JPH08218277A - High-strength polyvinyl alcohol-based fiber excellent in fatigue resistance and its production - Google Patents

Abstract

PURPOSE: To obtain polyvinyl alcohol-based fibers suitable as a rubber- or plastic-reinforcing material having high yarn strength and resistant to repeated flex or wear for a long time. CONSTITUTION: A dimethyl sulfoxide solution of a polyvinyl alcohol >=3000 in viscosity-average polymerization degree is subjected to dry-wet spinning into fibers, which are, in turn, passed through a coagulating bath containing >=50wt.% of ethanol and then subjected to wet orientation by a factor of 4 in an ethanol/methanol liquid along with desolvation. The resultant fibers are introduced into a hot oven where the fibers are subjected to dry heat orientation at 220 deg.C so that the whole draw ratio result in >=16. Subsequently, the resultant fibers are imparted with 0.5-7wt.% of a polyamide or polyurethane resin by a touch roller system to obtaint the objective polyvinyl alcohol-based fibers >=15g/d in yarn tenacity having on the surface lateral stripes nearly rectangular to the fiber axis at a number of 0-10 on average per 100μm in the fiber length direction.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は高強度でかつ長時間くり
返し屈曲や摩耗を受けるタイヤ、オイルブレーキホー
ス、ラジエーターホース、消防ホース、コンベアベル
ト、Ｖベルトなどのゴム補強材あるいはプラスチック補
強材、さらにはロープ、漁網などの一般産業資材に適し
た耐疲労性に優れたポリビニルアルコール（以下、ＰＶ
Ａと略記する）系繊維とその製造法に関するものであ
る。BACKGROUND OF THE INVENTION The present invention relates to a rubber reinforcing material or a plastic reinforcing material for a tire, an oil brake hose, a radiator hose, a fire hose, a conveyor belt, a V-belt, etc., which has high strength and is repeatedly bent or worn for a long time. Is a polyvinyl alcohol with excellent fatigue resistance suitable for general industrial materials such as ropes and fishing nets (hereinafter PV
A type fiber and its manufacturing method.

【０００２】[0002]

【従来の技術】従来ＰＶＡ系繊維は強度、弾性率、接着
性、耐薬品性、耐候性などの点でポリアミド、ポリエス
テル、ポリアクリロニトリル系繊維に比べて優れおり、
産業資材分野を中心に独自の用途を開拓してきた。高強
度、高弾性率のＰＶＡ系繊維を得る方法としては、特開
昭５９−１００７１０号公報、特開昭６１−１０８７１
１号公報、特開昭６３−９９３１５号公報などの方法が
公知である。2. Description of the Related Art Conventional PVA fibers are superior to polyamide, polyester and polyacrylonitrile fibers in strength, elastic modulus, adhesion, chemical resistance and weather resistance.
We have pioneered unique applications centered on the industrial materials field. As a method for obtaining a PVA fiber having high strength and high elastic modulus, JP-A-59-100170 and JP-A-61-10871 are known.
Methods such as JP-A No. 1 and JP-A No. 63-99315 are known.

【０００３】しかしこれらの方法は非抽出系で冷却ゲル
化後メタノールで溶剤を抽出したり、メタノール系で凝
固する為、溶剤抽出が速くて不均一ゲルとなり易く、高
倍率延伸で横じま（白化）によるボイドや欠陥部を生
じ、屈曲疲労性や衝撃に対し満足したものは得られなか
った。一方、発明者らは多価アルコール系溶剤を用いエ
タノール系の遅延凝固で均一なゲル構造をつくり、強度
や耐疲労性に優れたＰＶＡ系繊維を得る方法を特開平２
−３０７９０８号公報に開示したが、これでも耐疲労性
は不十分であった。またＰＶＡ系コードに液状ゴムを含
浸させて耐ゴム疲労性を向上させる方法が特開昭６３−
６６３８２号公報、特開昭６３−１９６７７８号公報に
開示されているが、本発明の如く強度と耐疲労性を同時
に満足するものではなかった。However, in these methods, since the solvent is extracted with methanol after cooling gelation in a non-extracting system or coagulating in methanol system, the solvent extraction is fast and a non-uniform gel is apt to be formed, and horizontal stretching occurs at a high draw ratio. Voids and defects were generated due to (whitening), and no product satisfying flexural fatigue resistance and impact was obtained. On the other hand, the inventors of the present invention have disclosed a method for producing a PVA-based fiber excellent in strength and fatigue resistance by producing a uniform gel structure by delayed coagulation of ethanol using a polyhydric alcohol solvent.
Although it was disclosed in Japanese Patent Publication No. 307908, fatigue resistance was still insufficient. A method of impregnating a PVA cord with liquid rubber to improve rubber fatigue resistance is disclosed in JP-A-63-
Although disclosed in Japanese Patent No. 66382 and Japanese Patent Laid-Open No. 63-196778, the strength and fatigue resistance are not satisfied at the same time as in the present invention.

【０００４】[0004]

【発明が解決しようとする課題】本発明者らは、さらな
る耐疲労性向上を目指して鋭意検討した結果、均一構造
で外力を分散させると同時に繊維表面に応力緩和層を形
成させて屈曲によるキンクバンドの発生や成長を抑えた
り、摩耗を抑える事が有効であると考えた。さらに応力
緩和層を形成させる為には、繊維強度をあまり低下させ
ずに高温にも耐える樹脂を繊維表面にコートするのが良
いことが判った。本発明は耐疲労性に優れた高強度ＰＶ
Ａ系繊維を提供するものである。DISCLOSURE OF THE INVENTION As a result of intensive studies aimed at further improving fatigue resistance, the inventors of the present invention have found that an external force is dispersed in a uniform structure and at the same time a stress relaxation layer is formed on the fiber surface to form a kink due to bending. We thought that it was effective to suppress the generation and growth of bands and to suppress wear. Further, in order to form the stress relaxation layer, it has been found that it is preferable to coat the fiber surface with a resin that can withstand high temperature without significantly lowering the fiber strength. The present invention is a high strength PV with excellent fatigue resistance.
A type fiber is provided.

【０００５】[0005]

【課題を解決するための手段】本発明は、粘度平均重合
度が３０００以上のＰＶＡ系ポリマーからなる繊維にお
いて、繊維表面に、繊維軸とほぼ直角方向に横じまが繊
維長さ１００μｍ当たり平均０〜１０本存在しており、
かつ繊維表面にポリアミド系又はポリウレタン系の樹脂
が０．５〜７重量％付着しており、さらにヤーン強度が
１５ｇ／ｄ以上であるＰＶＡ系繊維であり、そしてその
製造方法として、粘度平均重合度が３０００以上のＰＶ
Ａ系ポリマーの溶液をノズルより吐出して紡糸する方法
において、凝固浴としてエタノールを５０重量％以上含
む液を用い、紡糸後に総延伸倍率が１６倍以上となるよ
うに２２０℃以上で乾熱延伸を行い、その後にポリアミ
ド系又はポリウレタン系の樹脂を繊維に対して０．５〜
７重量％付与することを特徴とするＰＶＡ系繊維の製造
方法である。Means for Solving the Problems The present invention relates to a fiber made of a PVA polymer having a viscosity average degree of polymerization of 3000 or more. There are 0-10,
A PVA-based fiber having a polyamide-based or polyurethane-based resin attached to the fiber surface in an amount of 0.5 to 7% by weight and further having a yarn strength of 15 g / d or more. PV of 3000 or more
In a method of spinning a solution of an A-based polymer through a nozzle for spinning, a liquid containing 50% by weight or more of ethanol is used as a coagulation bath, and dry heat drawing is performed at 220 ° C. or more so that the total draw ratio becomes 16 times or more after spinning. Then, a polyamide-based or polyurethane-based resin is added to the fiber in an amount of 0.5 to
7% by weight of the PVA-based fiber is added.

【０００６】すなわち本発明は、ＰＶＡ系繊維を紡糸す
る際に、エタノール系の遅延凝固で均一ゲル構造を形成
させたあと高温高倍率に延伸し、白化による横じまが１
００μ長さ当たり平均１０本以下としたのち、耐熱性の
ポリアミド系樹脂又はポリウレタン系樹脂を繊維表面に
付着させることを特徴とする耐疲労性に優れた高強度ポ
リビニルアルコール系繊維及びその製造法に関するもの
である。That is, according to the present invention, when spinning a PVA fiber, a uniform gel structure is formed by delayed solidification of an ethanol system, and then stretched at a high temperature and a high ratio to obtain a horizontal stripe of 1 due to whitening.
A high-strength polyvinyl alcohol-based fiber excellent in fatigue resistance, characterized in that a heat-resistant polyamide-based resin or polyurethane-based resin is adhered to the fiber surface after the average number of fibers per 00 μ length is 10 or less, and a method for producing the same. It is a thing.

【０００７】以下、本発明の内容をさらに詳細に説明す
る。本発明に言うＰＶＡ系重合体とは、３０℃の水溶液
で粘度法により求めた平均重合度が３０００以上のもの
であり、好ましくはケン化度が９８．５モル％以上で分
岐度の低い直鎖状のものである。ＰＶＡの平均重合度が
高いほど欠陥部になり易い分子鎖末端が少なく、かつ結
晶間を連結するタイ分子が多くなる為、高強度で耐疲労
性に強い繊維となる。好ましくは平均重合度が６０００
以上、さらに好ましくは１００００以上である。ケン化
度が９８．５モル％未満では分子鎖の乱れが大きすぎて
結晶化が進まず強度や耐熱性が低下するなどの問題が生
じやすい。また、必要に応じて酸化防止剤、顔料、架橋
剤、油剤などを添加又は付着しても何んら問題ないが、
強度や耐疲労性を低下させない程度に添加量を抑えるの
が好ましい。The contents of the present invention will be described in more detail below. The PVA polymer referred to in the present invention is one having an average degree of polymerization of 3000 or more as determined by a viscosity method in an aqueous solution of 30 ° C., preferably a saponification degree of 98.5 mol% or more and a straight chain having a low branching degree. It is a chain. The higher the average degree of polymerization of PVA, the smaller the number of molecular chain ends that tend to become defects and the more tie molecules that connect the crystals, resulting in a fiber having high strength and high fatigue resistance. Preferably the average degree of polymerization is 6000
Or more, and more preferably 10000 or more. When the degree of saponification is less than 98.5 mol%, the disorder of the molecular chain is so large that crystallization does not proceed and the strength and heat resistance tend to deteriorate. Further, if necessary, there is no problem even if an antioxidant, a pigment, a cross-linking agent, an oil agent or the like is added or attached,
It is preferable to control the addition amount to the extent that strength and fatigue resistance are not deteriorated.

【０００８】ＰＶＡ系重合体の溶剤としては、グリセリ
ン、エチレングリコール、ジエチレングリコール、トリ
エチレングリコール、３−メチルペンタン−１，３，５
−トリオールなどの多価アルコールやジメチルスルホキ
シド（ＤＭＳＯ）、ジメチルホルムアミド、ジメチルア
セトアミド、Ｎ−メチルピロリドン、１，３−ジメチル
−２−イミダゾリジノン、エチレンジアミン、ジエチレ
ントリアミンおよび水などが単独または混合して使用さ
れる。さらに塩化亜鉛、塩化マグネシウム、ロダンカル
シウム、臭化リチウムなどの無機塩水溶液など該重合体
を溶解するものも使用可能である。冷却でゲル化するよ
うな多価アルコールやそれらと水との混合溶剤あるいは
ジメチルスルホキシド、ジメチルホルムアミドやそれら
と水との混合溶剤などが紡糸安定となり易いので好まし
い。Solvents for PVA type polymers include glycerin, ethylene glycol, diethylene glycol, triethylene glycol, 3-methylpentane-1,3,5.
-A polyhydric alcohol such as triol, dimethyl sulfoxide (DMSO), dimethylformamide, dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, ethylenediamine, diethylenetriamine and water are used alone or in combination. To be done. Further, it is also possible to use a solution that dissolves the polymer, such as an aqueous solution of an inorganic salt such as zinc chloride, magnesium chloride, calcium rhodanide or lithium bromide. A polyhydric alcohol that gels upon cooling, a mixed solvent of them and water, dimethyl sulfoxide, dimethylformamide, a mixed solvent of them and water, and the like are preferable because spinning stability tends to occur.

【０００９】紡糸方式としては湿式または乾湿式いずれ
でもよいが、均一ゲル繊維を得る為にノズル温度と凝固
温度に大きな差がつけられ急冷が可能な乾湿式紡糸が望
ましい。凝固浴は一般に溶剤を抽出するメタノールやエ
タノールなどの第１級アルコールやアセトン、アルカリ
水溶液、アルカリ金属塩水溶液などが使用されるが、本
発明では５０重量％以上がエタノールである必要があ
る。エタノールが５０重量％未満で、残りが前記抽出剤
の場合凝固速度が早くなり均一ゲル化が起こりずらく、
延伸時白化して横じまが多数発生する。また、凝固速度
を遅くする為に該溶剤をエタノールに混合しても問題な
いが、エタノール含有量が５０重量％未満では凝固が弱
く、糸切れや膠着などの問題を生じて好ましくない。最
適なエタノール含有量は、６５〜９５重量％であり、残
りはポリマーを溶解した溶剤であるのが好ましい。The spinning system may be either wet or dry, but in order to obtain a uniform gel fiber, dry-wet spinning is preferred because of a large difference between the nozzle temperature and the coagulation temperature and rapid cooling is possible. For the coagulation bath, generally, a primary alcohol such as methanol or ethanol for extracting a solvent, acetone, an aqueous alkali solution, an aqueous alkali metal salt solution, or the like is used, but in the present invention, 50% by weight or more must be ethanol. When the amount of ethanol is less than 50% by weight and the rest is the above-mentioned extractant, the coagulation rate becomes faster and uniform gelation is less likely to occur,
Whitening occurs during stretching and many horizontal stripes occur. Further, there is no problem even if the solvent is mixed with ethanol in order to slow the coagulation rate, but if the ethanol content is less than 50% by weight, coagulation is weak, and problems such as thread breakage and sticking occur, which is not preferable. The optimum ethanol content is preferably 65 to 95% by weight, the remainder being solvent in which the polymer is dissolved.

【００１０】凝固温度は３０℃以下、好ましくは１５℃
以下、より好ましくは５℃以下にし、急冷により均一な
微結晶構造（透明ゲル）にするのが望ましい。次いで得
られた繊維の断面変形や膠着を防止する為に、溶剤を含
んだままで２倍以上、好ましくは４倍以上湿延伸するの
が良い。続いてエタノール又はメタノールの抽出剤で該
溶剤のほとんど全部を除去したあと、乾燥により該抽出
剤を蒸発させる。The solidification temperature is 30 ° C. or lower, preferably 15 ° C.
Hereafter, it is more preferable that the temperature is 5 ° C. or lower, and rapid cooling to obtain a uniform fine crystal structure (transparent gel). Next, in order to prevent the cross-section deformation and sticking of the obtained fiber, it is preferable to wet-stretch it with the solvent contained at least 2 times, preferably 4 times or more. Subsequently, almost all of the solvent is removed with an ethanol or methanol extractant, and the extractant is evaporated by drying.

【００１１】その後２２０℃以上、好ましくは２３０〜
２６０℃で乾熱オイルバス、窒素ガス中、空気中などい
ずれかの乾熱方式で延伸を行なう。延伸温度が２２０℃
未満では配向結晶化が進まず、延伸倍率が低くなって高
強度のものは得られない。また２００℃以下で高倍率に
無理に延伸すると白化による横じまが多数でき易く、耐
疲労性が低下する恐れがある。一方、２６０℃以上では
ＰＶＡの分解が激しく、ＰＶＡ分子鎖のフローが起こっ
て、高強度とならない。延伸は、総延伸倍率１６倍以
上、好ましくは１８倍以上に行なうのが良い。１６倍未
満では分子鎖の配向が不十分で低強度のものしか得られ
ない。なお本発明で言う総延伸倍率とは、湿延伸倍率と
乾熱延伸倍率との積で表される値である。本発明で得ら
れる延伸糸は均一で断面が円形であり、マクロボイドが
出来ず、横じまがほとんどない為メタノール系凝固の延
伸糸よりも光沢がある。このような方法で得られた繊維
は、ボイドにより生じる横じまが極めて少なく、繊維長
さ１００μｍ当たり平均１０本以下であり、好ましくは
５本以下である。通常繊維を高強度とするために高倍率
に延伸を行なうと、必然的に横じまが生じることとな
る。本発明のＰＶＡ系繊維は高強度であるにもかかわら
ず横じまが少ないことが大きな特長的である。After that, 220 ° C. or higher, preferably 230-
Stretching is performed at 260 ° C. by a dry heat oil bath, nitrogen gas, air, or any other dry heat method. Stretching temperature is 220 ℃
If it is less than the above range, oriented crystallization does not proceed, the draw ratio becomes low, and a high strength product cannot be obtained. Further, if the film is forcibly stretched at a high magnification at 200 ° C. or less, a large number of horizontal stripes due to whitening are likely to occur, and the fatigue resistance may be reduced. On the other hand, at 260 ° C. or higher, PVA is severely decomposed and the PVA molecular chain flows, so that high strength is not obtained. The stretching may be performed at a total stretching ratio of 16 times or more, preferably 18 times or more. If it is less than 16 times, the orientation of the molecular chain is insufficient and only low strength can be obtained. The total draw ratio in the present invention is a value represented by the product of the wet draw ratio and the dry heat draw ratio. The drawn yarn obtained according to the present invention is uniform and has a circular cross section, has no macrovoids, and has almost no horizontal stripes, and thus is more glossy than a methanol-based coagulated drawn yarn. The fibers obtained by such a method have extremely few horizontal stripes caused by voids, and the average number of fibers per 100 μm is 10 or less, preferably 5 or less. Usually, when a fiber is stretched at a high ratio to have high strength, horizontal stripes are inevitably generated. The PVA-based fiber of the present invention has a great advantage in that it has a small amount of horizontal stripes despite its high strength.

【００１２】次いで本発明では、耐屈曲疲労性、耐摩耗
性など長期間使用される時の耐久性をさらに付与する為
に得られた高強度ＰＶＡ系延伸糸に０．５〜７重量％の
樹脂を付着させる必要がある。樹脂は比較的耐熱性があ
りＰＶＡと相溶性が良いポリアミド系又はポリウレタン
系のものである。例えば融点が８０〜２００℃のナイロ
ン６，６６，１２などを共重合したポリアミド系樹脂や
ハードセグメントが多くビカット軟化温度が８０〜１６
０℃のエステル系又はエーテル系のポリウレタン系樹脂
が良い。融点や軟化温度が低い樹脂はくり返し屈曲や摩
擦時の発熱で効果を失ない易く、高い樹脂は繊維を硬く
し、疲労性を悪化させて好ましくない。好ましくは融点
が１００〜１５０℃のポリアミド系樹脂又はビカット軟
化温度が１１０〜１５０℃のポリウレタン系樹脂であ
る。付着量が０．５重量％未満では耐疲労性や耐摩耗性
が十分満足できなくなり、７重量％を超えると強度低下
を招いたり、繊維が硬くなって逆に屈曲などでキンクバ
ンドを集中的に誘発増長させる可能性が出て来て好まし
くない。好ましい付着量は１〜５重量％である。Next, in the present invention, the high-strength PVA drawn yarn obtained for further imparting durability such as bending fatigue resistance and abrasion resistance when used for a long time is added in an amount of 0.5 to 7% by weight. It is necessary to attach resin. The resin is a polyamide-based or polyurethane-based resin that is relatively heat resistant and has good compatibility with PVA. For example, a polyamide-based resin having a melting point of 80 to 200 ° C. and copolymerized with nylon 6,66,12 or the like and a large amount of hard segments have a Vicat softening temperature of 80 to 16
Ester- or ether-based polyurethane resins at 0 ° C are preferable. A resin having a low melting point or softening temperature is likely to lose its effect due to repeated bending or heat generation during friction, and a resin having a high melting point hardens the fiber and deteriorates the fatigue property, which is not preferable. Polyamide resin having a melting point of 100 to 150 ° C. or polyurethane resin having a Vicat softening temperature of 110 to 150 ° C. is preferable. If the adhesion amount is less than 0.5% by weight, fatigue resistance and wear resistance cannot be sufficiently satisfied, and if it exceeds 7% by weight, strength is reduced, or the fiber becomes hard and the kink band is concentrated due to bending and the like. It is not preferable because the possibility of eliciting prolongation may appear. The preferable amount of adhesion is 1 to 5% by weight.

【００１３】該樹脂は水や有機溶剤に溶解又は乳化させ
て、ローラータッチ方式やデイップニップ方式、ギアポ
ンプオイリング方式などにて繊維表面にコートされる。
次いで樹脂付着後、乾燥を含めた熱処理を施し、樹脂と
繊維を反応させたり、樹脂の被膜を形成させるが、その
場合少なくとも０．２ｇ／ｄ以上の張力下で処理するの
が良い。０．２ｇ／ｄ未満の張力では繊維の収縮が起こ
り易く、強度や弾性率の低下を来たす。一方高張力の場
合単糸切れによる性能低下が起こり易く、好ましい張力
は０．５〜１．５ｇ／ｄである。The resin is dissolved or emulsified in water or an organic solvent and coated on the fiber surface by a roller touch method, a dip nip method, a gear pump oiling method or the like.
Next, after the resin is adhered, heat treatment including drying is performed to react the resin with the fibers or form a resin film. In that case, it is preferable to treat under a tension of at least 0.2 g / d or more. If the tension is less than 0.2 g / d, the fiber tends to contract, resulting in a decrease in strength and elastic modulus. On the other hand, in the case of high tension, performance deterioration due to single yarn breakage easily occurs, and the preferable tension is 0.5 to 1.5 g / d.

【００１４】また、その後の工程通過性やコードの強力
利用率を高める為に摩擦係数の低い油剤を樹脂付着熱処
理後の繊維表面に付与させることは望ましい。本発明に
よりヤーン強度が１５ｇ／ｄ以上と高く、かつ耐屈曲疲
労性や耐摩耗性に優れた耐久性のあるＰＶＡ系繊維が得
られ、ゴムやプラスチックの補強材や一般産業資材に適
した高付加価値繊維となった。Further, it is desirable to add an oil agent having a low friction coefficient to the fiber surface after the heat treatment for resin adhesion, in order to enhance the subsequent processability and the strength utilization factor of the cord. INDUSTRIAL APPLICABILITY According to the present invention, a durable PVA-based fiber having a high yarn strength of 15 g / d or more and excellent bending fatigue resistance and abrasion resistance is obtained, which is suitable for a rubber or plastic reinforcing material and a general industrial material. It became a value-added fiber.

【００１５】[0015]

【実施例】以下実施例により本発明をさらに具体的に説
明するが、本発明は実施例のみに限定されるものではな
い。なお実施例中における各種の物性値は以下の方法に
より測定された。 （１）ＰＶＡ系重合体の粘度平均重合度（Ｐ_A） ＪＩＳ Ｋ−６７２６に準じて、ＰＶＡ系重合体を熱水
に溶かして希薄水溶液を作製し、３０℃における比粘度
を３点測定し、それらの値から固有粘度〔η〕を求め、
Ｐ_A＝（〔η〕×１０⁴／８．２９）^1.63により粘度平均
重合度を求めた。 （２）横じまの本数 １万倍の電子顕微鏡で繊維表面を観察し、１０点の平均
値を採用する。通常、横じまは、繊維表面を螺旋状に取
り巻くように存在しており、繊維表面を電子顕微鏡で見
ると、この螺旋状の横じまがほぼ一定周期で繊維表面を
旋回して存在しているように見える。横じまの本数はこ
の旋回して現れる回数毎に一本と数える。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the examples. Various physical properties in the examples were measured by the following methods. (1) Viscosity average degree of polymerization (P _A ) of PVA-based polymer According to JIS K-6726, a PVA-based polymer is dissolved in hot water to prepare a dilute aqueous solution, and specific viscosity at 30 ° C. is measured at 3 points. , The intrinsic viscosity [η] is calculated from these values,
The viscosity average degree of polymerization was determined by P _A = ([η] × 10 ⁴ /8.29) ^1.63 . (2) Number of horizontal stripes The fiber surface is observed with an electron microscope with a magnification of 10,000 times, and an average value of 10 points is adopted. Usually, the horizontal stripes are present so as to surround the fiber surface in a spiral shape, and when the fiber surface is viewed with an electron microscope, the spiral horizontal stripes exist around the fiber surface in a substantially constant cycle. It looks like The number of horizontal stripes is counted as one every time this swirling appears.

【００１６】（３）樹脂付着量 試料約５ｇを精秤し、１００℃以上の熱水にて繊維のみ
を溶解してその残渣重量より算出するか、又は無水酢酸
と過酸化水素水より得られる過酢酸を用いて樹脂のみを
溶解して試料の重量減少より求めた。 （４）ヤーン引張強度、初期弾性率 ＪＩＳ−Ｌ１０１３に準じ、ヤーンに予め８０回／ｍの
撚りをかけ２０℃，６５％ＲＨにて２４時間放置後、２
０℃，６５％ＲＨの標準状態で試長２０ｃｍ，引張速度
１０ｃｍ／ｍｉｎ，初荷重１／２０ｇ／ｄにてインスト
ロンＴＭ−Ｍ型エアー式コード用グリップを用いて、切
断強力及び伸度を測定した。さらに該８０回／撚りのヤ
ーンを１／２０ｇ／ｄ張力下で９０ｍ長のかせ捲きを作
り、重量測定によりヤーンデニールを算出し、該切断強
力をデニールで除して強度（ｇ／ａｒ）を求めた。ま
た、強力−伸度曲線の初期勾配より伸度１００％に相当
する強力を求め、それを該デニールで除して初期弾性率
を求めた。いずれもｎ＝１０の平均値を採用した。(3) Adhesion amount of resin About 5 g of a sample is precisely weighed, and only the fiber is dissolved in hot water at 100 ° C. or higher and calculated from the residue weight, or obtained from acetic anhydride and hydrogen peroxide solution. Only the resin was dissolved using peracetic acid, and the weight loss of the sample was determined. (4) Yarn Tensile Strength, Initial Elastic Modulus According to JIS-L1013, the yarn was twisted 80 times / m in advance and left at 20 ° C. and 65% RH for 24 hours, and then 2
Using the Instron TM-M type pneumatic cord grip at a test length of 20 cm, a tensile speed of 10 cm / min and an initial load of 1/20 g / d at 0 ° C. and 65% RH, the cutting strength and elongation are improved. It was measured. Furthermore, the 80 times / twisted yarn was made into a skein of 90 m length under a tension of 1/20 g / d, the yarn denier was calculated by gravimetric measurement, and the breaking strength was divided by the denier to obtain the strength (g / ar). I asked. Further, the strength corresponding to the elongation of 100% was obtained from the initial gradient of the strength-elongation curve, and this was divided by the denier to obtain the initial elastic modulus. In each case, the average value of n = 10 was adopted.

【００１７】（５）耐ゴム疲労性 １５００ｄｒの樹脂付着ＰＶＡヤーンを所定の撚数でＺ
方向に下撚したあと２本合せて同撚数でＳ方向に上撚し
て生コードを作成する。次いでＲＦＬ（レゾルシン、ホ
ルマリン、ゴム乳液）を付着してディップコードを作成
する。次いで圧縮側と伸長側に該コードを２０本並べた
２つのコード層を作成し、その中間及び外側にゴム層を
配して、サンドイッチ状の巾２５．４ｍｍ×長４２０ｍ
ｍ×厚さ約８ｍｍのゴムシートを作成したあと、１５０
℃×４５分９０ｋｇ／ｃｍ²で加硫してベルトを作成す
る。該ベルトをプーリー径２０ｍｍ〜８０ｍｍ（２０φ
〜８０φ）のベルト屈曲試験機に装置し、荷重４２ｋ
ｇ、往復速度１２０回／分、雰囲気温度１００℃で１万
回〜５０万回屈曲させたあと、圧縮側のコードをベルト
より取出し、屈曲前後のコード強力より保持率を求め耐
ゴム疲労性を評価した。(5) Rubber Fatigue Resistance A resin-adhered PVA yarn of 1500 dr is subjected to Z with a predetermined twist number.
After twisting in the direction, the two cords are combined and twisted in the S direction with the same number of twists to create a raw cord. Next, RFL (resorcin, formalin, rubber emulsion) is attached to prepare a dip code. Next, two cord layers are formed by arranging 20 cords on the compression side and the extension side, and a rubber layer is arranged in the middle and outside thereof to form a sandwich-like width 25.4 mm x length 420 m.
After making a rubber sheet of mx thickness of about 8 mm, 150
A belt is prepared by vulcanizing at 90 ° C. for 45 minutes at 90 kg / cm ² . The belt has a pulley diameter of 20 mm to 80 mm (20 φ
~ 80φ) belt bending tester, load 42k
g, reciprocating speed of 120 times / min, and bending at 10,000 ° C to 500,000 times at an ambient temperature of 100 ° C, the cord on the compression side is taken out from the belt, and the holding ratio is obtained from the cord strength before and after bending to obtain rubber fatigue resistance. evaluated.

【００１８】（６）耐摩耗性（撚合せ摩耗） １５００ｄｒの樹脂付着ＰＶＡヤーンを８０ｔ／ｍＺ方
向に撚をかけて輪を作成したあと、輪の中央部で３回Ｓ
方向に撚をかけ、室温で上下に糸同志を摩耗させ、切断
する時の回数を読んだ。(6) Abrasion resistance (twisting abrasion) After a 1500 dr resin-adhered PVA yarn is twisted in the direction of 80 t / mZ to form a ring, S is repeated three times at the center of the ring.
Twisted in the same direction, the threads were worn up and down at room temperature, and the number of cuts was read.

【００１９】実施例１，２および比較例１ 粘度平均重合度が４０００（実施例１）と８０００（実
施例２）でケン化度がいずれも９９．５モル％のＰＶＡ
をそれぞれ濃度１０重量％と７重量％になるようにジメ
チルスルホキシド（以下ＤＭＳＯと略記する）に１００
℃で溶解し、得られた各溶液を４００ホールのノズルよ
り吐出させ、エタノール／メタノール／ＤＭＳＯ＝６．
１／０．９／３．０重量比、５℃の凝固浴で湿式紡糸し
た。得られたゲル繊維は透明な円型断面を有していた。
さらに４０℃エタノール／メタノール＝８７／１３重量
比の液中で４倍湿延伸したあと、エタノール／メタノー
ル＝８７／１３重量比で該溶剤をほとんど全部除去し
た。得られた紡糸原糸を実施例１は１７０℃，２００
℃，２４０℃の３セクションからなる熱風炉で総延伸倍
率１９．２倍になるように乾熱延伸した。実施例２は、
１７０℃，２００℃，２５０℃にて総延伸倍率１８．７
倍の延伸を施した。得られた延伸糸の横じまは実施例１
が１００μ長さ当たり平均６．３本、実施例２が平均
４．８本と少なく、共にやや光沢を有していた。両延伸
糸はいずれも１５００ｄ／４００ｆで実施例１の強度は
１７．５ｇ／ｄ、弾性率は３６０ｇ／ｄを示し、実施例
２は強度２０．１ｇ／ｄ、弾性率４１０ｇ／ｄであっ
た。Examples 1 and 2 and Comparative Example 1 PVA having a viscosity average degree of polymerization of 4000 (Example 1) and 8000 (Example 2) and a saponification degree of 99.5 mol%.
Dimethylsulfoxide (hereinafter abbreviated as DMSO) to a concentration of 10% by weight and 7% by weight, respectively.
Dissolve at 0 ° C., discharge each solution obtained from a nozzle of 400 holes, ethanol / methanol / DMSO = 6.
Wet spinning was performed in a coagulation bath at a weight ratio of 1 / 0.9 / 3.0 of 5 ° C. The resulting gel fiber had a transparent circular cross section.
Further, after 4 times wet stretching in a liquid of ethanol / methanol = 87/13 weight ratio at 40 ° C., almost all of the solvent was removed at an ethanol / methanol = 87/13 weight ratio. The obtained spun raw yarn was used in Example 1 at 170 ° C., 200
Dry hot drawing was carried out in a hot-air oven consisting of three sections of ℃ and 240 ℃ so that the total draw ratio was 19.2 times. Example 2 is
Total stretch ratio of 18.7 at 170 ° C, 200 ° C, 250 ° C
Double stretching was performed. The horizontal stripes of the obtained drawn yarn are shown in Example 1.
The average number was 6.3 per 100 μm, and the average value in Example 2 was 4.8, which was a little, and both had a slight gloss. Both of the drawn yarns were 1500 d / 400 f, the strength of Example 1 was 17.5 g / d, and the elastic modulus was 360 g / d, and the strength of Example 2 was 20.1 g / d and the elastic modulus was 410 g / d. .

【００２０】次いで該延伸糸にローラータッチ方式でナ
イロン６，ナイロン６６，ナイロン１２の三者が共重合
し、融点が１１０℃のグリルテックス１Ｐ（ＥＭＳジャ
パン社製）の２％メタノール液を付着せしめ、張力１．
０ｇ／ｄ下で１００℃乾燥後２１０℃×３０秒熱処理を
施した。樹脂付着量は実施例１が３．３重量％、実施例
２が３．５重量％であった。次いで引続き低摩擦係数を
有するシリコン系油剤を０．７重量％付着させ１２０℃
にて乾燥した。実施例１で得た樹脂付着ヤーンの強度
は、１６．４ｇ／ｄ、弾性率は３４０ｇ／ｄを示し、実
施例２では強度１８．９ｇ／ｄ、弾性率３８０ｇ／ｄを
示し、樹脂付着前の性能と大差なかった。また耐ゴム疲
労性を評価すべく１５００ｄ／１×２、５０×５０ｔ／
１０ｃｍの生コードをＲＦＬ処理してデイップコードを
作成した。１００℃、２５φ×５０万回ベルト屈曲後の
強力保持率は実施例１が９３％、実施例２が９１％と屈
曲疲労性に優れており、自動車タイヤのカーカス補強材
として付加価値の高い繊維となった。一方、撚合せ摩耗
の切断回数は実施例１が３４０５回、実施例２が３８１
１回と耐摩耗性も良好であった。Then, the drawn yarn was copolymerized with nylon 6, nylon 66 and nylon 12 by a roller touch method, and a 2% methanol solution of Grilltex 1P (made by EMS Japan Co.) having a melting point of 110 ° C. was attached. , Tension 1.
After drying at 100 ° C. under 0 g / d, heat treatment was performed at 210 ° C. for 30 seconds. The resin adhesion amount was 3.3% by weight in Example 1 and 3.5% by weight in Example 2. Then, continue to deposit 0.7% by weight of a silicone oil having a low friction coefficient at 120 ° C.
It was dried at. The resin-adhered yarn obtained in Example 1 had a strength of 16.4 g / d and an elastic modulus of 340 g / d, and Example 2 had a strength of 18.9 g / d and an elastic modulus of 380 g / d. It was not much different from the performance of. To evaluate rubber fatigue resistance, 1500 d / 1 × 2, 50 × 50 t /
A 10 cm raw cord was RFL processed to form a dip cord. The strength retention after bending the belt at 100 ° C. and 25φ × 500,000 times is 93% in Example 1 and 91% in Example 2, which is excellent in bending fatigue, and has high added value as a carcass reinforcing material for automobile tires. Became. On the other hand, the number of cuts due to twisting wear was 3405 times in Example 1 and 381 in Example 2.
Once, wear resistance was also good.

【００２１】なお、比較例１として実施例１でエタノー
ルの代りにメタノールを用いて、紡糸し同様に延伸した
が、横じまが１００μ長さ当たり平均１８．４本と多く
白化とボイドのある繊維となった。次いで同様に該共重
合ナイロンを３．６％付着させてヤーン強度１６．１ｇ
／ｄ、弾性率３２０ｇ／ｄの樹脂付着ヤーンを得たが、
１００℃、２５φ×２５万回ベルト屈曲後の強力保持率
は８１％、撚合せ摩耗の切断回数は２８３０回といずれ
も実施例１より劣っていた。As Comparative Example 1, methanol was used in place of ethanol in Example 1, and spinning was carried out and stretched in the same manner. However, horizontal stripes had an average of 18.4 lines per 100 μ length, and many whitening and voids were present. Became a fiber. Then, similarly, 3.6% of the copolymerized nylon was attached to give a yarn strength of 16.1 g.
Although a resin-adhered yarn having an elastic modulus of / d and an elastic modulus of 320 g / d was obtained,
The strength retention after belt bending at 100 ° C. and 25φ × 250,000 times was 81%, and the number of cuts due to twisting abrasion was 2,830 times, which were all inferior to those of Example 1.

【００２２】実施例３及び比較例２ 粘度平均重合度が１７０００、ケン化度が９９．８モル
％のＰＶＡを用い濃度５．５重量％になるようにＤＭＳ
Ｏにて１１０℃で溶解し、得られた溶液を２００ホール
のノズルより吐出させ、エタノール／メタノール／ＤＭ
ＳＯ＝７／１／２重量比、７℃の凝固浴で乾湿式紡糸し
た。さらにエタノール／メタノール＝８７／１３浴で４
倍湿延伸したあとエタノール／メタノール＝８７／１３
浴で該溶剤を全部除去した。得られた紡糸原糸を１７０
℃と２５５℃の２つの輻射炉を用いて総延伸倍率１８．
４倍になるように乾熱延伸した。得られた延伸糸は７５
０ｄ／２００ｆで横じまが平均５．７本と少なく光沢の
ある円型断面を有しており、強度は２３．１ｇ／ｄ、弾
性率は５１０ｇ／ｄと高い値であった。次いで該延伸糸
を２本合せて１５００ｄ／４００ｆとし、ローラータッ
チ方式で１２５℃のビカット軟化温度を有するポリエー
テル系ポリウレタン（クラミロン９１９６クラレ製）の
３％ＤＭＦ溶液を付着させ、張力０．９ｇ／ｄ下で１０
０℃乾燥−１６０℃熱処理を施した。該ウレタン樹脂付
着量は２．４重量％であった。引続きシリコン系油剤を
０．５重量％付着させて１１０℃で乾燥した。得られた
樹脂付着ヤーンの強度は２１．２ｇ／ｄ、弾性率４５０
ｇ／ｄと高いレベルを維持していた。Example 3 and Comparative Example 2 PVA having a viscosity average degree of polymerization of 17,000 and a degree of saponification of 99.8 mol% was used so that the concentration was 5.5% by weight.
Dissolve in O at 110 ° C., discharge the resulting solution from a 200-hole nozzle, and use ethanol / methanol / DM
SO = 7/1/2 weight ratio, dry-wet spinning was performed in a coagulation bath at 7 ° C. Further ethanol / methanol = 87/13 bath 4
After double-moisture stretching, ethanol / methanol = 87/13
The bath removed all of the solvent. 170 of the obtained spun raw yarn
Total draw ratio of 18.
It was dry-heat stretched so as to be quadrupled. The drawn yarn obtained is 75
It had a circular cross-section with 0d / 200f, which had a few horizontal stripes and an average of 5.7, and had a high strength of 23.1 g / d and an elastic modulus of 510 g / d. Then, the two drawn yarns were combined to make 1500 d / 400 f, and a 3% DMF solution of a polyether polyurethane (made by Kuramilon 9196 Kuraray) having a Vicat softening temperature of 125 ° C. was attached by a roller touch method, and a tension of 0.9 g / 10 under d
Drying was performed at 0 ° C. and heat treatment was performed at 160 ° C. The amount of the urethane resin attached was 2.4% by weight. Subsequently, 0.5% by weight of a silicon-based oil agent was attached and dried at 110 ° C. The resin-bonded yarn obtained has a strength of 21.2 g / d and an elastic modulus of 450.
The high level of g / d was maintained.

【００２３】さらに該樹脂付着ヤーンで１５００ｄ／１
×２、３１．５×３１．５ｔ／１０ｃｍの生コードを作
成したあとＲＦＬ処理によりデイップコードを得た。１
００℃、２０φ×１万回及び１００℃、８０φ×１０万
回後のベルト屈曲強力保持率は各８２％及び９４％を示
し、高強力高弾性率で大歪及び小歪の両疲労性に優れ
た、従来に見られない耐久性のある繊維となった。これ
は自動車タイヤのベルト部やカーカス部、さらにはコン
ベアベルトなどの補強材として利用価値の高いものであ
った。さらに撚合せ摩耗の切断回数が５２１０回と耐摩
耗性も向上し、陸上ロープやネットあるいは帆布などに
も効果を発揮する事が判った。一方、比較例２として、
実施例３でウレタン樹脂を付着しない場合を実施した
が、１００℃、２０φ×１万回及び８０φ×１０万回ベ
ルト屈曲の強力保持率は各７３％及び８５％に低下し、
撚合せ摩耗も３１９０回と劣っていた。Further, the resin-adhered yarn is 1500 d / 1.
After forming a raw cord of x2, 31.5 x 31.5t / 10 cm, a dip code was obtained by RFL treatment. 1
The belt flexural strength retention rates after 00 ° C, 20φ × 10,000 times and 100 ° C, 80φ × 100,000 times are 82% and 94%, respectively, and have high strength and high elastic modulus and have both large strain and small strain fatigue resistance. It has become a superior, durable fiber that has never been seen before. This has a high utility value as a reinforcing material for a belt portion and a carcass portion of an automobile tire, and a conveyor belt. Further, it was found that the number of times of twisting abrasion cutting was 5210 times, the abrasion resistance was improved, and it was also effective for land ropes, nets, canvas and the like. On the other hand, as Comparative Example 2,
Although the case where no urethane resin was adhered was carried out in Example 3, the strength retention ratio of the belt bending at 100 ° C., 20φ × 10,000 times and 80φ × 100,000 times decreased to 73% and 85%, respectively.
The twisting wear was also inferior at 3190 times.

【００２４】実施例４ 粘度平均重合度が１２０００でケン化度が９９．４モル
％のＰＶＡを濃度６重量％になるように１８０℃のグリ
セリンに溶解し、エタノール／グリセリン＝８／２、−
５℃の凝固浴にて乾湿式紡糸した。次いで５０℃エタノ
ールで４．５倍湿延伸し、さらにエタノールで該溶剤を
ほとんど全部除去した。得られた紡糸原糸は透明感のあ
る円型断面を有し、１８０−２００−２５８℃の熱風炉
で総延伸倍率が１９．５倍になるように延伸された。横
じまは平均８．１本であり、１５００ｄ／５００ｆヤー
ンの強度は２２．５ｇ／ｄ、弾性率は５７０ｇ／ｄであ
った。次いで該延伸糸をデイップニップ方式で実施例１
で用いた共重合ナイロンに乳化剤を添加して２重量％の
水エマルジョン液を付着させ、張力１．１ｇ／ｄ下で１
００℃乾燥−２００℃熱処理を施した。該ナイロン樹脂
付着量は３．８重量％であった。引続き鉱物油系の水エ
マルジョン油剤を０．４重量％付着させ１２０℃で乾燥
した。得られた樹脂付着ヤーンの強度は２０．９ｇ／
ｄ、弾性率は５１０ｇ／ｄを示し、１５００ｄ／１×
２、３１．５×３１．５ｔ／１０ｃｍのデイップコード
による１００℃、２０φ×１万回及び８０φ×１０万回
ベルト屈曲の強力保持率は各々８０％及び９６％と耐ゴ
ム疲労性に優れている事が判明した。また撚合せ摩耗も
４０１０回と高く、くり返しの屈曲や摩耗に対し耐久性
のある高強力ＰＶＡ繊維となった。Example 4 PVA having a viscosity average degree of polymerization of 12000 and a degree of saponification of 99.4 mol% was dissolved in glycerin at 180 ° C. to a concentration of 6% by weight, and ethanol / glycerin = 8/2,-
Dry-wet spinning was performed in a coagulation bath at 5 ° C. Then, the film was wet-stretched 4.5 times with ethanol at 50 ° C., and almost all the solvent was removed with ethanol. The obtained spun raw yarn had a transparent circular cross section and was drawn in a hot air oven at 180-200 to 258 ° C. so that the total draw ratio was 19.5 times. The number of horizontal stripes was 8.1, the 1500d / 500f yarn had a strength of 22.5 g / d and an elastic modulus of 570 g / d. Then, the drawn yarn was processed by the dip nip method in Example 1.
An emulsifier was added to the copolymerized nylon used in Step 2 to attach a 2% by weight aqueous emulsion solution, and the tension was 1.1 g / d under 1
It was dried at 00 ° C. and heat-treated at 200 ° C. The amount of the nylon resin adhered was 3.8% by weight. Subsequently, 0.4% by weight of a mineral oil-based water emulsion oil agent was adhered and dried at 120 ° C. The strength of the obtained resin-adhered yarn is 20.9 g /
d, elastic modulus is 510 g / d, 1500 d / 1 ×
2,31.5 × 31.5t / 10cm dip cord at 100 ° C, 20φ × 10,000 times and 80φ × 100,000 times The belt flexural strength retention rate is 80% and 96% respectively, which is excellent in rubber fatigue resistance. It turned out that Moreover, the twisting abrasion was as high as 4010 times, and the high-strength PVA fiber was durable against repeated bending and abrasion.

【００２５】[0025]

【発明の効果】本発明により、ヤーン強度が１５ｇ／ｄ
以上と高く、かつ長時間の耐くり返し屈曲や耐摩耗性に
優れた耐久性に優れたＰＶＡ系繊維が得られ、ゴム補強
材、プラスチックスの補強材、あるいはロープ、ネッ
ト、帆布などの一般産業資材に適したＰＶＡ系繊維が得
られる。According to the present invention, the yarn strength is 15 g / d.
Higher than the above, PVA-based fiber with excellent durability that is durable against repeated bending and abrasion for a long time is obtained, and it is used for rubber reinforcing materials, plastic reinforcing materials, or general industries such as ropes, nets, and canvas. PVA-based fibers suitable for materials can be obtained.

Claims (2)

【特許請求の範囲】[Claims] 【請求項１】 粘度平均重合度が３０００以上のポリビ
ニルアルコール系ポリマーからなる繊維において、繊維
表面に、繊維軸とほぼ直角方向に横じまが繊維長さ１０
０μｍ当たり平均０〜１０本存在しており、かつ繊維表
面にポリアミド系又はポリウレタン系の樹脂が０．５〜
７重量％付着しており、さらにヤーン強度が１５ｇ／ｄ
以上であるポリビニルアルコール系繊維。1. A fiber made of a polyvinyl alcohol-based polymer having a viscosity average degree of polymerization of 3000 or more, and a fiber length of 10 is provided on the fiber surface in a direction substantially perpendicular to the fiber axis.
There is an average of 0 to 10 fibers per 0 μm, and 0.5 to 0.5 of polyamide-based or polyurethane-based resin on the fiber surface.
Adhesion is 7% by weight and yarn strength is 15 g / d
The polyvinyl alcohol fiber as described above. 【請求項２】 粘度平均重合度が３０００以上のポリビ
ニルアルコール系ポリマーの溶液をノズルより吐出して
紡糸する方法において、凝固浴としてエタノールを５０
重量％以上含む液を用い、紡糸後に総延伸倍率が１６倍
以上となるように２２０℃以上で乾熱延伸を行い、その
後にポリアミド系又はポリウレタン系の樹脂を繊維に対
して０．５〜７重量％付与することを特徴とするポリビ
ニルアルコール系繊維の製造方法。2. A method in which a solution of a polyvinyl alcohol polymer having a viscosity average degree of polymerization of 3000 or more is discharged from a nozzle and spinning is performed.
Using a liquid containing at least wt%, dry heat drawing is performed at 220 ° C. or more so that the total draw ratio becomes 16 times or more after spinning, and then a polyamide-based or polyurethane-based resin is added to the fiber in an amount of 0.5 to 7 A method for producing a polyvinyl alcohol-based fiber, which comprises imparting weight%.