強用ポ
リエステル繊維に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber reinforcing polyester fiber having improved adhesion to rubber and excellent strength and fatigue resistance.
【０００２】[0002]
【従来の技術】ポリエチレンテレフタレート、ポリエチ
レンナフタレート、またはこれらを主体とするポリエス
テル繊維は優れた物理的、化学的性質を有し、各分野で
多用されている極めて有用な繊維であり、ゴムの補強材
料としても非常に好適な素材である。しかしながら、ポ
リエステル繊維はゴムとの接着性が良好でないといった
欠点を有しているため、タイヤ、ベルトなどの補強材用
途では、これまでポリエステル繊維とゴムとの接着性を
改良するため、エポキシ化合物などの接着性向上剤や、
その硬化剤を付着させた繊維が提案されている。2. Description of the Related Art Polyethylene terephthalate, polyethylene naphthalate and polyester fibers based on these materials have excellent physical and chemical properties, are extremely useful fibers that are widely used in various fields, and are used for reinforcing rubber. It is also a very suitable material. However, polyester fibers have the drawback of poor adhesion to rubber, and in reinforcing materials such as tires and belts, epoxy compounds and other materials have been used to improve the adhesion between polyester fibers and rubber. Adhesive improver,
Fibers having the curing agent attached have been proposed.
【０００３】例えば、紡出した糸条にエポキシ化合物の
硬化剤として脂肪族アミンアルキレンオキサイド化合物
を含有させた紡糸油剤を付与し、熱延伸後、エポキシ化
合物と該硬化剤とを含有させた仕上油剤で処理した繊維
（特開平８−２１８２２８号公報）、また、紡糸油剤は
これと同様のものを使用し、仕上油剤としてさらにゴム
との接着性を上げるため、エポキシ化合物と該硬化剤に
加え、ブロックドイソシアネート化合物およびシランカ
ップリング剤を配合した仕上油剤で処理した繊維（特開
平９−１５８０５３号公報）が提案されており、これら
の繊維を撚糸してコードとし、ＲＦＬ処理を行うことに
よりゴムとの接着性に優れたゴム補強材が得られるとさ
れている。For example, a spinning oil containing an aliphatic amine alkylene oxide compound as a curing agent for an epoxy compound is applied to a spun yarn, and after hot drawing, a finishing oil containing an epoxy compound and the curing agent is added. (Japanese Unexamined Patent Publication No. Hei 8-218228), and the same spinning oil as above, and in addition to the epoxy compound and the curing agent, as a finishing oil, to further increase the adhesion to rubber. Fibers treated with a finishing oil containing a blocked isocyanate compound and a silane coupling agent (Japanese Patent Application Laid-Open No. Hei 9-158053) have been proposed. These fibers are twisted into cords and subjected to RFL treatment to obtain rubber. It is said that a rubber reinforcing material having excellent adhesiveness with the rubber can be obtained.
【０００４】しかし、上記の硬化剤はエポキシ化合物と
の反応性が低いため、十分なゴムとの接着性を得ようと
すれば、該硬化剤の付着量を多くする必要があり、その
結果上記のポリエステル繊維は非常に硬いものしか得ら
れない。さらにこのポリエステル繊維をコードとし、Ｒ
ＦＬ処理することによって、該コードはより硬くなり、
処理前と比較して強力が著しく低下しており、これをゴ
ム中に埋め込み疲労性を測定したところ耐疲労性も劣っ
ているといった問題がある。かかる問題に対して、該硬
化剤の付着量を減らすことにより、ＲＦＬ処理後のコー
ドが硬くなるのを抑制し、強力やゴム中の耐疲労性が低
下をある程度抑えることができるものの、ゴムとの接着
性が不十分となり、両方を同時に満足するものが得られ
ない。[0004] However, since the above-mentioned curing agent has low reactivity with the epoxy compound, it is necessary to increase the amount of the curing agent to obtain sufficient adhesion to rubber. Only very hard polyester fibers can be obtained. Further, the polyester fiber is used as a cord,
By FL processing, the code becomes harder,
The strength is remarkably reduced as compared with that before the treatment, and when this is embedded in rubber and the fatigue resistance is measured, there is a problem that the fatigue resistance is inferior. To cope with such a problem, by reducing the amount of the curing agent attached, it is possible to suppress the cord from being hardened after the RFL treatment, and it is possible to suppress the strength and the fatigue resistance in the rubber to some extent. Becomes insufficient, and a product satisfying both at the same time cannot be obtained.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、上記
従来技術の有する問題点を解決し、ＲＦＬ処理を行うだ
けで、ゴムとの接着性が改善され、かつ、強力とゴム中
での耐疲労性にも優れたゴム補強用繊維が得られるポリ
エステル繊維およびその製造方法を提供することにあ
る。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art, to improve the adhesiveness to rubber by simply performing an RFL treatment, and to improve the strength and strength in rubber. An object of the present invention is to provide a polyester fiber from which a rubber reinforcing fiber excellent in fatigue resistance can be obtained, and a method for producing the same.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、かかる目
的を達成すべく鋭意検討を重ねた結果、ポリエチレンイ
ミンとエポキシ化合物とを併用して付着させた繊維は、
ポリエチレンイミンが極少量でもエポキシ硬化剤として
優れた性能を発揮し、ＲＦＬ処理を行うだけで優れたゴ
ムとの接着性を示し、かつ、従来使用されている硬化剤
とエポキシ化合物とを併用して付着させたものと比較し
てＲＦＬ処理後のコードは硬くなく、強力およびゴム中
での耐疲労性も著しく改善されていることを見出し本発
明を完成させるに至った。Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to achieve the above object, and as a result, the fibers adhered by using a combination of polyethyleneimine and an epoxy compound are as follows:
Polyethyleneimine exhibits excellent performance as an epoxy curing agent even in a very small amount, exhibits excellent adhesion to rubber only by RFL treatment, and uses a combination of a conventional curing agent and epoxy compound. It was found that the cord after RFL treatment was not hard, and the strength and the fatigue resistance in rubber were remarkably improved as compared with the cord with the cord attached, and the present invention was completed.
【０００７】かくして本発明では、繊維の表面に、該繊
維重量に対して、０．０００１〜０．０３０重量％のポ
リエチレンイミン、および、０．０５〜０．４０重量％
のエポキシ化合物が付着していることを特徴とするゴム
補強用ポリエステル繊維、および、ポリエステル繊維を
溶融紡糸するに際し、紡出した糸条に該繊維重量に対し
て０．０００１〜０．０３０重量％のポリエチレンイミ
ンを付与し、熱延伸した後、該繊維重量に対して０．０
５〜０．４０重量％のエポキシ化合物を付与することを
特徴とするゴム補強用ポリエステル繊維の製造方法が提
案される。Thus, in the present invention, 0.0001 to 0.030% by weight of polyethyleneimine and 0.05 to 0.40% by weight based on the weight of the fiber are provided on the surface of the fiber.
A rubber fiber reinforced polyester fiber having an epoxy compound adhered thereto, and when the polyester fiber is melt-spun, 0.0001 to 0.030% by weight based on the fiber weight of the spun yarn. Of polyethyleneimine, and hot-stretched.
There is proposed a method for producing a polyester fiber for reinforcing rubber, which comprises adding 5 to 0.40% by weight of an epoxy compound.
【０００８】[0008]
【発明の実施の形態】本発明においてポリエステル繊維
とは、ポリエチレンテレフタレート、ポリエチレンナフ
タレート、およびこれらを主体とするポリエステルから
なるマルチフィラメントであり、分子量、デニール、フ
ィラメント数、断面形状、糸質物性、微細構造、添加剤
含有の有無、ポリマー性状（末端カルボキシ基濃度）は
特に限定されない。DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, the polyester fiber is a multifilament composed of polyethylene terephthalate, polyethylene naphthalate and a polyester mainly composed of these, and has a molecular weight, denier, number of filaments, cross-sectional shape, yarn property, The microstructure, the presence or absence of additives, and the properties of the polymer (terminal carboxy group concentration) are not particularly limited.
【０００９】本発明においては、上記のポリエステル繊
維の表面に、ポリエチレンイミンおよびエポキシ化合物
の両方が、それぞれ後述する付着量で併用して付着され
ていることが、ＲＦＬ処理して、ゴムとの接着性、強度
およびゴム中での耐疲労性に優れたコードを得る上で肝
要である。In the present invention, the fact that both the polyethyleneimine and the epoxy compound are adhered to the surface of the above-mentioned polyester fiber together in the amounts described below, respectively, is carried out by RFL treatment, It is important to obtain a cord having excellent properties, strength and fatigue resistance in rubber.
【００１０】上記のポリエステル繊維においては、ポリ
エチレンイミンが極少量でエポキシ化合物の硬化剤とし
て優れた性能を発揮し、該繊維表面に強固にエポキシ化
合物を固着でき、その結果該繊維とゴムとの接着性を著
しく向上させることができる。また、ポリエチレンイミ
ンを後述する量付着させた繊維は、従来使用されている
硬化剤をエポキシ化合物と併用して付着させた繊維と比
べて硬くなく、さらに該繊維をコードとし、これをＲＦ
Ｌ処理した後のコードを比較しても従来の硬化剤を用い
たもののように硬くならないため、強度およびゴム中で
の耐疲労性を著しく改善することができるのである。In the above-mentioned polyester fiber, polyethyleneimine exhibits excellent performance as a curing agent for an epoxy compound in a very small amount, so that the epoxy compound can be firmly fixed on the fiber surface, and as a result, the adhesion between the fiber and rubber can be improved. Properties can be significantly improved. Further, the fiber to which polyethyleneimine is attached in an amount described below is not harder than the fiber to which a conventionally used curing agent is attached in combination with an epoxy compound, and the fiber is used as a cord.
Even when the cords after the L treatment are compared, they do not become hard as in the case of using the conventional curing agent, so that the strength and the fatigue resistance in rubber can be remarkably improved.
【００１１】本発明で使用するポリエチレンイミンは分
子量が高いものが耐熱性に優れていおり、例えば、ポリ
エチレンイミンを紡糸工程で付与するような場合は、続
いて行われる延伸工程で、延伸ローラや熱処理ローラな
どにポリエチレンイミンの熱分解物がほとんど付着しな
いため特に好ましい。このため、ポリエチレンイミンの
分子量は３０万以上が好ましく、特に好ましくは４０万
以上である。The polyethyleneimine used in the present invention has a high molecular weight and is excellent in heat resistance. For example, when polyethyleneimine is applied in a spinning step, a stretching roller or heat treatment is performed in a subsequent stretching step. This is particularly preferable because a thermally decomposed product of polyethyleneimine hardly adheres to a roller or the like. Therefore, the molecular weight of polyethyleneimine is preferably 300,000 or more, particularly preferably 400,000 or more.
【００１２】ポリエチレンイミンの付着量は、繊維重量
に対して０．０００１〜０．０３０重量％、好ましくは
０．０００５〜０．０２０重量％とする必要がある。該
付着量が０．０００１重量％未満では、エポキシ化合物
の硬化剤としての効果が低く、結果としてゴムとの接着
性が不十分となる。逆に、該付着量が０．０３０重量％
を越えると、ＲＦＬ処理の際コードがアミン分解によっ
て劣化し、また、該処理後のコードも硬くなり、その結
果、強度が低下し耐疲労性も十分なものが得られない。It is necessary that the amount of polyethyleneimine adhered is 0.0001 to 0.030% by weight, preferably 0.0005 to 0.020% by weight, based on the weight of the fiber. If the amount is less than 0.0001% by weight, the effect of the epoxy compound as a curing agent is low, and as a result, the adhesion to rubber becomes insufficient. Conversely, the amount of adhesion is 0.030% by weight.
If it exceeds 40, the cord will be degraded due to amine decomposition during the RFL treatment, and the cord after the treatment will also be hard, and as a result, the strength will be reduced and sufficient fatigue resistance will not be obtained.
【００１３】また、本発明で使用するエポキシ化合物と
しては、例えば、グリセリン、プロピレングリコール、
エチレングリコール、へキサントリオール、ソルビトー
ルトリメチロールプロパン、ポリエチレングリコール、
ポリグリセリンなどの脂肪族多価アルコール類とエピク
ロルヒドリンとの反応生成物、レゾルシン、カテコー
ル、ハイドロキノン、１，３，５−トリヒドロキシベン
ゼン、ビス（４−ヒドロキシフェニル）メタンなどのフ
ェノール類とエピクロルヒドリンとの反応生成物などの
グリシジルエーテル、ビニルシクロヘキセンジエポキシ
ド、３’，４’−エポキシ−６’−メチルシクロヘキシ
ルメチル３，４−エポキシ−６−メチルシクロヘキサン
カルボキシレートなどの過酢酸などで不飽和結合部を酸
化して得られるエポキシ化合物などを挙げることができ
る。The epoxy compound used in the present invention includes, for example, glycerin, propylene glycol,
Ethylene glycol, hexanetriol, sorbitol trimethylolpropane, polyethylene glycol,
Reaction products of aliphatic polyhydric alcohols such as polyglycerin with epichlorohydrin, phenols such as resorcinol, catechol, hydroquinone, 1,3,5-trihydroxybenzene and bis (4-hydroxyphenyl) methane with epichlorohydrin Glycidyl ether such as a reaction product, vinylcyclohexene diepoxide, peracetic acid such as 3 ', 4'-epoxy-6'-methylcyclohexylmethyl 3,4-epoxy-6-methylcyclohexanecarboxylate, etc. Examples thereof include an epoxy compound obtained by oxidation.
【００１４】かかるエポキシ化合物のうち市販されてい
るものの具体例として、例えば、グリセロールポリグリ
シジルエーテル（「デナコールＥＸ−３１３」、「デナ
コールＥＸ−３１４」）、ポリグリセロールポリグリシ
ジルエーテル（「デナコールＥＸ−５１２」）、ジグリ
セロールポリグリシジルエーテル（「デナコールＥＸ−
４２１」）、レゾルシンジググリシジルエーテル（「デ
ナコールＥＸ−２０１」）、ソルビトールポリグリシジ
ルエーテル（「デナコールＥＸ−６１１」、「デナコー
ルＥＸ−６１４」）、エチレングリコールジグリシジル
エーテル（「デナコールＥＸ−８１１」）などが挙げら
れる（かっこ内はナガセ化成工業社から市販されている
製品の商品名を示す）。Specific examples of commercially available epoxy compounds include, for example, glycerol polyglycidyl ether (“Denacol EX-313” and “Denacol EX-314”) and polyglycerol polyglycidyl ether (“Denacol EX-512”). "), Diglycerol polyglycidyl ether (" Denacol EX-
421 "), resorcin dig glycidyl ether (" Denacol EX-201 "), sorbitol polyglycidyl ether (" Denacol EX-611 "," Denacol EX-614 "), ethylene glycol diglycidyl ether (" Denacol EX-811 "). (In parentheses indicate the product name of a product commercially available from Nagase Kasei Kogyo Co., Ltd.).
【００１５】エポキシ化合物の付着量は、繊維重量に対
して０．０５〜０．４０重量％、好ましくは０．１０〜
０．３０重量％とする必要がある。該付着量が０．０５
重量％未満では、ゴムとの接着性が不十分であり、逆
に、０．４０重量を越えるとＲＦＬ処理後のコードが硬
くなり、強度およびゴム中での耐疲労性が低下する。The amount of the epoxy compound to be attached is 0.05 to 0.40% by weight, preferably 0.10 to 0.4% by weight based on the weight of the fiber.
It must be 0.30% by weight. The adhesion amount is 0.05
If the amount is less than 0% by weight, the adhesion to the rubber is insufficient. If the amount exceeds 0.40% by weight, the cord after RFL treatment becomes hard, and the strength and the fatigue resistance in the rubber decrease.
【００１６】上記のポリエチレンイミンおよびエポキシ
化合物をポリエステル繊維の表面に付着させるには、従
来公知の方法によって行うことができるが、延伸ローラ
や熱処理ローラなどの汚れの付着低減や、付与する剤の
調製のし易さ・安定性などの観点から、紡出した糸条に
ポリエチレンイミンを付与し、熱延伸した後、エポキシ
化合物を付与する方法が特に好ましい。The above-mentioned polyethyleneimine and epoxy compound can be adhered to the surface of the polyester fiber by a conventionally known method. However, it is possible to reduce the adhesion of dirt on a stretching roller or a heat treatment roller and to prepare an agent to be applied. From the viewpoints of ease of workability and stability, a method in which polyethyleneimine is applied to the spun yarn, and the resultant is hot-drawn, and then an epoxy compound is applied is particularly preferable.
【００１７】上記方法を採用する場合、ポリエチレンイ
ミンの付与は、例えばポリエチレンイミンを平滑剤、乳
化剤などと共に水エマルジョンとした紡糸油剤を紡出し
た糸条に付与する方法により行なえば良い。また、ポリ
エチレンイミンと共に紡糸油剤に配合しうる成分として
は、鉱物油、脂肪酸エステル類などの平滑剤、高級アル
コール類またはエチレンオキサイド（ＥＯ）付加物など
の乳化剤、アニオン系、カチオン系の界面活性剤などの
帯電防止剤などが挙げられる。この紡糸油剤の調製する
際、ポリエチレンイミンは塩基性が非常に高く、紡糸油
剤にそのまま添加すると塩析効果により沈殿物が生ずる
場合があるため、ポリエチレンイミンを予め酢酸などの
有機酸でｐＨを５〜６に中和して紡糸油剤に添加するこ
とが特に好ましい。In the case of employing the above method, the application of polyethyleneimine may be carried out by, for example, a method in which polyethyleneimine is applied to a spun yarn from a spinning oil agent in the form of a water emulsion together with a smoothing agent and an emulsifier. Components that can be blended with the spinning oil together with polyethyleneimine include mineral oils, leveling agents such as fatty acid esters, emulsifiers such as higher alcohols or ethylene oxide (EO) adducts, and anionic and cationic surfactants. And the like. In preparing this spinning oil, polyethyleneimine has a very high basicity, and if added directly to the spinning oil, a precipitate may be formed due to a salting-out effect. Therefore, the polyethyleneimine is previously adjusted to pH 5 with an organic acid such as acetic acid. It is particularly preferable to neutralize the mixture to ~ 6 and add it to the spinning oil.
【００１８】また、エポキシ化合物の付与は、ストレー
トか、あるいは、前述の平滑剤、界面活性剤などと共に
水エマルジョンの形で付与すれば良い。The epoxy compound may be applied in the form of a straight emulsion or a water emulsion together with the above-mentioned leveling agent and surfactant.
【００１９】なお、上記の紡糸油剤、エポキシ化合物あ
るいはエポキシ化合物を配合したエマルジョンの付与
は、公知の方法によって行うことができ、特にローラ式
給油法やノズル式給油法が好ましく採用される。The application of the spinning oil, the epoxy compound or the emulsion containing the epoxy compound can be performed by a known method, and a roller lubrication method and a nozzle lubrication method are particularly preferably employed.
【００２０】なお、上記方法によらず、ポリエチレンイ
ミンを紡糸油剤に含有せず、エポキシ化合物と共にエマ
ルジョンとして熱延伸後の糸条に付与しても良い。ま
た、ポリエチレンイミンを含有した紡糸油剤を付与し、
さらに上記と同様に熱延伸後にもエポキシ化合物と共に
ポリエチレンイミンを再度付与してもかまわない。In addition, regardless of the above method, polyethyleneimine may not be contained in the spinning oil agent, and may be applied to the yarn after hot drawing as an emulsion together with the epoxy compound. In addition, a spinning oil containing polyethyleneimine is provided,
Further, similarly to the above, polyethyleneimine may be applied again together with the epoxy compound even after the hot stretching.
【００２１】[0021]
【実施例】以下、実施例により発明を詳細に説明する。
なお、実施例における性能評価は、次の方法によって行
った。The present invention will be described below in detail with reference to examples.
The performance evaluation in the examples was performed by the following method.
【００２２】（１）コードの強力 引張荷重測定器（島津製、オートグラフ）を用い、ＪＩ
Ｓ Ｌ−１０７４−６４に従って測定した。(1) Power of cord Using a tensile load measuring device (Autograph, manufactured by Shimadzu), JI
Measured according to SL-1074-64.
【００２３】（２）製糸性 延伸ローラーおよび熱処理ローラーに熱分解物が堆積
し、延伸困難となり、清掃を行う必要となるまでの時間
により３段階で評価した。 ○：２日以上、△：８時間〜２日、×：８時間未満 （３）コード硬さ ガーレ式硬さ測定機（テスター産業製）を用い、ＪＩＳ
Ｌ−１０９６−６．２０に従って測定し、相対評価：
○＝良好、△＝やや不良、×＝不良でもって示した。(2) Yarn-producing properties Thermal decomposition products were deposited on the stretching roller and the heat-treating roller, making stretching difficult, and the time required for cleaning was evaluated in three stages. ○: 2 days or more, Δ: 8 hours to 2 days, ×: less than 8 hours (3) Cord hardness JIS using a Gurley hardness meter (manufactured by Tester Sangyo)
Measured according to L-1096-6.20, relative evaluation:
＝= good, Δ = slightly poor, × = bad.
【００２４】（４）接着性評価 ＪＩＳ Ｌ１０１７の接着力−Ａ法（Ｔテスト）に準じ
て評価した。(4) Evaluation of Adhesion Evaluation was carried out according to the adhesion-A method (T test) of JIS L1017.
【００２５】（５）疲労性評価 未加硫ゴムに接着処理コード１本を埋め込み１５０℃、
３０分、５０ｋｇ／ｃｍ2の条件で加硫すると同時にゴ
ムに接着させた試験片を用い、ＪＩＳ Ｌ−１０１７の
ディスク疲労（グッドリッチ法）に従って、伸張率：＋
６．０％、圧縮率：−１２．６、疲労回数：１００万
回、室温下の条件で行った時の疲労前後の強力維持率を
評価した。(5) Fatigue evaluation One adhesive treatment cord was embedded in unvulcanized rubber at 150 ° C.
Using a test piece which was vulcanized under the conditions of 50 kg / cm 2 for 30 minutes and simultaneously adhered to rubber, according to JIS L-1017 disk fatigue (Goodrich method), elongation ratio: +
6.0%, compression ratio: -12.6, number of fatigue: 1,000,000 times, and the strength retention before and after fatigue when performed under the condition at room temperature were evaluated.
【００２６】［実施例１〜６，比較例１〜６］ （ａ）紡糸油剤Ａ〜Ｆ 表１に示す組成においてポリエチレンイミンを除いた油
剤組成分を５０℃に加温し、５０℃の軟化水中に添加し
ながら攪拌した。さらに表１の組成となるように秤取っ
たポリエチレンイミンを酢酸で中和したものをこれに添
加し攪拌した後、室温に冷却し１０％エマルジョンとし
た。[Examples 1 to 6, Comparative Examples 1 to 6] (a) Spinning oils A to F In the compositions shown in Table 1, the oil components excluding polyethyleneimine were heated to 50 ° C and softened at 50 ° C. Stir while adding to the water. Further, a mixture obtained by neutralizing polyethyleneimine with acetic acid and weighed so as to have the composition shown in Table 1 was added thereto, followed by stirring, followed by cooling to room temperature to obtain a 10% emulsion.
【００２７】（ｂ）紡糸油剤Ｇ〜Ｈ 表１に示す組成の油剤成分を５０℃に加温し、５０℃の
軟化水中に添加しながら攪拌後、室温に冷却し１０％エ
マルジョンとした。(B) Spinning oils G to H Oil components having the compositions shown in Table 1 were heated to 50 ° C., stirred in softened water at 50 ° C., stirred, and then cooled to room temperature to form a 10% emulsion.
【００２８】[0028]
【表１】 [Table 1]
【００２９】（ｃ）ポリエステル繊維の製造 固有粘度（３５℃オルソクロロフェノール溶媒にて測
定）０．９７のポリエチレンテレフタレートチップより
溶融紡糸方法により下記要領で１０００ｄ／１９２ｆの
ヤーン得た。紡糸口金より紡出され、冷却固化した１９
２ｆの未延伸糸条に、上記の方法で調整した紡糸油剤を
繊維１００重量部に対して油剤付着分０．４重量部とな
るようにローラ給油法で付与した後、６０℃の第１ロー
ラで引取り、第１ローラと第２ローラとの間で３．５倍
に第１段延伸し、さらに、第２ローラと２２０℃の第３
ローラとの間で合計延伸倍率が６．１倍になるように第
２段延伸し、引き続き第３ローラと第４ローラとの間で
３％のリラックスを与えるとともに仕上油剤であるエポ
キシ化合物（デナコールＥＸ−３１３）を繊維１００重
量部に対して油剤付着分が所定量となるように計量ノズ
ル式給油法で付与し、３０００ｍ／分の速度で巻取っ
た。(C) Production of polyester fiber A 1000 d / 192 f yarn was obtained from a polyethylene terephthalate chip having an intrinsic viscosity of 0.97 (measured in an orthochlorophenol solvent at 35 ° C.) by a melt spinning method as follows. 19 spun from the spinneret and solidified by cooling
After applying the spinning oil prepared by the above method to the undrawn yarn of 2f by a roller lubrication method so that the amount of oil adhering to the fiber is 0.4 part by weight based on 100 parts by weight of the fiber, the first roller at 60 ° C. And the first roller is stretched 3.5 times between the first roller and the second roller.
The film is stretched in the second stage so that the total stretching ratio becomes 6.1 times with the rollers, and then 3% is relaxed between the third roller and the fourth roller, and an epoxy compound (denacol) which is a finishing oil agent EX-313) was applied to 100 parts by weight of the fiber by a metering nozzle type lubricating method so that the amount of the oil agent attached was a predetermined amount, and was wound at a speed of 3000 m / min.
【００３０】（ｄ）コードの処理 上記の方法で得られた１０００ｄ／１９２ｆのヤーン２
本を下撚４９０回／ｍ、上撚４９０回／ｍの撚数で撚糸
してコードとした。このコードをＲＦＬ（レゾルシン・
ホルマリン・ラテックス系接着液）に浸透し、１００℃
で２分間乾燥した後、２３０℃で２分間熱処理した。(D) Processing of the cord 1000d / 192f yarn 2 obtained by the above method
The book was twisted with a twist number of 490 turns / m and a twist of 490 turns / m to form a cord. This code is called RFL (Resorcinol
Formalin / latex adhesive)
And heat-treated at 230 ° C. for 2 minutes.
【００３１】以上より得られたＲＦＬ処理後のコードの
ゴムとの接着性、強力およびゴム中での疲労性の評価を
行った。結果を表２に示す。The obtained RFL-treated cord was evaluated for its adhesion to rubber, strength, and fatigue in rubber. Table 2 shows the results.
【００３２】[0032]
【表２】 [Table 2]
【００３３】[0033]
【発明の効果】以上のように本発明のポリエステル繊維
からは、ＲＦＬ処理を行うだけで、ゴムとの接着性が良
好であり、かつ、強力およびゴム中での耐疲労性が著し
く改善された補強用繊維を得ることができ、該繊維はタ
イヤ、ベルト、ホースなどの補強材料として極めて優れ
た性能を発揮する。また、該ポリエステルの製造方法と
して、紡出した糸条にポリエチレンイミンを付与し、熱
延伸後エポキシ化合物を付与する方法を採用すれば、延
伸ローラや熱処理ローラなどに汚れが発生し難く、安定
した生産が可能となるといった効果を奏するものであ
る。As described above, from the polyester fiber of the present invention, the adhesion to rubber is good and the strength and the fatigue resistance in rubber are remarkably improved only by performing the RFL treatment. A reinforcing fiber can be obtained, and the fiber exhibits extremely excellent performance as a reinforcing material for tires, belts, hoses and the like. Further, as a method for producing the polyester, if a method in which polyethyleneimine is applied to the spun yarn and an epoxy compound is applied after hot stretching is adopted, dirt does not easily occur on a stretching roller, a heat treatment roller, and the like. This has the effect of enabling production.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｄ０６Ｍ 13/11 Ｄ０６Ｍ 13/11 // Ｄ０６Ｍ 101:32 (72)発明者 牧野 昭二 愛媛県松山市北吉田町77番地 帝人株式会 社松山事業所内 Ｆターム(参考） 4J002 AC00W CF06X CF08X FA04X FA06X GN01 GT00 4L033 AA07 AB01 AC11 BA08 CA32 CA34 CA68 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) D06M 13/11 D06M 13/11 // D06M 101: 32 (72) Inventor Shoji Makino Kitayoshida, Matsuyama City, Ehime Prefecture 77-machi Teijin Limited Matsuyama Office F-term (reference) 4J002 AC00W CF06X CF08X FA04X FA06X GN01 GT00 4L033 AA07 AB01 AC11 BA08 CA32 CA34 CA68
Claims (3)
０．０００１〜０．０３０重量％のポリエチレンイミ
ン、および、０．０５〜０．４０重量％のエポキシ化合
物が付着していることを特徴とするゴム補強用ポリエス
テル繊維。Claims: 1. The surface of a fiber, based on the weight of the fiber,
A polyester fiber for rubber reinforcement, to which 0.0001 to 0.030% by weight of polyethyleneimine and 0.05 to 0.40% by weight of an epoxy compound are adhered.
上である請求項１記載のゴム補強用ポリエステル繊維。2. The rubber reinforcing polyester fiber according to claim 1, wherein the molecular weight of the polyethyleneimine is 300,000 or more.
し、紡出した糸条に該繊維重量に対して０．０００１〜
０．０３０重量％のポリエチレンイミンを付与し、熱延
伸した後、該繊維重量に対して０．０５〜０．４０重量
％のエポキシ化合物を付与することを特徴とするゴム補
強用ポリエステル繊維の製造方法。3. The polyester fiber is melt-spun and the spun yarn has a weight of 0.0001 to 0.001% based on the weight of the fiber.
Production of a polyester fiber for rubber reinforcement, wherein 0.030% by weight of polyethyleneimine is applied, and after hot stretching, 0.05 to 0.40% by weight of an epoxy compound is applied to the fiber weight. Method.
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|---|---|---|---|
| JP17521099A JP4190663B2 (en) | 1999-06-22 | 1999-06-22 | Manufacturing method of polyester fiber for rubber reinforcement |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17521099A JP4190663B2 (en) | 1999-06-22 | 1999-06-22 | Manufacturing method of polyester fiber for rubber reinforcement |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001003273A true JP2001003273A (en) | 2001-01-09 |
| JP4190663B2 JP4190663B2 (en) | 2008-12-03 |
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| JP17521099A Expired - Fee Related JP4190663B2 (en) | 1999-06-22 | 1999-06-22 | Manufacturing method of polyester fiber for rubber reinforcement |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US7669626B1 (en) * | 2008-11-07 | 2010-03-02 | The Goodyear Tire & Rubber Company | Tire with component containing polyketone short fiber and polyethyleneimine |
| WO2010101745A1 (en) | 2009-03-04 | 2010-09-10 | Dow Global Technologies Inc. | Thermosettable composition containing a glycidylether based on trimethyolpropane octadecaethoxilate |
| WO2016100817A1 (en) * | 2014-12-19 | 2016-06-23 | Basf Se | A composite article |
| WO2018166823A1 (en) * | 2017-03-13 | 2018-09-20 | Basf Se | Coat fiber and method |
| WO2024068700A1 (en) | 2022-09-29 | 2024-04-04 | Basf Se | Improving adhesion of fibre materials in rubber composites |
-
1999
- 1999-06-22 JP JP17521099A patent/JP4190663B2/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7669626B1 (en) * | 2008-11-07 | 2010-03-02 | The Goodyear Tire & Rubber Company | Tire with component containing polyketone short fiber and polyethyleneimine |
| WO2010101745A1 (en) | 2009-03-04 | 2010-09-10 | Dow Global Technologies Inc. | Thermosettable composition containing a glycidylether based on trimethyolpropane octadecaethoxilate |
| WO2016100817A1 (en) * | 2014-12-19 | 2016-06-23 | Basf Se | A composite article |
| CN107250304A (en) * | 2014-12-19 | 2017-10-13 | 巴斯夫欧洲公司 | composite article |
| US10611929B2 (en) | 2014-12-19 | 2020-04-07 | Basf Se | Composite article |
| WO2018166823A1 (en) * | 2017-03-13 | 2018-09-20 | Basf Se | Coat fiber and method |
| CN110418813A (en) * | 2017-03-13 | 2019-11-05 | 巴斯夫欧洲公司 | Coated fiber and method |
| JP2020511602A (en) * | 2017-03-13 | 2020-04-16 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Coated fiber and method |
| JP7227149B2 (en) | 2017-03-13 | 2023-02-21 | ビーエーエスエフ ソシエタス・ヨーロピア | Coated fiber and method |
| US11692078B2 (en) | 2017-03-13 | 2023-07-04 | Basf Se | Coated fiber and method |
| WO2024068700A1 (en) | 2022-09-29 | 2024-04-04 | Basf Se | Improving adhesion of fibre materials in rubber composites |
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| Publication number | Publication date |
|---|---|
| JP4190663B2 (en) | 2008-12-03 |
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