JP2858925B2 - Method for producing hot water-resistant polyvinyl alcohol fiber - Google Patents
Method for producing hot water-resistant polyvinyl alcohol fiberInfo
- Publication number
- JP2858925B2 JP2858925B2 JP28269190A JP28269190A JP2858925B2 JP 2858925 B2 JP2858925 B2 JP 2858925B2 JP 28269190 A JP28269190 A JP 28269190A JP 28269190 A JP28269190 A JP 28269190A JP 2858925 B2 JP2858925 B2 JP 2858925B2
- Authority
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- Japan
- Prior art keywords
- fiber
- hot water
- weight
- pva
- polymerization
- 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.)
- Expired - Lifetime
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- 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)
Description
【発明の詳細な説明】 (産業上の利用分野) 本発明は高強度を有し、かつ耐熱水性にすぐれたポリ
ビニルアルコール(以下PVAと略記する)系繊維に関す
るものであり、特に産業資材用および複合材強化用で耐
熱水性が要求されるような用途に適したPVA系繊維に関
するものである。The present invention relates to a polyvinyl alcohol (hereinafter abbreviated as PVA) fiber having high strength and excellent hot water resistance, particularly for industrial materials and The present invention relates to a PVA-based fiber suitable for use in reinforcing composite materials and requiring hot water resistance.
(従来の技術) 従来PVA系繊維は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強度弾性率が高く、その主
用途である産業資材用繊維として利用されている以外に
もアスベスト繊維代替としてセメント補強用繊維等にも
利用されてきている。(Prior art) Conventional PVA fiber has higher strength and elastic modulus than polyamide polyester and polyacrylonitrile fiber, and is used as a substitute for asbestos fiber for cement reinforcement in addition to being used as industrial material fiber, which is its main use. It has also been used for fibers and the like.
最近の技術ではさらに高強度弾性率を有するPVA系繊
維を得る方法として、高分子量ポリスチレンのゲル紡糸
−超延伸の考え方を応用した特開昭59-100710号、特開
昭59-130314号、特開昭61-108711号等が提案されてい
る。In recent technology, JP-A-59-100710, JP-A-59-130314, and JP-A-59-130314, which apply the concept of gel spinning and ultra-drawing of high molecular weight polystyrene as a method for obtaining a PVA-based fiber having a higher strength elastic modulus. Japanese Utility Model Application Laid-Open No. 61-108711 has been proposed.
しかしながら、これらの方法では高強度高弾性率のPV
A系繊維は得られても、一部の用途分野で要求されるよ
うな高度な耐熱水性を具備することはできなかつた。However, in these methods, high-strength, high-modulus PV
Even if the A-based fiber is obtained, it cannot have high hot water resistance required in some application fields.
PVA系繊維の耐熱水性を高めようとする試みは古くア
セタール化による水不溶化処理に始まるが、最近の高重
合度高強力PVA系繊維では、非晶部の分子配向が進み水
に対する寸法安定性は上述の水不溶化処理を行なわなく
ても達成できるようになつた。しかし、例えば120℃の
熱水中ではたちまち溶断しオートクレーブ養生のセメン
ト成形物の補強材や摩擦熱を受け易いロープ等の用途に
はまだまだ不満足である。Attempts to increase the hot water resistance of PVA fibers have long begun with water insolubilization treatment by acetalization.However, in recent high-polymerization and high-strength PVA fibers, the molecular orientation of the amorphous part has progressed, and the dimensional stability to water is poor. This can be achieved without performing the water insolubilization treatment described above. However, it is still unsatisfactory for applications such as reinforcing materials for cement molded products for autoclave curing and ropes that are susceptible to frictional heat, for example, which melts quickly in hot water at 120 ° C.
また、特開昭平1-156517号や特開昭平1-207435号、あ
るいは特開昭平1-104815号や特開昭平2-84587号にみら
れる如く、パーオキサイド系化合物やイソシアネート化
合物あるいはホウ酸やリン酸などにより架橋処理を施し
て耐熱水性を向上させる方法は公知である。しかしこれ
らの方法は延伸前に架橋すると延伸性が損われ、分子配
向が不十分なため強度や弾性率を低下させる。一方延伸
後に架橋させようとした場合は、架橋剤の繊維内部浸透
を強化させるため繊維を膨潤させたり、高温熱処理をす
る必要があり、その結果分子配向乱れやPVAの分解、損
傷が起こり、強度弾性率の低下を招き易い問題があつ
た。Further, as seen in JP-A-1-156517 and JP-A-1-207435, or JP-A-1-048815 and JP-A-2-84587, a peroxide compound, an isocyanate compound or boric acid or A method for improving the hot water resistance by performing a crosslinking treatment with phosphoric acid or the like is known. However, when these methods are crosslinked before stretching, the stretchability is impaired, and the molecular orientation is insufficient, so that the strength and the elastic modulus are reduced. On the other hand, if it is attempted to crosslink after stretching, it is necessary to swell the fiber or to perform high-temperature heat treatment in order to strengthen the penetration of the crosslinking agent into the fiber, resulting in disordered molecular orientation, decomposition and damage of PVA, and strength. There is a problem that the elastic modulus tends to decrease.
(発明が解決しようとする課題) 以上の背景をふまえて本発明は、その引張強度16g/d
以上といつた高強度高弾性率であり、かつオートクレー
ブにも耐えられる如き耐熱水性に優れたPVA系繊維を得
んとするものであり、そのために高重合度PVA繊維を延
伸する際に延伸倍率を低下させずに前記高性能繊維を得
んとするものである。また本発明は、かくの如き繊維を
長時間かつ特殊な処理工程でもつて処理して得るのでな
く、短時間かつ簡潔な処理工程でもつて実現せんとする
ものである。(Problems to be solved by the invention) Based on the above background, the present invention has a tensile strength of 16 g / d.
It is intended to obtain a PVA-based fiber having a high strength and a high elastic modulus as described above, and having excellent hot water resistance so as to be able to withstand an autoclave. It is intended to obtain the above-mentioned high-performance fiber without lowering the fiber. Further, the present invention is not intended to realize such a fiber in a short and simple processing step, instead of being obtained by performing a long and special processing step.
(課題を解決するための手段) 本発明者等は上記課題につき検討した結果、ある種の
油剤を適正量付着させてから高温延伸することにより繊
維表面でPVAの水酸基と反応するか又は脱水反応を起こ
させて耐熱水性の表皮構造を形成させることが有効であ
ることを見出した。(Means for Solving the Problems) As a result of examining the above problems, the present inventors have found that an appropriate amount of a certain oil agent is applied and then drawn at a high temperature to react with hydroxyl groups of PVA on the fiber surface or to cause a dehydration reaction. It has been found that it is effective to cause a hot water-resistant skin structure by causing the heat treatment.
即ち本発明は、 「粘度平均重合度が3,000以上のPVA系繊維に、その紡
糸から延伸直前までの間で、ホスヘートアミン化合物、
アミン又はアミドのホスヘート化合物、アミン又はアミ
ドのスルホネート化合物、並びにチオ化合物の中より選
ばれた1種又は2種以上の界面活性剤0.2〜3重量%と
エステル系又は鉱物油系集束平滑剤0.5〜5重量%とを
付着せしめ、240℃以上の高温にて総延伸倍率が17倍以
上となるように延伸することを特徴とする、熱水溶断温
度WTbが次式を満足する耐熱水性PVA系繊維の製造法。That is, the present invention relates to a PVA-based fiber having a viscosity-average degree of polymerization of 3,000 or more, from spinning to immediately before drawing, a phosphate amine compound,
One or two or more surfactants selected from amine or amide phosphate compounds, amine or amide sulfonate compounds and thio compounds, and 0.2 to 3% by weight of an ester or mineral oil-based focusing and leveling agent 0.5 to 5% by weight and stretched at a high temperature of 240 ° C. or more so that the total draw ratio becomes 17 times or more. Manufacturing method.
WTb≧1.2A0.35+125 (A≧3,000) 」に関するものである。WTb ≧ 1.2A 0.35 +125 (A ≧ 3,000) ”.
以下、本発明を詳しく説明する。 Hereinafter, the present invention will be described in detail.
本発明に使用されるPVA系ポリマーとは、30℃の水溶
液の極限粘度から求めた粘度平均重合度が3,000以上、
好ましくは6,000以上、さらに好ましくは10,000以上の
ものであり、ケン化度が98モル%以上で分岐度の低い直
鎖状のPVAが好ましい。なお2モル%以下の他のビニル
化合物を共重合したものや3重量%以下のホウ酸、酸化
防止剤、紫外線吸収剤などの添加剤を加えることもでき
る。The PVA-based polymer used in the present invention has a viscosity average degree of polymerization of 3,000 or more determined from the intrinsic viscosity of an aqueous solution at 30 ° C.,
It is preferably 6,000 or more, more preferably 10,000 or more, and is preferably a linear PVA having a degree of saponification of 98 mol% or more and a low degree of branching. It is also possible to add a copolymer of 2 mol% or less of another vinyl compound or 3 wt% or less of additives such as boric acid, an antioxidant and an ultraviolet absorber.
PVAの重合度が高重合度ほど結晶間を連結するタイ分
子が強固となり、強度や耐熱水性が増大するが、特に高
重合度ほど分子鎖のからみが多いためかより高温で分子
運動を盛んにさせて延伸する必要がある。この結果、本
発明で用いる界面活性剤が繊維表面でPVAの水酸基と反
応するか又はPVAの脱水反応を起こさせて耐熱水性のあ
る表皮構造をとり易くなる。従つて重合度3,000未満で
は延伸温度が低く効果が現われ難い。高重合度で高温延
伸など本発明の効果が発揮される。The higher the degree of polymerization of PVA, the stronger the tie molecules that connect the crystals, and the higher the strength and hot water resistance.However, the higher the degree of polymerization, the more the molecular chains are entangled, and the more the molecular movement becomes active at higher temperatures. It is necessary to stretch it. As a result, the surfactant used in the present invention reacts with the hydroxyl group of PVA on the fiber surface or causes a dehydration reaction of PVA to easily form a skin structure having heat-resistant water. Therefore, when the degree of polymerization is less than 3,000, the stretching temperature is low and the effect is hard to appear. The effects of the present invention, such as high temperature stretching, are exhibited at a high degree of polymerization.
本発明に使用されるPVA系ポリマーの溶剤としては、
エチレングリコール、トリメチレングリコール、ジエチ
レングリコール、グリセリン等の多価アルコールやジメ
チルスルホキシド、ジメチルホルムアミド、ジエチレン
トリアミン、水、さらにはこれらの2種以上の混合系あ
るいはロダン塩水溶液、プロパノール水溶液などが挙げ
られる。特にこれらの中でも透明で均一なゲル状繊維を
得る上では多価アルコールやジメチルスルホキシドおよ
びそれらと水との混合溶剤が好ましい。As the solvent for the PVA-based polymer used in the present invention,
Examples thereof include polyhydric alcohols such as ethylene glycol, trimethylene glycol, diethylene glycol, and glycerin, dimethyl sulfoxide, dimethylformamide, diethylene triamine, water, and a mixed system of two or more of these, or a rodane salt aqueous solution and a propanol aqueous solution. Among these, polyhydric alcohol, dimethyl sulfoxide, and a mixed solvent thereof with water are preferable for obtaining transparent and uniform gel fibers.
紡糸方式は通常用いられる乾式、湿式、乾湿式のいず
れでもよいが、急冷により均一ゲル繊維を得る乾湿式紡
糸が望ましい。The spinning method may be any of a dry method, a wet method, and a dry-wet method, which are usually used, but dry-wet spinning for obtaining uniform gel fibers by quenching is desirable.
凝固浴はメタノールやエタノールなどのアルコールや
アセトン、あるいはアルカリ又は/及び芒硝などの無機
塩水溶液などいずれも支障はないが、均一ゲル繊維の生
成し易いアルコールと溶剤の混合系が高倍率延伸ひいて
は高性能繊維を得るのに適している。均一ゲル化を起こ
すには凝固浴中に10重量%以上の該溶剤を含有させ、20
℃以下の急冷でゆつくりと該溶剤を抽出するのが好まし
い。次いで該溶剤を含んだ状態の湿延伸を2倍以上、好
ましくは4倍以上施すのが良く、これにより繊維間の膠
着を少なくし、かつ紡糸初期に生成した微結晶を一部こ
わして後の延伸を容易にさせる事が出来る。The coagulation bath does not interfere with alcohol such as methanol or ethanol, acetone, or an aqueous solution of an inorganic salt such as alkali and / or sodium sulfate. Suitable for obtaining performance fibers. To cause uniform gelation, the coagulation bath contains 10% by weight or more of the solvent,
It is preferable to extract the solvent slowly by quenching at a temperature of not more than ℃. Next, the wet drawing in a state containing the solvent is preferably performed at least twice, preferably at least four times, thereby reducing the sticking between the fibers and partially breaking the microcrystals generated at the beginning of spinning, and Stretching can be facilitated.
続いてメタノール、エタノールなどのアルコール類や
アセトン、水などの抽出剤で該溶剤のほとんど全部を除
去するが、この時本発明に言う界面活性剤と集束平滑剤
を抽出浴の中に添加し、繊維に付着しても何んら支障は
ないが、繊維内部まで浸透したり、付着斑を起こすのは
好ましくない。Subsequently, almost all of the solvent is removed with an extracting agent such as alcohols such as methanol and ethanol or acetone and water.At this time, the surfactant and the convergence smoothing agent according to the present invention are added to the extraction bath, There is no problem even if it adheres to the fiber, but it is not preferable that it penetrates into the fiber or causes adhesion spots.
界面活性剤と集束平滑剤を別々に又は同時に抽出後の
乾燥前に付着させたり、乾燥後乾熱延伸直前までに付着
させても問題はないが、水溶液又は水エマルジヨンの型
で繊維に付着させ、未乾燥のまま紡糸原糸を放置する
と、水により繊維間の膠着が起こり延伸倍率や性能の低
下となるので注意を要する。There is no problem if the surfactant and the sizing smoothing agent are separately or simultaneously attached before drying after extraction, or attached immediately before drying and before hot drawing, but it is not necessary to attach them to the fiber in the form of an aqueous solution or water emulsion. Care must be taken because if the spun yarn is left undried, water will cause agglomeration between the fibers and the draw ratio or performance will be reduced.
本発明に用いる界面活性剤はPVA繊維表面の水酸基と
反応するか脱水反応を起こさせるもので次の3つに大別
される。The surfactant used in the present invention reacts with a hydroxyl group on the surface of the PVA fiber or causes a dehydration reaction, and is roughly classified into the following three.
(1)ホスヘートアミン化合物。(1) A phosphate amine compound.
例えばR-OP(O)‐(ONR2)2,(RO)2-P(O)-NR2,(RO)2‐
P(O)‐ORNR,RO(CH2CH2O)n-P(O)-O-NR2などで表わさ
れるアニオン界面活性剤。式中Rは例えばアルキル基、
アルコキシ基、フエニール基、フエノール基、H、OHな
どがあるが、これに限定されるものではない。For example, R-OP (O)-(ONR 2 ) 2 , (RO) 2 -P (O) -NR 2 , (RO) 2-
Anionic surfactants represented by P (O) -ORNR, RO (CH 2 CH 2 O) n -P (O) -O-NR 2 and the like. In the formula, R is, for example, an alkyl group,
Examples include, but are not limited to, alkoxy, phenyl, phenol, H, and OH.
(2)アミン又はアミドのホスヘート化合物。(2) Amine or amide phosphate compounds.
例えばR-NR-O−P(O)‐OR2,R-CON-R−O-P(O)‐
OR2R‐N-CH2‐CONR-O-P(O)‐OR2などのアニオン活性
剤。For example, R-NR-OP (O) -OR 2 , R-CON-R-OP (O)-
Anionic activators such as OR 2 R-N-CH 2 -CONR-OP (O) -OR 2 .
(3)アミン又はアミドのスルホネート化合物やチオ化
合物。(3) Amine or amide sulfonate compounds and thio compounds.
例えばR-NR-SO3M,R-CONR-SO3Na,(R3NO)2‐CH-RSO3M,R
3N‐O−R-SO3M,R−S−R-NR2,R−S−R-CONR2などで表
わされるアニオン活性剤。For example, R-NR-SO 3 M, R-CONR-SO 3 Na, (R 3 NO) 2 -CH-RSO 3 M, R
3 N-O-R-SO 3 M, R-S-R-NR 2, R-S-R-CONR 2 anionic active agent represented by like.
式中MはH又はアルカリ金属塩を表わす。本発明の集
束平滑剤は延伸時の毛羽断糸を抑え高倍率延伸を可能に
ならしめるために必要なものであるが、例えばアルキル
エステル、ソルビタンエステル、ひまし油エステル、グ
リセリンエステル、グリコールエステルあるいはそれら
の分子内にエチレンオキサイドが付加したものなどエス
テル系のノニオン活性剤、さらには鉱物油又はそれにエ
チレンオキサイドが付加したものが含まれる。In the formula, M represents H or an alkali metal salt. The convergence smoothing agent of the present invention is necessary for suppressing fluff breakage during stretching and enabling high-magnification stretching.For example, alkyl esters, sorbitan esters, castor oil esters, glycerin esters, glycol esters or their esters Ester nonionic activators, such as those having ethylene oxide added to the molecule, and mineral oils or ethylene oxide added thereto are also included.
前記界面活性剤と集束平滑剤はお互に相溶性があり繊
維に均一付着するのが好ましくそのために他の乳化剤や
浸透剤を少量用いても良い。It is preferable that the surfactant and the convergence smoothing agent are compatible with each other and adhere to the fiber uniformly, and therefore, other emulsifiers and penetrants may be used in small amounts.
該界面活性剤の付着量は繊維に対し0.2〜3重量%、
好ましくは0.5〜2重量%であり、0.2重量%未満では繊
維表面でのOH基との反応または脱水反応が不十分で耐熱
水性の良い繊維が得難い。3重量%を越えると耐熱性の
高いものとなるが延伸倍率が低下し、強度の低い繊維し
か得られない。The amount of the surfactant attached is 0.2 to 3% by weight with respect to the fiber,
Preferably it is 0.5 to 2% by weight, and if it is less than 0.2% by weight, the reaction with the OH group on the fiber surface or the dehydration reaction is insufficient, and it is difficult to obtain a fiber having good hot water resistance. If it exceeds 3% by weight, the heat resistance becomes high, but the draw ratio decreases, and only fibers with low strength can be obtained.
該集束平滑剤の付着量は繊維に対し0.5〜5重量%、
好ましくは1〜3重量%であり、0.5重量%未満では繊
維がバラケ易くて単糸毛羽を発生したり延伸倍率を低下
させる。5重量%を超えると粘着気味で強度低下となつ
たり該界面活性剤の反応を阻害したり延伸時の発煙を招
いて好ましくない。The amount of the bunched smoothing agent is 0.5 to 5% by weight based on the fiber;
Preferably, the content is 1 to 3% by weight, and if it is less than 0.5% by weight, the fibers are liable to be scattered, causing single yarn fluff and lowering the draw ratio. If it exceeds 5% by weight, the strength is lowered due to a slight tackiness, the reaction of the surfactant is inhibited, and smoke is generated during stretching, which is not preferable.
付着方法はメタノールなどのアルコール類やアセト
ン、ヘキサン、水などで希釈した溶液又はエマルジヨン
液をローラタツチ方式でデイツプ−ニツプ方式、ギヤポ
ンプオイリング方式などで繊維に付着させる方法がとら
れるが、繊維表面に均一付着する条件が好ましい。As a method of attachment, a solution diluted with alcohols such as methanol, acetone, hexane, water or the like or an emulsion liquid is attached to the fiber by a roller-touch method such as a dipping-nip method or a gear pump oiling method. Conditions for adhering are preferred.
該界面活性剤および集束平滑剤を所定量付着した紡糸
原糸を乾熱延伸する場合、延伸温度を240℃以上して、
総延伸倍率を17倍以上にする必要がある。この理由は、
繊維表面のPVA水酸基と該界面活性剤の反応を十分行な
わせ、かつPVA分子鎖の配向と結晶化を進ませて高強度
で耐熱水性にすぐれた繊維を得るためである。延伸雰囲
気は一般に空気、N2などの不溶性ガス、水蒸気、油浴な
どが考えられるが界面活性剤の反応性や操作性、コスト
などから考えて加熱空気が適している。また熱板や加熱
ローラを用いた接触タイプと熱風炉を用いた非接触タイ
プがあるがどちらでも支障はない。高重合度ほど分子鎖
のからみが多くなるためか延伸倍率が低下し易くそれを
カバーするために延伸温度は高くなる。例えば重合度3,
000で240℃、10,000で250℃、20,000では260℃程度とな
るが、高温ほど界面活性剤が反応して耐熱水性のある表
皮構造をとり易い。なお265℃以上あるいは1分以上の
滞留はPVAの分解が激しく強度低下を招くので好ましく
ない。When dry spinning the spun yarn to which a predetermined amount of the surfactant and the bunching smoothing agent are attached, the drawing temperature is set to 240 ° C. or higher,
The total stretching ratio needs to be 17 times or more. The reason for this is
This is because the reaction between the PVA hydroxyl group on the fiber surface and the surfactant is sufficiently performed, and the orientation and crystallization of the PVA molecular chain are advanced to obtain a fiber having high strength and excellent hot water resistance. The stretching atmosphere is generally considered to be air, an insoluble gas such as N 2 , water vapor, an oil bath, etc., but heating air is suitable in consideration of the reactivity of the surfactant, operability, cost and the like. There are a contact type using a hot plate or a heating roller and a non-contact type using a hot blast stove. The higher the degree of polymerization, the more likely the entanglement of the molecular chains is, or the lower the draw ratio, and the higher the draw temperature, in order to cover the draw ratio. For example, polymerization degree 3,
The temperature is about 240 ° C. for 000, about 250 ° C. for 10,000, and about 260 ° C. for 20,000. However, the higher the temperature, the more easily the surfactant reacts to form a skin structure with hot water resistance. It is to be noted that staying at 265 ° C. or more or 1 minute or more is not preferable because PVA is greatly decomposed and the strength is reduced.
総延伸倍率は湿延伸倍率と乾熱延伸倍率の積で表わさ
れるが、17倍以上好ましくは19倍以上である。The total draw ratio is represented by the product of the wet draw ratio and the dry heat draw ratio, and is 17 times or more, preferably 19 times or more.
以上で述べた製造条件にしたがつて繊維製造を行なう
ことによつて基本的に引張強度が16g/d以上といつた高
強力繊維が得られるが、前記のように本発明では特定の
界面活性剤と集束平滑剤との処理を組合わせたことによ
り、さらに耐熱水性が極めて優れた繊維となるものであ
る。By performing fiber production in accordance with the production conditions described above, a high-strength fiber having a tensile strength of at least 16 g / d can be basically obtained. The combination of the agent and the treatment with the convergence smoothing agent results in a fiber having extremely excellent hot water resistance.
PVA系繊維の熱水溶断温度WTbは一般に高重合度ほど高
い値を示すが、本発明では実験データに基づいた次式を
満足する繊維が得られる。In general, the higher the degree of polymerization, the higher the thermal water-breaking temperature WTb of the PVA-based fiber. The higher the degree of polymerization, the higher the degree of polymerization.
WTb≧1.2A0.35+125(A≧3,000) 即ち、本発明により得られた繊維はいずれの重合度に
おいても従来品より10〜50℃高い熱水溶断温度を示す。WTb ≧ 1.2A 0.35 +125 (A ≧ 3,000) That is, the fiber obtained by the present invention exhibits a hot water-breaking temperature higher by 10 to 50 ° C. than the conventional product at any degree of polymerization.
本発明は従来に見られない高耐熱水性高強度のPVA系
繊維が得られ、ロープ、帆布等の産業資材、オートクレ
ーブ養生セメント補強材、タイヤ補強材、高温高圧ホー
ス補強材、FRP用補強材、ブレーキオイルホース補強材
など幅広い活用が期待できる。The present invention provides a PVA-based fiber having a high heat-resistant and high-strength property not found in the past, ropes, industrial materials such as canvas, an autoclave-cured cement reinforcement, a tire reinforcement, a high-temperature high-pressure hose reinforcement, a reinforcement for FRP, A wide range of applications such as brake oil hose reinforcement can be expected.
以下、実施例により本発明をさらに具体的に説明す
る。なお以下に述べる実施例中の各種物性値は以下の方
法で測定されたものである。Hereinafter, the present invention will be described more specifically with reference to examples. The various physical properties in the examples described below were measured by the following methods.
1)PVA繊維の重合度低下率 密閉容器にPVA繊維と蒸留水を入れ、130℃以上で溶解
したあとJISK-6726に準じ〔η〕より次式で重合度A
を求めPVAポリマーの重合度に対する低下率を算出す
る。1) Decrease in polymerization degree of PVA fiber Put PVA fiber and distilled water in a closed container, dissolve it at 130 ° C or higher, and then polymerize according to JISK-6726 [η] by the following formula according to [η].
And the rate of decrease with respect to the degree of polymerization of the PVA polymer is calculated.
A=(〔η〕×104/8.29)1.63 2)ヤーンの引張強伸度、弾性率 JISL-1013に準じ予め調湿されたヤーンを試長20cmで
0.25g/dの初荷重および50%/分の引張速度にて破断伸
度および初期弾性率を求め、10点以上の平均値を採用し
た。デニールは重量法により求めた。A = ([η] × 10 4 /8.29) 1.63 2) Tensile strength and elongation, elastic modulus of yarn Yarn conditioned in advance according to JISL-1013 was tested at a test length of 20 cm.
The elongation at break and the initial elastic modulus were determined at an initial load of 0.25 g / d and a tensile speed of 50% / min, and an average value of 10 or more points was adopted. Denier was determined by the gravimetric method.
3)耐熱水性(WTb) 単繊維25本にデニール当り200mgの荷重をかけ、水を
満たしたガラス製円筒状密閉容器の中間に吊し、周囲よ
り水を1〜2℃/分の速度で加熱昇温させていき繊維が
溶断したときの温度を読んだ。3) Hot water resistance (WTb) A load of 200 mg per denier is applied to 25 single fibers, suspended in the middle of a water-filled cylindrical glass container, and water is heated from the surroundings at a rate of 1-2 ° C / min. As the temperature was raised, the temperature at which the fiber was melted was read.
4)界面活性剤又は油剤の付着率 予め界面活性剤又は油剤の付着した繊維を100℃4時
間真空乾燥したあと重量W1を測定する。次いでメタノー
ル/ベンゼン=1/1の混合液で8時間界面活性剤又は油
剤をソツクスレー抽出したあと100℃4時間真空乾燥し
て重量W2を測定し より算出した。4) measuring the after weight W 1 in which the vacuum drying 100 ° C. 4 h deposited fibers surfactant or adhesion rate previously surfactant or oils of oil. Then, the surfactant or oil was soxhlet extracted with a mixed solution of methanol / benzene = 1/1 for 8 hours, dried at 100 ° C. for 4 hours under vacuum, and the weight W 2 was measured. It was calculated from:
実施例1および比較例1 平均重合度21,500のPVAを濃度4.2%になるようにグリ
セリンに溶解し、該溶液を孔数300、孔径0.20mmのノズ
ルより吐出させ、乾湿式紡糸によりメタノール/グリセ
リン=8/2、−10℃の凝固浴中に落下させ透明なゲル糸
を得た。次にグリセリンを含んだ状態で4倍の湿延伸を
施したあとメタノールで該溶剤をほぼ完全に抽出してか
らアニオン界面活性剤のラウリルホスヘートトリイソプ
ロパノールアミンを2重量%とPOE(20)ソルビタンモ
ノステアレート5重量%を含むメタノール溶液をギヤポ
ンプオイリング方式で繊維に対し40重量%付着させて90
℃にて乾燥した。アニオン活性剤0.8重量%と集束平滑
剤2.0重量%を繊維に付着させた。得られた紡糸原糸を1
70℃と260℃の熱風炉を用い総延伸倍率が17.9倍になる
ように延伸した。なお260℃熱風炉の滞留時間は32秒で
あり繊維は灰紫色に着色したが膠着は見られなかつた。
得られた延伸糸の断面写真より繊維の表層部のみが灰紫
色であり内部は白色であつた。ヤーンの引張強度は21.2
g/d、熱水溶断温度WTbは182℃を示し、従来のPVA繊維で
は得られない耐熱水性にすぐれた高強度繊維であり、17
0℃のオートクレーブ養生によるセメント補強が可能と
なりさらに高温高湿のゴム補強材やロープ漁網など幅広
い用途展開の出来る高付加価値繊維となつた。Example 1 and Comparative Example 1 PVA having an average degree of polymerization of 21,500 was dissolved in glycerin so as to have a concentration of 4.2%, and the solution was discharged from a nozzle having a number of holes of 300 and a diameter of 0.20 mm. It was dropped into a coagulation bath at 8/2 at -10 ° C to obtain a transparent gel thread. Next, the film is stretched by a factor of 4 with glycerin in it, and the solvent is almost completely extracted with methanol. Then, 2% by weight of anionic surfactant lauryl phosphate triisopropanolamine and POE (20) sorbitan are added. A methanol solution containing 5% by weight of monostearate was attached to the fiber by 40% by weight using a gear pump oiling method, and 90%
Dry at ℃. 0.8% by weight of anionic activator and 2.0% by weight of sizing smoother were applied to the fibers. 1 spun yarn obtained
The film was stretched using a hot air oven at 70 ° C. and 260 ° C. so that the total stretching ratio was 17.9 times. The residence time in the hot-air stove at 260 ° C. was 32 seconds, and the fibers were colored gray-violet, but no sticking was observed.
From the photograph of the cross section of the obtained drawn yarn, only the surface layer of the fiber was gray purple and the inside was white. Yarn tensile strength is 21.2
g / d, hot water break temperature WTb is 182 ° C, a high strength fiber with excellent hot water resistance that cannot be obtained with conventional PVA fiber,
Cement reinforcement by autoclave curing at 0 ° C has become possible, and it has become a high-value-added fiber that can be used in a wide range of applications, such as high-temperature and high-humidity rubber reinforcements and rope fishing nets.
比較例1として、実施例1で該界面活性剤を入れずに
集束平滑剤のPOE(20)ソルビタンモノステアレートの
みを付着させ同様に延伸したが、延伸時若干黄色に着色
し、膠着があつた。総延伸倍率は18.6倍、ヤーン強度は
20.8g/dを示し、WTbは152℃と明らかに実施例1に比べ
て耐熱水性が低くなつた。As Comparative Example 1, only the POE (20) sorbitan monostearate as a convergence smoothing agent was attached and stretched in the same manner as in Example 1 except that the surfactant was not added. Was. The total draw ratio is 18.6 times and the yarn strength is
It showed 20.8 g / d, and the WTb was found to be 152 ° C., and the hot water resistance was clearly lower than that of Example 1.
実施例2および比較例2 平均重合度17,000のPVAを濃度4.5%になるようにジメ
チルスルホキシドに溶解し、孔数500、孔径0.15mmのノ
ズルでメタノール/ジメチルホキシド=7/3、5℃の凝
固浴を用いて湿式紡糸した。引続いて4.5倍の湿延伸を
したあとメタノールで該溶剤をほとんど完全に除去し90
℃の熱風で乾燥した。次いでチオジプロピオン酸ラウリ
ルアミンのアニオン活性剤を1.5重量とPOE(150)カス
ターワツクス4重量%のメタノール溶液をローラタツチ
方式にて繊維に対し80重量%付着(アニオン活性剤1.2
重量%と集束平滑剤3.2重量%を付着)させ、180℃の熱
風炉で1.5倍255℃の熱風炉で2.8倍(総延伸倍率18.9
倍)延伸した。255℃熱風炉の滞留時間は38秒であつ
た。得られた延伸糸の表層部は灰茶に着色したがヤーン
強度は20.7g/d、WTbが169℃を示し、高強度で耐熱水性
のあるPVA繊維となつた。Example 2 and Comparative Example 2 PVA having an average degree of polymerization of 17,000 was dissolved in dimethyl sulfoxide so as to have a concentration of 4.5%, and methanol / dimethyloxide = 7/3, 5 ° C. with a nozzle having 500 holes and a hole diameter of 0.15 mm. Wet spinning was performed using a coagulation bath. Subsequently, the film was stretched by a factor of 4.5, and the solvent was almost completely removed with methanol.
It dried with the hot air of ° C. Then, 80% by weight of a methanol solution of 1.5% by weight of laurylamine thiodipropionate and 4% by weight of POE (150) Custerwax was attached to the fiber by a roller touch method (anionic surfactant 1.2%).
Wt% and a convergence smoothing agent of 3.2 wt%), 1.5 times in a 180 ° C hot air stove and 2.8 times in a 255 ° C hot stove (total stretching ratio of 18.9%).
Times) stretched. The residence time in the hot stove at 255 ° C was 38 seconds. The surface layer of the obtained drawn yarn was colored in ash brown, but had a yarn strength of 20.7 g / d and a WTb of 169 ° C., resulting in a PVA fiber having high strength and hot water resistance.
比較例2として、実施例2において延伸温度を255℃
から235℃に低下させたところ延伸糸はほとんど着色せ
ず総延伸倍率も16.2倍に低下した。ヤーン強度は18.9g/
d、WTbは149℃であり、明らかに実施例2より性能が低
いものとなつた。As Comparative Example 2, the stretching temperature was set to 255 ° C. in Example 2.
When the temperature was lowered to 235 ° C., the drawn yarn was hardly colored, and the total draw ratio was also reduced to 16.2 times. Yarn strength is 18.9g /
d, WTb was 149 ° C., which was clearly lower than that of Example 2.
実施例3 粘度平均重合度が7,000のPVAを濃度8重量%になるよ
うに水に添加し、同時にホウ酸をPVAに対し2重量%添
加して105℃で溶解した。得られた溶液を1000ホール0.1
mm孔径のノズルよりアルカリと芒硝の混合水溶液40℃の
中に吐出させ湿式紡糸を行なつた。引続き5.3倍の湿延
伸を行ない、引続き中和、水洗を経たあとローラタツチ
方式により乾燥前に油剤に付与した。油剤はステアリル
アミドプロピルスルホネートNaのアニオン活性剤2重量
%とグリセリントリオレエート3重量%およびPOE(1
1)オイルエーテル0.5重量%の水エマルジヨン溶液であ
り、繊維に対する油剤付着量は4.1重量%であつた。延
伸は180-210-248℃の熱風炉を用い総延伸倍率を24.6倍
とした。延伸ヤーンの強度は18.2g/d WTbは155℃の高い
値を示した。Example 3 PVA having a viscosity average degree of polymerization of 7,000 was added to water so as to have a concentration of 8% by weight. At the same time, 2% by weight of boric acid was added to PVA and dissolved at 105 ° C. The resulting solution was placed in 1000 holes 0.1
The mixture was discharged into a mixed aqueous solution of alkali and sodium sulfate at 40 ° C. from a nozzle having a hole diameter of mm, and wet spinning was performed. Subsequently, the sheet was subjected to 5.3 times wet stretching, subsequently neutralized and washed with water, and then applied to the oil before drying by a roller touch method. The oil was 2% by weight of an anionic surfactant of sodium stearylamidopropylsulfonate, 3% by weight of glycerin trioleate and POE (1%).
1) It was a water emulsion solution containing 0.5% by weight of oil ether, and the amount of the oil agent attached to the fibers was 4.1% by weight. The stretching was performed using a hot-air stove at 180-210-248 ° C, and the total stretching ratio was 24.6 times. As for the strength of the drawn yarn, 18.2 g / d WTb showed a high value of 155 ° C.
フロントページの続き (72)発明者 大森 昭夫 岡山県倉敷市酒津1621番地 株式会社ク ラレ内 審査官 真々田 忠博 (56)参考文献 特許2826183(JP,B2) (58)調査した分野(Int.Cl.6,DB名) D01F 6/14Continued on the front page (72) Inventor Akio Omori 1621 Sazu, Kurashiki-shi, Okayama Pref. Kuraray Co., Ltd. Examiner Tadahiro Sanada (56) References Patent 2826183 (JP, B2) 6 , DB name) D01F 6/14
Claims (1)
アルコール系繊維に、その紡糸から乾熱延伸直前までの
間で、ホスヘートアミン化合物、アミン又はアミドのホ
スヘート化合物、アミン又はアミドのスルホネート化合
物、並びにチオ化合物の中より選ばれた1種又は2種以
上の界面活性剤0.2〜3重量%とエステル系又は鉱物油
系集束平滑剤0.5〜5重量%とを付着せしめ、240℃以上
の高温にて総延伸倍率が17倍以上となるように延伸する
ことを特徴とする、熱水溶断温度WTbが次式を満足する
耐熱水性ポリビニルアルコール系繊維の製造法。 WTb≧1.2A0.35+125 (A≧3000) ここでWTbは荷重200mg/d下の熱水溶断温度(℃)、A
はポリビニルアルコール系ポリマーの粘度平均重合度。1. A polyvinylamine fiber having a viscosity-average degree of polymerization of 3,000 or more, from the spinning to immediately before dry heat drawing, of a phosphateamine compound, a phosphate compound of an amine or an amide, a sulfonate compound of an amine or an amide, and a thione compound. One or two or more surfactants selected from the compounds are applied in an amount of 0.2 to 3% by weight and an ester or mineral oil-based sizing and leveling agent in an amount of 0.5 to 5% by weight. A method for producing a hot water-resistant polyvinyl alcohol-based fiber, wherein the hot-water-water break temperature WTb satisfies the following expression, wherein the drawing is performed so that the draw ratio becomes 17 times or more. WTb ≧ 1.2A 0.35 +125 (A ≧ 3000) where WTb is the hot water temperature (° C) under the load of 200mg / d, A
Is the viscosity average degree of polymerization of the polyvinyl alcohol polymer.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP28269190A JP2858925B2 (en) | 1990-10-19 | 1990-10-19 | Method for producing hot water-resistant polyvinyl alcohol fiber |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP28269190A JP2858925B2 (en) | 1990-10-19 | 1990-10-19 | Method for producing hot water-resistant polyvinyl alcohol fiber |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH04163311A JPH04163311A (en) | 1992-06-08 |
JP2858925B2 true JP2858925B2 (en) | 1999-02-17 |
Family
ID=17655803
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Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP28269190A Expired - Lifetime JP2858925B2 (en) | 1990-10-19 | 1990-10-19 | Method for producing hot water-resistant polyvinyl alcohol fiber |
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JP (1) | JP2858925B2 (en) |
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JP5607930B2 (en) | 2006-10-12 | 2014-10-15 | ビーエイチアイ リミテッド パートナーシップ | Methods, compounds, compositions and vehicles for delivering 3-amino-1-propanesulfonic acid |
JP2015001031A (en) * | 2013-06-14 | 2015-01-05 | 株式会社クラレ | Polyvinyl alcohol fiber for rubber reinforcement |
-
1990
- 1990-10-19 JP JP28269190A patent/JP2858925B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
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JPH04163311A (en) | 1992-06-08 |
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