JPH0860449A - Production of polyvinyl alcohol-based yarn - Google Patents
Production of polyvinyl alcohol-based yarnInfo
- Publication number
- JPH0860449A JPH0860449A JP18950894A JP18950894A JPH0860449A JP H0860449 A JPH0860449 A JP H0860449A JP 18950894 A JP18950894 A JP 18950894A JP 18950894 A JP18950894 A JP 18950894A JP H0860449 A JPH0860449 A JP H0860449A
- Authority
- JP
- Japan
- Prior art keywords
- yarn
- pva
- weight
- oil agent
- aliphatic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Artificial Filaments (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は，産業資材用，特にベル
ト用に適した高強力，高耐熱水性ポリビニルアルコール
（以下，ＰＶＡと略記する。）系繊維の製造法に関する
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing high-strength, highly heat-resistant water-soluble polyvinyl alcohol (hereinafter abbreviated as PVA) fiber suitable for industrial materials, especially for belts.
【０００２】[0002]
【従来の技術】ＰＶＡ系繊維は，ナイロン繊維やポリエ
ステル繊維等の汎用繊維素材に比べ，強度，弾性率が高
く，熱に対する寸法安定性もよく，また接着性も良好で
あり，産業資材用繊維として極めて優れた特性を有して
いる。また，最近は，その強度，弾性率をさらに高めよ
うとする試みが種々なされており，その結果，いわゆる
ゲル紡糸法によるポリエチレン繊維には及ばないもの
の，高強度・高弾性率繊維の代表とされるポリパラフェ
ニレンテレフタルアミド繊維に匹敵する強度・弾性率の
繊維が得られている。2. Description of the Related Art PVA-based fibers have higher strength and elastic modulus, better dimensional stability against heat, and better adhesiveness than general-purpose fiber materials such as nylon fibers and polyester fibers. It has extremely excellent characteristics. In addition, recently, various attempts have been made to further increase the strength and elastic modulus, and as a result, it is regarded as a representative of high-strength and high-modulus fibers, although it is not as good as polyethylene fibers by the so-called gel spinning method. Fibers with strength and elastic modulus comparable to that of polyparaphenylene terephthalamide fibers have been obtained.
【０００３】しかしながら，ナイロン繊維やポリエステ
ル繊維が熱水に不溶であるのに対し，ＰＶＡ系繊維は熱
水に溶解するため，その適用分野が限られていた。この
欠点を解消するため，これまでに古くはホルマリンなど
でアセタール化する方法が提案され，また最近では，例
えば特開平2-133605号公報に見られるように，アクリル
酸系重合体をブレンド紡糸する方法や，特開平4-126829
号公報にあるように脱水反応促進用触媒を付与した後，
熱処理して脱水反応を行わせることにより耐熱水性を改
良する方法などが提案されている。However, nylon fibers and polyester fibers are insoluble in hot water, whereas PVA-based fibers are soluble in hot water, so that their application fields have been limited. In order to overcome this drawback, a method of acetalizing with formalin has been proposed in the past, and recently, as shown in, for example, Japanese Patent Laid-Open No. 2-133605, an acrylic acid polymer is blend-spun. Method and JP-A-4-126829
As described in Japanese Patent Publication No.
There has been proposed a method of improving hot water resistance by performing heat treatment and dehydration reaction.
【０００４】一方，伝動ベルトで代表されるリブＶベル
ト，タイミングベルトなどは，製造工程を簡略化してコ
ストを低減するために，予め筒状に成型され，加硫され
たＰＶＡ系繊維補強ゴム複合体を輪切り状に切断して製
品化されている。しかし，繊維軸方向に切断されたベル
ト側面に露出されたＰＶＡ系繊維から単糸がほつれ，毛
羽状に突出することがある。その場合，製品の品位が低
下するばかりか，そのままプーリーにセットして運転す
ると，この単糸のほつれた部分がプーリーに摩擦されて
ほつれた単糸が飛び散ったり，このほつれが原因となっ
てベルトの耐久性を低下させるという問題がある。On the other hand, rib V belts, timing belts, etc., typified by transmission belts, are PVA-based fiber-reinforced rubber composites that have been preliminarily molded into a tubular shape and vulcanized in order to simplify the manufacturing process and reduce costs. It is commercialized by cutting the body into slices. However, a single yarn may fray from the PVA-based fiber exposed on the side surface of the belt cut in the fiber axis direction, and may protrude in a fluff shape. In that case, not only the quality of the product will deteriorate, but if the product is set in the pulley and operated as it is, the frayed part of this single yarn will be rubbed by the pulley and the frayed single yarn will scatter, and this fraying will cause the belt to break. However, there is a problem that the durability is reduced.
【０００５】この問題を解決する方法として，ＰＶＡ系
繊維に撚を掛けてコードとした後，このコードにエポキ
シ系接着剤及び／又はイソシアネート系接着剤を含浸
し，熱処理を施すことによってＰＶＡ系繊維の単糸間を
接着する方法がある。しかし，従来の紡糸油剤，例えば
脂肪族エステル系化合物主体の油剤を主成分とし，鉱物
油を希釈剤とするいわゆるストレート油剤を付与したも
のは，油剤と接着剤との相溶性が乏しく，油剤と接着剤
とが分離したり，接着剤が繊維の内部まで浸透しなかっ
たりして十分な効果が得られない。一方，このような問
題のない紡糸油剤，例えば脂肪族アミド化合物，脂肪族
アミン化合物，脂肪族アルコール又は脂肪酸のエチレン
オキシド及び／又はプロピレンオキシド付加物などを用
いると，ＰＶＡ系繊維の製造工程において，供給ローラ
や延伸ローラ上での糸条間に集束性がないため，単糸切
れが多発するという問題がある。As a method for solving this problem, after twisting the PVA-based fiber into a cord, the cord is impregnated with an epoxy adhesive and / or an isocyanate adhesive and heat-treated to give a PVA-based fiber. There is a method of bonding between the single yarns. However, a conventional spinning oil agent, for example, an oil agent containing an aliphatic ester compound as a main ingredient and a so-called straight oil agent having a mineral oil as a diluent has a poor compatibility between the oil agent and the adhesive agent, and is not compatible with the oil agent. A sufficient effect cannot be obtained because the adhesive separates and the adhesive does not penetrate into the fiber. On the other hand, when a spinning oil agent which does not have such a problem, such as an aliphatic amide compound, an aliphatic amine compound, an ethylene oxide and / or a propylene oxide adduct of a fatty alcohol or a fatty acid, is used, it can be supplied in the production process of PVA-based fibers. There is a problem in that single yarn breakage occurs frequently because the yarns on the roller and draw roller do not have a bundling property.
【０００６】[0006]
【発明が解決しようとする課題】本発明は，高強力・高
弾性率で耐熱水性に優れ，コードにしてエポキシ系接着
剤及び／又はイソシネート系接着剤で処理し，通常のレ
ゾルシン・ホルマリン・ゴムラテックス（以下，ＲＦＬ
と略記する。）処理を行うだけでゴムとの接着性が良好
となり，かつ，このコードを用いてＰＶＡ系繊維補強ゴ
ム複合体を作成し，繊維軸方向に切断したとき，切断面
に露出したＰＶＡ系繊維の単糸のほつれや，切断面から
ほつれが毛羽状に突出することのないＰＶＡ系繊維を操
業性よく製造する方法を提供することを技術的な課題と
するものである。DISCLOSURE OF THE INVENTION The present invention has a high strength, a high elastic modulus, and excellent hot water resistance, and is treated with an epoxy adhesive and / or an isocyanate adhesive as a cord to obtain a normal resorcin / formalin rubber. Latex (hereinafter RFL
Abbreviated. ) Adhesion with rubber is improved only by treatment, and when a PVA fiber reinforced rubber composite is prepared using this cord and cut in the fiber axis direction, the PVA fiber exposed on the cut surface is It is a technical object to provide a method for producing a PVA-based fiber with good operability, which does not cause fray of a single yarn or fray from the cut surface.
【０００７】[0007]
【課題を解決するための手段】本発明者らは，上記の課
題を解決するために鋭意研究した結果，ＰＶＡを有機溶
媒に溶解して調製した紡糸原液を，凝固浴中に乾湿式紡
糸して凝固糸条を得，この凝固糸条に脱水反応促進用触
媒を混合した油剤を付与した後，乾熱延伸して高強力,
高耐熱水性ＰＶＡ系繊維を製造するに際し，前記油剤と
して特定の組成の油剤を付与すれば，この目的を達成で
きることを見出して本発明に到達した。Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors dry-wet-spin a stock solution prepared by dissolving PVA in an organic solvent in a coagulation bath. The coagulated yarn is obtained by applying an oil agent mixed with a dehydration reaction accelerating catalyst to the coagulated yarn, followed by dry heat drawing to obtain high strength,
The present invention has been found out that this object can be achieved by adding an oil agent having a specific composition as the above-mentioned oil agent in the production of highly heat-resistant water-based PVA fiber.
【０００８】すなわち，本発明は，ＰＶＡを有機溶媒に
溶解して調製した紡糸原液を，凝固浴中に乾湿式紡糸し
て凝固糸条を得，この凝固糸条に脱水反応促進用触媒
(以下, 触媒と略記する。) を混合した油剤を付与した
後，乾熱延伸して高強力，高耐熱水性ＰＶＡ系繊維を製
造するに際し，前記油剤として次のＡ，Ｂ，Ｃ３成分か
らなる組成物を主体とする油剤を用いることを特徴とす
るＰＶＡ系繊維の製造法を要旨とするものである。 Ａ：脂肪族アルコールと脂肪族カルボン酸とのエステルもしくはそのエチレンオ キシド及び／又はプロピレンオキシド付加物 …５〜30重量％ Ｂ：脂肪族アルコールのエチレンオキシド及び／又はプロピレンオキシド付加物 …20〜80重量％ Ｃ：脂肪族アミン化合物のエチレンオキシド及び／又はプロピレンオキシド付加 物 …10〜50重量％That is, according to the present invention, a spinning dope prepared by dissolving PVA in an organic solvent is dry-wet spun in a coagulating bath to obtain a coagulated filament, and the coagulated filament is a catalyst for promoting a dehydration reaction.
(Hereinafter, abbreviated as "catalyst") is applied, and then dry heat drawing is performed to produce a high-strength, high heat-resistant water-based PVA fiber, which comprises the following components A, B, and C3 The gist is a method for producing a PVA-based fiber, which is characterized in that an oil agent mainly composed of a composition is used. A: Ester of aliphatic alcohol and aliphatic carboxylic acid or its ethylene oxide and / or propylene oxide adduct 5 to 30% by weight B: Ethylene oxide and / or propylene oxide adduct of aliphatic alcohol 20 to 80% by weight C: Ethylene oxide and / or propylene oxide adduct of aliphatic amine compound ... 10 to 50% by weight
【０００９】以下，本発明について詳細に説明する。The present invention will be described in detail below.
【００１０】本発明で用いるＰＶＡの重合度やケン化度
は特に限定されるものではないが，重合度は1500以上，
7000以下，また，ケン化度は99モル％以上であることが
好ましい。ＰＶＡを溶解する有機溶媒としては，ジメチ
ルスルホキシド（以下，ＤＭＳＯと略記する。），グリ
セリン，エチレングリコール等を挙げることができ，中
でもＤＭＳＯが好ましい。また，紡糸原液中のＰＶＡの
濃度は，その重合度に応じて適宜調整すればよいが，重
合度が1500〜7000の場合, ５〜24重量％に調整するのが
好ましい。本発明においては，この紡糸原液に架橋剤，
顔料，耐熱剤等を適宜混入して用いてもよい。The degree of polymerization and the degree of saponification of PVA used in the present invention are not particularly limited, but the degree of polymerization is 1500 or more,
It is preferable that the saponification degree is 7,000 or less, and the saponification degree is 99 mol% or more. Examples of the organic solvent that dissolves PVA include dimethyl sulfoxide (hereinafter abbreviated as DMSO), glycerin, ethylene glycol, and the like, and DMSO is preferable. The concentration of PVA in the spinning dope may be appropriately adjusted according to the degree of polymerization, but when the degree of polymerization is 1500 to 7000, it is preferably adjusted to 5 to 24% by weight. In the present invention, a crosslinking agent is added to this spinning solution.
You may mix and use a pigment, a heat-resistant agent, etc. suitably.
【００１１】本発明では，この紡糸原液を凝固浴中に乾
湿式紡糸し，未延伸糸を形成する。乾湿式紡糸する際の
エアーギャップは20mm以上,100mm以下とするのが好まし
い。また，凝固浴液としては，メタノール，エタノー
ル，アセトン等を用いることができ，特にメタノールが
好ましい。本発明においては，この凝固浴液にＰＶＡの
溶媒を混合してもよい。In the present invention, this spinning solution is dry-wet spun in a coagulation bath to form an undrawn yarn. The air gap during dry-wet spinning is preferably 20 mm or more and 100 mm or less. As the coagulation bath liquid, methanol, ethanol, acetone or the like can be used, and methanol is particularly preferable. In the present invention, the coagulating bath solution may be mixed with a solvent for PVA.
【００１２】乾湿式紡糸に用いる紡糸口金は特に限定さ
れるものではないが，吐出線速度ｖ（cm/sec），紡糸口
金の孔径ｄ（cm），紡糸原液の粘度μ（g/cm・sec)及び
密度ρ(g/cm3) によって下記式で定義されるレイノイズ
数（Ｒｅ）が0.05〜200 となるように孔径及び吐出線速
度を選択するのが好ましい。 Ｒｅ＝（ｄ・ｖ・ρ）／μThe spinneret used for dry-wet spinning is not particularly limited, but the discharge linear velocity v (cm / sec), the hole diameter d (cm) of the spinneret, and the viscosity of the spinning dope μ (g / cm · sec). ) And the density ρ (g / cm 3 ) and the ray noise number (Re) defined by the following equation is preferably 0.05 to 200 and the hole diameter and the discharge linear velocity are preferably selected. Re = (dvvρ) / μ
【００１３】本発明においては，このようにして形成さ
れた凝固糸条をさらに溶媒で洗浄してから乾燥し，未延
伸糸とする。洗浄に用いる溶媒は凝固浴液として用いた
ものと同じものを用いるのが好ましい。また，洗浄の方
法は，溶媒を凝固糸条の進行方向と逆方向に流し，これ
に接触させて行うのがよい，この洗浄の間，凝固糸条を
いわゆる湿延伸してもよいが，その倍率は８倍未満とす
るのがよい。In the present invention, the coagulated yarn thus formed is further washed with a solvent and then dried to obtain an undrawn yarn. The solvent used for washing is preferably the same as that used as the coagulation bath solution. The washing method is preferably carried out by causing the solvent to flow in the direction opposite to the advancing direction of the coagulated yarn and contacting it. During this washing, the coagulated yarn may be so-called wet-stretched. The magnification is preferably less than 8 times.
【００１４】次いで，洗浄後の糸条に触媒を混合した油
剤を付与するが，その際，糸条の含液率（糸条全体の重
量に対する糸条中の上記洗浄溶媒の重量の比率。）が５
重量％以上，30重量％未満，特に７〜25重量％として油
剤を付与するのが好ましい。糸条の含液率が５重量％未
満であったり，逆に30重量％以上であると，触媒の糸条
への浸透が不十分となり，高い耐熱水性が得難くなる。
この理由は明確ではないが，糸条は乾燥するのに伴い収
縮するため，含液率が５重量％未満まで乾燥が進むと，
糸条が収縮し過ぎて触媒の浸透が不十分になるものと考
えられる。逆に含液率が30重量％以上の場合には触媒が
浸透すべきスペースを溶媒が占有しているため，触媒が
浸透し難くなるものと認められる。Next, an oil agent mixed with a catalyst is applied to the yarn after washing, in which case the liquid content of the yarn (the ratio of the weight of the washing solvent in the yarn to the weight of the entire yarn). Is 5
It is preferable to add the oil agent in an amount of not less than 30% by weight, especially 7 to 25% by weight. If the liquid content of the yarn is less than 5% by weight or, conversely, 30% by weight or more, the penetration of the catalyst into the yarn becomes insufficient and it becomes difficult to obtain high hot water resistance.
The reason for this is not clear, but the yarn shrinks as it dries, so if the liquid content goes below 5% by weight,
It is considered that the yarn contracts too much, resulting in insufficient catalyst penetration. On the contrary, when the liquid content is 30% by weight or more, the space occupied by the catalyst is occupied by the solvent, making it difficult for the catalyst to permeate.
【００１５】糸条の含液率をこの範囲とするためには，
溶媒での洗浄と触媒付与との間で乾燥を行うのが好まし
いが，含液率を上記の範囲にできるものであれば，その
方法は特に限定されるものではなく，例えば，加熱気体
中に糸条を通したり，表面を加熱したドラムに糸条を接
触させて乾燥することができる。In order to set the liquid content of the yarn in this range,
Drying is preferably performed between washing with a solvent and applying a catalyst, but the method is not particularly limited as long as the liquid content can be within the above range, and for example, in a heated gas. The yarn can be passed through or dried by contacting the yarn with a drum whose surface is heated.
【００１６】本発明で用いることのできる触媒として
は，リン酸，塩酸などの無機酸，パラトルエンスルホン
酸，テレフタル酸などの有機酸が挙げられ，特にリン酸
やパラトルエンスルホン酸が好適に用いられる。Examples of the catalyst that can be used in the present invention include inorganic acids such as phosphoric acid and hydrochloric acid, and organic acids such as paratoluenesulfonic acid and terephthalic acid. Particularly, phosphoric acid and paratoluenesulfonic acid are preferably used. To be
【００１７】また，触媒は油剤と共に，すなわち，油剤
に触媒を混合し，これを糸条に付与する。触媒と油剤を
別々に付与すると，工程が煩雑となり好ましくない。触
媒の油剤に対する混合量は，酸濃度が 0.005〜0.５規定
となるように触媒を油剤に混合するのが好ましい。The catalyst is mixed with the oil agent, that is, the catalyst is mixed with the oil agent and applied to the yarn. If the catalyst and the oil agent are separately provided, the process becomes complicated, which is not preferable. The amount of the catalyst mixed with the oil agent is preferably such that the acid concentration is 0.005 to 0.5 N in the catalyst.
【００１８】触媒を混合する油剤は，前記したＡ，Ｂ及
びＣの３成分からなる組成物を主体とし，好ましくは上
記組成物を80重量％以上含有するものを付与する。な
お，油剤成分の以後の説明において，ＥＯはエチレンオ
キシド，ＰＯはプロピレンオキシド，ＰＯＥはポリオキ
シエチレン化を意味し，かっこ内の数値は付加モル数を
表わす。The oil agent to be mixed with the catalyst is mainly composed of the composition consisting of the above-mentioned three components A, B and C, and preferably the one containing 80% by weight or more of the above composition. In the following description of the oil component, EO means ethylene oxide, PO means propylene oxide, POE means polyoxyethylenation, and the value in parentheses means the number of moles added.
【００１９】まず，Ａ成分は，脂肪族アルコールと脂肪
族カルボン酸とのエステルもしくはそのＥＯ及び／又は
ＰＯ付加物であり，製糸工程での糸条の集束性を高める
作用をするものである。脂肪族アルコール及び脂肪族カ
ルボン酸としては，炭素数６〜22のものが好ましく，Ｅ
Ｏ及び／又はＰＯ付加モル数は４〜20が好ましい。ま
た，耐熱性を上げるために，硫黄原子やリン原子などを
導入したものでもよい。Ａ成分の具体例としては，ジオ
レイルアジペート，オレイルオレエート，ラウリルオレ
エート，イソステアリルオレエート，イソトリデシルパ
ルミテート，ジグリシドールジオレエート，ジオレイル
チオジプロピオネート，POE(20) グリセリンジオレエー
ト，POE(20) 硬化ヒマシ油などが挙げられる。Ａ成分の
配合量は，５〜30重量％，特に10〜25重量％が好まし
い。この量が５重量％より少ないと製糸性が低下し，30
重量％より多いとほつれ防止効果が低下する。First, the component A is an ester of an aliphatic alcohol and an aliphatic carboxylic acid or an EO and / or PO adduct thereof, and has a function of enhancing the sizing property of the yarn in the yarn making process. As the aliphatic alcohol and the aliphatic carboxylic acid, those having 6 to 22 carbon atoms are preferable, and
The number of moles of added O and / or PO is preferably 4 to 20. Further, in order to improve heat resistance, a sulfur atom or phosphorus atom may be introduced. Specific examples of the component A include dioleyl adipate, oleyl oleate, lauryl oleate, isostearyl oleate, isotridecyl palmitate, diglycidol dioleate, dioleyl thiodipropionate, POE (20) glycerin diester. Examples include oleate and POE (20) hydrogenated castor oil. The content of the component A is preferably 5 to 30% by weight, particularly 10 to 25% by weight. If this amount is less than 5% by weight, the spinnability is reduced and
If it exceeds 5% by weight, the effect of preventing fraying decreases.
【００２０】Ｂ成分は，脂肪族アルコールのＥＯ及び／
又はＰＯ付加物であり，コードにして接着剤で処理する
際に，接着剤を深部まで浸透させる作用をするものであ
る。脂肪族アルコールとしては，炭素数が４〜22のもの
が好ましく，ＥＯ及び／又はＰＯの付加モル数は４〜20
が好ましい。Ｂ成分の具体例としては，POE(6)ステアリ
ルエーテル，POE(6)オレイルエーテル，POE(10) オレイ
ルエーテル，POE(10) セチルエーテル，POE(8)ラウリル
エーテル，PO(5)/EO(5) モノブチルエーテル，POE(20)
グリセリンエーテルなどが挙げられる。Ｂ成分の配合量
は，20〜80重量％，特に25〜70重量％が好ましい。この
範囲を外れると，ほつれ防止効果が低下する。Component B is an EO of an aliphatic alcohol and / or
Alternatively, it is a PO adduct, and has a function of permeating the adhesive to a deep portion when the cord is treated with the adhesive. The aliphatic alcohol preferably has 4 to 22 carbon atoms, and the added mole number of EO and / or PO is 4 to 20.
Is preferred. Specific examples of the component B include POE (6) stearyl ether, POE (6) oleyl ether, POE (10) oleyl ether, POE (10) cetyl ether, POE (8) lauryl ether, PO (5) / EO ( 5) Monobutyl ether, POE (20)
Examples thereof include glycerin ether. The blending amount of the component B is preferably 20 to 80% by weight, more preferably 25 to 70% by weight. Outside this range, the effect of preventing fraying is reduced.
【００２１】さらに，Ｃ成分は，脂肪族アミン化合物の
ＥＯ及び／又はＰＯ付加物であり，コードにして接着剤
で処理する際に，接着剤を深部まで浸透させるととも
に，接着剤を硬化させる作用をするものである。脂肪族
アミン化合物としては，炭素数４〜22のものが好まし
く，ＥＯ及び／又はＰＯの付加モル数は４〜20が好まし
い。Ｃ成分の具体例としては，POE(20) ラウリルアミノ
エーテル，POE(8)ステアリルアミノエーテル，EO(5)/PO
(5) エタノールアミノエーテル，POE(10) ラウリルアミ
ノエーテル，POE(10) ステアリルアミノエーテル，POE
(15) ラウリルエタノールアミン，POE(15) ラウリルジ
エタノールアミンなどが挙げられる。Ｃ成分の配合量
は，10〜50重量％，特に15〜45重量％が好ましい。この
範囲を外れると，ほつれ防止効果が低下したり，製糸性
が低下する。Further, the component C is an EO and / or PO adduct of an aliphatic amine compound, and has a function of penetrating the adhesive to a deep portion and curing the adhesive when the cord is treated with the adhesive. Is what you do. The aliphatic amine compound preferably has 4 to 22 carbon atoms, and the added mole number of EO and / or PO is preferably 4 to 20. Specific examples of the C component include POE (20) lauryl amino ether, POE (8) stearyl amino ether, EO (5) / PO
(5) Ethanol amino ether, POE (10) Lauryl amino ether, POE (10) Stearyl amino ether, POE
(15) Laurylethanolamine, POE (15) Lauryldiethanolamine and the like. The content of the C component is preferably 10 to 50% by weight, particularly 15 to 45% by weight. If it deviates from this range, the effect of preventing fraying is reduced, and the spinnability is reduced.
【００２２】本発明で使用する油剤は，Ａ，Ｂ，Ｃの３
成分が 100重量％となるようにし，この組成物を好まし
くは80重量％以上となるようにし，20重量％以下の範囲
で，乳化剤，静電防止剤，耐熱剤，触媒などを配合して
用いられる。油剤は，通常，低粘度鉱物油，メタノー
ル，エタノールなどで希釈したストレート油剤（非水油
剤）の形で使用されるが，水性エマルジョン油剤として
もよい。The oil agents used in the present invention are A, B and C.
The composition is 100% by weight, and the composition is preferably 80% by weight or more, and is mixed with an emulsifier, an antistatic agent, a heat-resistant agent, a catalyst, etc. within the range of 20% by weight or less. To be The oil agent is usually used in the form of a straight oil agent (non-water oil agent) diluted with low-viscosity mineral oil, methanol, ethanol or the like, but may be an aqueous emulsion oil agent.
【００２３】油剤は，通常のローラ式給油法やノズル式
給油法により糸条に付与されるが，油剤の付与量は0.05
〜1.０重量％，特に0.１〜0.５重量％が好ましい。The oil agent is applied to the yarn by a usual roller type oil supply method or nozzle type oil supply method, but the amount of the oil agent applied is 0.05.
~ 1.0 wt%, especially 0.1-0.5 wt% is preferred.
【００２４】油剤を付与した糸条は，いったん巻き取っ
た後，あるいは巻き取ることなく連続して乾熱延伸する
と同時に脱水反応を行わせるが，この乾熱延伸の際，乾
熱延伸倍率を15倍以上とすることが好ましい。乾熱延伸
倍率が15倍未満では，本発明の他の目的である高強力Ｐ
ＶＡ系繊維が得られ難くなる。The thread to which the oil agent is added is subjected to a dry heat drawing at the same time as being once wound or continuously being dry heat drawn without being wound, and at the time of this dry heat drawing, the dry heat draw ratio is 15 It is preferable that the number is twice or more. When the dry heat draw ratio is less than 15 times, the high strength P which is another object of the present invention is
It becomes difficult to obtain a VA fiber.
【００２５】乾熱延伸での糸条の加熱方法としては，熱
風加熱炉を用いる方法，接触型ヒータを用いる方法，輻
射熱ヒータを用いる方法，加熱ローラを用いる方法など
を採用することができ，また，これらのいくつかを組み
合わせて用いてもよい。乾熱延伸時の温度は特に限定さ
れるものではないが，例えば熱風加熱炉で延伸する場
合，糸条の入口温度を 150℃以上とし，出口温度を 270
℃以下とすることが好ましい。As a method for heating the yarn in the dry heat drawing, a method using a hot air heating furnace, a method using a contact type heater, a method using a radiant heat heater, a method using a heating roller, etc. can be adopted. ， Some of these may be used in combination. The temperature during dry heat drawing is not particularly limited. For example, when drawing in a hot air heating furnace, the yarn inlet temperature should be 150 ° C or higher and the outlet temperature should be 270 ° C.
It is preferable that the temperature is not higher than ° C.
【００２６】触媒を混合した油剤が付与された糸条を乾
熱延伸すると，熱延伸と脱水反応が同時に進行するが，
脱水反応を十分進行させるために乾熱延伸後さらに熱処
理を行ってもよい。熱処理は，乾熱延伸の最高温度より
５〜10℃高い温度で，定長（リラックス率０％）又は10
％以下のリラックス率で行うのが好ましい。When a yarn to which an oil agent mixed with a catalyst is applied is dry-heat drawn, hot drawing and dehydration reaction proceed simultaneously,
In order to sufficiently advance the dehydration reaction, a heat treatment may be further performed after the dry heat drawing. The heat treatment is performed at a temperature 5 to 10 ° C higher than the maximum temperature of dry heat drawing, with a constant length (relaxation rate 0%) or 10%.
It is preferable that the relaxation rate is not more than%.
【００２７】[0027]
【作用】本発明によれば，乾湿式紡糸して得た凝固糸条
に付与する，触媒を混合した油剤として，製糸工程での
糸条の集束性を高める成分と，コードにして接着剤で処
理する際に，接着剤を深部まで浸透させたり，接着剤を
硬化させたりする成分を配合した油剤を用いるので，製
糸性が向上するとともに，得られるＰＶＡ系繊維のコー
ドは，通常のＲＦＬ処理を行うだけでゴムとの接着性が
良好となる。また，このコードを用いてＰＶＡ系繊維補
強ゴム複合体を形成し，この複合体を繊維軸方向に切断
したとき，切断面に露出するＰＶＡ系繊維の単糸がほつ
れたり，このほつれが切断面から毛羽状に突出するのを
防止することが可能となる。According to the present invention, a catalyst-mixed oil agent applied to a coagulated yarn obtained by dry-wet spinning is used as a component for enhancing the yarn bundle converging property in the spinning process and an adhesive as a cord. At the time of processing, since an oil agent containing a component that permeates the adhesive to a deep portion or hardens the adhesive is used, the spinnability is improved and the cord of the PVA-based fiber obtained is a normal RFL treatment. Only by performing the above, the adhesiveness with rubber becomes good. Further, when a PVA-based fiber-reinforced rubber composite is formed using this cord and the composite is cut in the fiber axis direction, the PVA-based fiber single yarn exposed on the cut surface is frayed, and this fraying is a cut surface. It is possible to prevent fluffy protrusion from the.
【００２８】[0028]
【実施例】次に，本発明を実施例により具体的に説明す
る。なお，「部」は重量部を意味し，各物性の測定法は
次のとおりである。 (a) コード強伸度 オートグラフを使用し，JIS-L-1017に準じて測定した。 (b) 製糸性 製糸工程における引き取りローラ及び延伸ローラでの単
糸切れによるローラヘの単糸の巻き付き回数により，次
の３段階で評価した。 ○：０〜３回／１日 △：４〜10回／１日 ×：11回以上／１日 (c) 耐ほつれ性 処理コードを厚さが３mmのゴムシート２枚の間に平行に
並べて挟み，50kg/cm2の圧力下,150℃で30分間加硫し，
ゴムシートとする。このシートを，ゴム中に配列したコ
ードの繊維軸方向にカッターナイフを用いて切断し，切
断面にコード端面が露出するようにする。そして，端面
からのＰＶＡ系繊維の単糸の飛び出し状態を肉眼で観察
するとともに，この端面をサンドペーパー（＃AA-120)
で10回摩擦し，単糸のほつれ状態を観察し，次の３段階
で評価した。 ○：単糸の飛び出しと単糸のほつれが認められない。 △：単糸の飛び出しはないが，単糸のほつれが認められ
る。 ×：単糸の飛び出しと単糸のほつれが認められる。 (d) 接着性 表１に示した組成のゴム配合物を用い，JIS-L-1017のＡ
法に準じて測定した。EXAMPLES Next, the present invention will be specifically described by way of examples. In addition, "parts" means parts by weight, and the measuring methods of each physical property are as follows. (a) Cord strength and elongation were measured according to JIS-L-1017 using an autograph. (b) Spinning property The following three grades were evaluated according to the number of windings of the single yarn around the roller due to single yarn breakage at the take-up roller and the drawing roller in the yarn making process. ○: 0 to 3 times / 1 day △: 4 to 10 times / 1 day ×: 11 times or more / 1 day (c) Fray resistance The cords are arranged in parallel between two 3 mm thick rubber sheets. Sandwiched, vulcanized under a pressure of 50 kg / cm 2 at 150 ° C for 30 minutes,
Use a rubber sheet. This sheet is cut with a cutter knife in the fiber axis direction of the cords arranged in rubber so that the end faces of the cords are exposed on the cut surface. Then, while observing the protruding state of the single yarn of the PVA fiber from the end surface with the naked eye, the end surface is sandpaper (# AA-120)
Rubbing was performed 10 times, and the unraveled state of the single yarn was observed, and the following three grades were evaluated. ◯: Single yarn jumping out and single yarn fraying are not observed. Δ: The single yarn does not jump out, but the single yarn is frayed. X: Single yarn jumping out and single yarn fraying are recognized. (d) Adhesiveness Using a rubber composition having the composition shown in Table 1, JIS-L-1017 A
It measured according to the method.
【００２９】[0029]
【表１】 [Table 1]
【００３０】実施例１〜２，比較例１〜３ 〔油剤イ〜ホの調製〕ＲＷ30秒の低粘土鉱物油75部を40
℃に加温し，各成分を表２に示す割合（部）で配合した
油剤組成物25部を40℃に加温したものをゆっくり添加し
ながら撹拌した後，室温に冷却した。さらに，98重量％
リン酸0.03部をゆっくり添加しながら撹拌した。Examples 1 to 2 and Comparative Examples 1 to 3 [Preparation of oil agents a to h] 40 parts of 75 parts of low clay mineral oil having RW of 30 seconds
After warming to 40 ° C., 25 parts of the oil agent composition containing the respective components in the proportions (parts) shown in Table 2 and being heated to 40 ° C. was slowly added and stirred, and then cooled to room temperature. Furthermore, 98% by weight
The mixture was stirred while slowly adding 0.03 part of phosphoric acid.
【００３１】[0031]
【表２】 [Table 2]
【００３２】〔イソシアネート系接着剤の調製〕トルエ
ン75部に，固形分濃度27％のトリス（ｐ−イソシアネー
トフェニル）チオホスフェート；「デスモジュール RE
E」（住友バイエルウレタン社商品名）25部をゆっくり
添加しながら撹拌，溶解した。[Preparation of Isocyanate Adhesive] Tris (p-isocyanatephenyl) thiophosphate having a solid content of 27% was added to 75 parts of toluene;
Twenty-five parts of "E" (trade name of Sumitomo Bayer Urethane Co., Ltd.) was slowly added and dissolved by stirring.
【００３３】〔ＲＦＬ液の調製〕水 125部に，10％水酸
化ナトリウム水溶液19部を加えた後，レゾルシン17部を
添加して撹拌，溶解し，次いで37％ホルムアルデヒド水
溶液30部を加えて撹拌し，25℃で30分間反応させた。得
られた反応液を固形分濃度41％のＶＰラテックス；「ピ
ラテックスJ-1904」(住友ダウ社商品名） 190部と固形
分濃度40％のＳＢＲラテックス；「JSR-2108」（日本合
成ゴム社商品名） 190部の混合液に撹拌しながら加え，
さらに，水431部を撹拌しながら加え，10分間撹拌，混
合した後，25℃で24時間熟成させた。[Preparation of RFL Solution] To 125 parts of water, 19 parts of 10% sodium hydroxide aqueous solution was added, and then 17 parts of resorcinol was added and stirred and dissolved, and then 30 parts of 37% formaldehyde aqueous solution was added and stirred. Then, the mixture was reacted at 25 ° C for 30 minutes. The obtained reaction liquid was VP latex having a solid content of 41%; "Pilatex J-1904" (trade name of Sumitomo Dow) 190 parts and SBR latex having a solid content of 40%; "JSR-2108" (Japan Synthetic Rubber) Company brand name) Add to 190 parts of the mixed solution with stirring,
Further, 431 parts of water was added with stirring, stirred for 10 minutes, mixed, and then aged at 25 ° C for 24 hours.
【００３４】〔ＰＶＡ系繊維の製造〕重合度4000，ケン
化度99.9モル％のＰＶＡ15部を，ＤＭＳＯ85部に溶解し
て紡糸原液を調製した。この紡糸原液を孔径 0.3mm，孔
数 300の紡糸口金から30mmのエアーギャップを通して，
ＤＭＳＯ15重量％を含むメタノール凝固浴中に乾湿式紡
糸して凝固糸条を得た。吐出条件はレイノズル数が 2と
なるように選定した。この凝固糸条をメタノールで洗浄
した後，加熱ドラムを用いて乾燥し，糸条の含液率を10
重量％としてから，ローラ式給油方式によって表３に示
す紡糸油剤を糸条に対し 0.3重量％になるように付与
し，さらに80℃で乾燥して未延伸糸を得た。次いで，こ
の未延伸糸を表面温度80℃，表面速度10ｍ／分の供給ロ
ーラに掛け，入口温度が 160℃，出口温度が 220℃に設
定された長さ３ｍの熱風加熱炉を通した後，表面温度 1
60℃，表面速度90ｍ／分の第１延伸ローラとの間で９倍
に延伸し，次いで第１延伸ローラを出た糸条を，入口温
度が 210℃，出口温度が240℃に設定された長さ5mの熱
風加熱炉を通した後, 表面温度 180℃，表面速度190ｍ
／分の第２延伸ローラとの間で2.11倍に延伸した。さら
に，第２延伸ローラを出た糸条を，入口温度が 230℃，
出口温度が 250℃に設定された熱風加熱炉に通した後，
表面温度50℃，表面速度 185ｍ／分の熱処理ローラとの
間で0.97倍の弛緩熱処理を行った後，巻き取り，1500d/
300fのＰＶＡ系繊維を得た。[Production of PVA Fiber] 15 parts of PVA having a polymerization degree of 4000 and a saponification degree of 99.9 mol% were dissolved in 85 parts of DMSO to prepare a spinning dope. This spinning dope is passed through a 30 mm air gap from a spinneret with a hole diameter of 0.3 mm and 300 holes,
Coagulated yarn was obtained by dry and wet spinning in a methanol coagulation bath containing 15% by weight of DMSO. The discharge conditions were selected so that the number of Reynolds was 2. The coagulated yarn was washed with methanol and dried using a heating drum to reduce the liquid content of the yarn to 10
Then, the spinning oil agent shown in Table 3 was applied to the yarn in an amount of 0.3% by weight based on the roller type oiling method, and further dried at 80 ° C. to obtain an undrawn yarn. Then, this undrawn yarn was put on a supply roller having a surface temperature of 80 ° C and a surface speed of 10 m / min, and passed through a hot air heating furnace having a length of 3 m and an inlet temperature of 160 ° C and an outlet temperature of 220 ° C. Surface temperature 1
The yarn which was drawn 9 times with the first drawing roller at a surface speed of 90 m / min at 60 ° C and then exited the first drawing roller was set to have an inlet temperature of 210 ° C and an outlet temperature of 240 ° C. After passing through a hot air heating furnace with a length of 5 m, the surface temperature is 180 ° C and the surface speed is 190 m.
It was stretched 2.11 times with a second stretching roller of 1 / min. In addition, the yarn exiting the second drawing roller has an inlet temperature of 230 ° C,
After passing through a hot-air heating furnace with the outlet temperature set to 250 ° C,
After heat treatment of 0.97 times relaxation with a heat treatment roller with surface temperature of 50 ℃ and surface speed of 185m / min.
300 f of PVA fiber was obtained.
【００３５】〔コードの処理〕得られたＰＶＡ系繊維を
2本合糸しながら 115回／ｍの撚りを掛けて下撚りコー
ドとし，次いで下撚りしたコード３本を合糸しながら下
撚りと逆方向に95回／ｍの撚り数で上撚コードとし，上
記の方法で調製したイソシアネート系接着剤溶液に浸漬
（固形分付着量2.５〜3.５重量％）し,120℃の熱風で乾
燥後, 180℃で100秒間熱処理した。次いで，前記の方
法で調製したＲＦＬ浴に浸漬（固形分付着量4.5 〜5.5
重量％）し,120℃で60秒間乾燥した後,180℃で 100秒間
熱処理した。[Treatment of Cord] The obtained PVA fiber is
While twisting 2 yarns, twist 115 times / m to make a lower twist cord, and then twist 3 twisted cords to make an upper twist cord at a twist number of 95 times / m in the opposite direction to the lower twist. Then, it was immersed in the isocyanate-based adhesive solution prepared by the above method (solid content: 2.5 to 3.5% by weight), dried with hot air at 120 ° C, and then heat-treated at 180 ° C for 100 seconds. Then, dip it in the RFL bath prepared by the above method (solid content of 4.5 to 5.5).
%), Dried at 120 ° C for 60 seconds, and then heat-treated at 180 ° C for 100 seconds.
【００３６】このようにして得られた処理コードの強伸
度，耐ほつれ性，接着性及び原糸製造工程の製糸性など
を表３に示す。Table 3 shows the strength and elongation of the thus obtained treated cord, the resistance to fraying, the adhesiveness, and the spinnability in the raw yarn manufacturing process.
【００３７】[0037]
【表３】 [Table 3]
【００３８】表３から明かなように，本発明の実施例１
では，製糸性，処理コードの耐ほつれ性，接着性のすべ
てにおいて良好であった。また，実施例２では，製糸性
に若干問題は残るものの，処理コードの耐ほつれ性と接
着性は優れたものであった。一方，Ａ成分が本発明を満
足しない比較例１及び３成分とも本発明を満足しない比
較例２では，処理コードの耐ほつれ性と接着性に問題が
あり，また，Ａ成分が本発明を満足しない比較例３で
は，製糸性，処理コードの耐ほつれ性と接着性において
満足できないものであった。As is clear from Table 3, Example 1 of the present invention
In the case of, the spinnability, the fraying resistance of the treated cord, and the adhesiveness were all good. Further, in Example 2, although there were some problems in the spinnability, the treated cord was excellent in fraying resistance and adhesiveness. On the other hand, in Comparative Example 1 in which the A component does not satisfy the present invention and Comparative Example 2 in which neither of the 3 components satisfies the present invention, there is a problem in the fraying resistance and the adhesiveness of the treated cord, and the A component satisfies the present invention. In Comparative Example 3, which was not performed, the spinnability, the fraying resistance of the treated cord, and the adhesiveness were unsatisfactory.
【００３９】[0039]
【発明の効果】本発明によれば，高強度で，熱に対する
寸法安定性に優れ，コードにしてエポキシ系接着剤及び
／又はイソシアネート系接着剤で処理し，通常のＲＦＬ
処理を行うだけでゴムとの接着性が良好となり，かつ，
このコードを用いて繊維補強ゴム複合体を形成し，この
複合体を繊維軸方向に切断したとき，切断面に露出した
繊維の単糸がほつれたり，ほつれが切断面から毛羽状に
突出することのないＰＶＡ系繊維を操業性よく製造する
ことが可能となる。According to the present invention, a high strength, excellent dimensional stability against heat, a cord is treated with an epoxy adhesive and / or an isocyanate adhesive, and a conventional RFL is used.
Adhesion with rubber becomes good just by treating, and
When a fiber reinforced rubber composite is formed using this cord and the composite is cut in the fiber axis direction, the single fiber of the fiber exposed on the cut surface is frayed or the fray protrudes like fluff from the cut surface. It becomes possible to produce a PVA-based fiber free of operability with good operability.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｄ０６Ｍ 13/224 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display location D06M 13/224
Claims (1)
して調製した紡糸原液を，凝固浴中に乾湿式紡糸して凝
固糸条を得，この凝固糸条に脱水反応促進用触媒を混合
した油剤を付与した後，乾熱延伸して高強力，高耐熱水
性ポリビニルアルコール系繊維を製造するに際し，前記
油剤として次のＡ，Ｂ，Ｃ３成分からなる組成物を主体
とする油剤を用いることを特徴とするポリビニルアルコ
ール系繊維の製造法。 Ａ：脂肪族アルコールと脂肪族カルボン酸とのエステルもしくはそのエチレンオ キシド及び／又はプロピレンオキシド付加物 …５〜30重量％ Ｂ：脂肪族アルコールのエチレンオキシド及び／又はプロピレンオキシド付加物 …20〜80重量％ Ｃ：脂肪族アミン化合物のエチレンオキシド及び／又はプロピレンオキシド付加 物 …10〜50重量％1. A spinning dope prepared by dissolving polyvinyl alcohol in an organic solvent is dry-wet spun in a coagulation bath to obtain coagulated filaments, and an oil agent prepared by mixing a dehydration reaction accelerating catalyst with the coagulated filaments is prepared. When applied to produce a high-strength, highly heat-resistant, water-soluble polyvinyl alcohol fiber after being applied, it is characterized in that an oil agent mainly comprising a composition comprising the following components A, B, and C3 is used as the oil agent. A method for producing a polyvinyl alcohol fiber. A: Ester of aliphatic alcohol and aliphatic carboxylic acid or its ethylene oxide and / or propylene oxide adduct 5 to 30% by weight B: Ethylene oxide and / or propylene oxide adduct of aliphatic alcohol 20 to 80% by weight C: Ethylene oxide and / or propylene oxide adduct of aliphatic amine compound ... 10 to 50% by weight
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18950894A JP3450905B2 (en) | 1994-08-11 | 1994-08-11 | Method for producing polyvinyl alcohol fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18950894A JP3450905B2 (en) | 1994-08-11 | 1994-08-11 | Method for producing polyvinyl alcohol fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0860449A true JPH0860449A (en) | 1996-03-05 |
| JP3450905B2 JP3450905B2 (en) | 2003-09-29 |
Family
ID=16242449
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18950894A Expired - Fee Related JP3450905B2 (en) | 1994-08-11 | 1994-08-11 | Method for producing polyvinyl alcohol fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3450905B2 (en) |
-
1994
- 1994-08-11 JP JP18950894A patent/JP3450905B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP3450905B2 (en) | 2003-09-29 |
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