JPH05263312A - Production of polyvinyl alcoholic fiber excellent in strength - Google Patents
Production of polyvinyl alcoholic fiber excellent in strengthInfo
- Publication number
- JPH05263312A JPH05263312A JP8798492A JP8798492A JPH05263312A JP H05263312 A JPH05263312 A JP H05263312A JP 8798492 A JP8798492 A JP 8798492A JP 8798492 A JP8798492 A JP 8798492A JP H05263312 A JPH05263312 A JP H05263312A
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- Prior art keywords
- bath
- solvent
- pva
- godet roller
- spinning
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
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- 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、主として強度の優れた
ポリビニルアルコール（以下ＰＶＡと略記する）系繊維
を製造するために利用される湿式紡糸方法に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wet spinning method mainly used for producing a polyvinyl alcohol (hereinafter abbreviated as PVA) fiber having excellent strength.
【０００２】[0002]
【従来の技術】汎用繊維の中で、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、弾性率が高いため、漁網、ロープなどの産
業資材用としてばかりでなく、セメント、プラスチック
などの補強材用としても利用されている。一方では社会
の高度化に伴い、ＰＶＡ系繊維に対してもより高強度化
の要望が高まっている。2. Description of the Related Art Among general-purpose fibers, PVA-based fibers have higher strength and elastic modulus than polyamide, polyester and polyacrylonitrile-based fibers, so that they are not only used for industrial materials such as fishing nets and ropes, but also for cement, It is also used for reinforcing materials such as plastics. On the other hand, with the advancement of society, there is an increasing demand for higher strength of PVA-based fibers.
【０００３】このような要望に応えるべく、より高強度
なＰＶＡ系繊維を製造する方法として、超高分子量ポリ
エチレンのゲル紡糸−超延伸の考え方をＰＶＡに適用し
た特開昭５９−１３０３１４号公報などが提案され、さ
らには高重合度ＰＶＡを用い、有機溶媒を使用して湿式
あるいは乾湿式法により凝固紡糸することが特開昭５９
−１００７１０号公報、特開昭６０−１２６３１２号公
報や特開昭６３−９９３１５号公報などにおいて提案さ
れている。なお本発明においては、ゲル紡糸とは紡糸原
液が組成変化を伴わずとも冷却のみで固化する場合をい
い、凝固紡糸とは紡糸原液が冷却のみでは固化せず、固
化浴が紡糸原液に浸透し組成変化して固化する場合をい
う。In order to meet such demands, as a method for producing a higher strength PVA-based fiber, JP-A-59-130314, which applies the concept of gel spinning-ultra-drawing of ultra-high molecular weight polyethylene to PVA, etc. Japanese Patent Laid-Open No. Sho 59-59, in which PVA with a high degree of polymerization is used and coagulated spinning is performed by a wet or dry-wet method using an organic solvent.
-100710, JP-A-60-126312, JP-A-63-99315 and the like. In the present invention, gel spinning means a case where the spinning dope is solidified only by cooling without accompanying a composition change, and coagulating spinning is that the spinning dope does not solidify only by cooling, and the solidification bath permeates the spinning dope. It refers to the case where the composition changes and solidifies.
【０００４】しかし、ゲル紡糸は、工業的に実施しよう
として多ホールで紡糸すると極めて硬着し易く、工業的
に実施するには凝固紡糸が有利であるが、従来の公知技
術で採用されている凝固紡糸の場合、高重合度ＰＶＡを
用いた際、必ずしもゲル紡糸ほどの高強度なＰＶＡ繊維
を得ることができない。この原因について種々追及し、
その顕著な一因が紡糸原液の固化抽出過程にあることを
見出し、これを解決する手段として本発明者らは先に特
願平３−２６７２０３号を提案した。すなわち第１ゴデ
ットローラー部での固化糸の溶媒残存率を原液溶媒量の
２５〜８０％と高くすることが重要であることを見出し
た。[0004] However, gel spinning is extremely easy to settle when it is spun in a large number of holes for industrial purposes, and coagulated spinning is advantageous for industrial purposes, but it has been adopted in conventional known techniques. In the case of coagulation spinning, when PVA having a high degree of polymerization is used, it is not always possible to obtain PVA fibers having a strength as high as gel spinning. We will investigate various causes of this,
One of the prominent causes was found to be the solidification extraction process of the spinning dope, and the inventors previously proposed Japanese Patent Application No. 3-267203 as a means for solving this. That is, it has been found that it is important to increase the solvent residual rate of the solidified yarn in the first godet roller portion to 25 to 80% of the amount of the stock solution solvent.
【０００５】一方ゲル紡糸と凝固紡糸は先述の如く固化
機構の観点から溶液紡糸を分類したものであるが、紡糸
形態の観点から分類すると、ノズル面と固化浴の間に空
気などの不活性気体層を介在させる乾湿式紡糸法と、ノ
ズル面を固化浴と直接接触させる湿式紡糸法があり、湿
式紡糸には、原液をノズル面より鉛直上方に吐出させる
流上湿式紡糸法、原液をノズル面より鉛直下方に吐出さ
せる流下湿式紡糸法、原液をノズル面より水平に吐出さ
せる横型湿式紡糸などがあるが、ＰＶＡ系繊維で操業化
され、最も実績のある紡糸形態は流上湿式紡糸法であ
る。そこで特開平３−２６７２０３号提案の紡糸法を流
上湿式紡糸に適用しようとしたところ、特に第１ゴデッ
トローラー速度が高速の場合、工程通過性及び繊維性能
が不安定となることがわかった。On the other hand, gel spinning and coagulation spinning are classified into solution spinning from the viewpoint of the solidification mechanism as described above, but from the viewpoint of the spinning form, an inert gas such as air is present between the nozzle surface and the solidification bath. There are a dry-wet spinning method in which a layer is interposed and a wet spinning method in which the nozzle surface is brought into direct contact with the solidifying bath. There are a falling wet spinning method that discharges more vertically downward, and a horizontal wet spinning method that discharges the stock solution horizontally from the nozzle surface. .. Therefore, when the spinning method proposed in JP-A-3-267203 was applied to the upstream wet spinning, it was found that the process passability and the fiber performance became unstable especially when the first godet roller speed was high. ..
【０００６】[0006]
【発明が解決しようとする課題】従って本発明は、原液
溶媒と凝固浴のいずれもが有機溶媒系を使用するＰＶＡ
系繊維の凝固紡糸を流上湿式紡糸法で高速で実施する場
合、如何にしたら高重合度でもゲル紡糸法に匹敵する高
強度のＰＶＡ系繊維を安定に製造できるかを追及したも
のである。Accordingly, the present invention is a PVA in which both the stock solution solvent and the coagulation bath use an organic solvent system.
When the coagulating spinning of the system fibers is carried out at a high speed by the flow-up wet spinning method, how to stably produce PVA fibers having a high degree of polymerization and having a high strength comparable to the gel spinning method is pursued.
【０００７】[0007]
【課題を解決するための手段】すなわち本発明は、粘度
平均重合度１５００以上のＰＶＡ系ポリマーを有機溶媒
に溶解して得られる紡糸原液を、凝固能を有する有機溶
媒系の固化浴中にバスドラフト１未満の状態で押し出
し、形成された固化糸を１０ｍ／分以上の第１ゴデット
ローラー速度で引き取る流上湿式紡糸において、固化糸
の固化浴中での滞留時間をＴ↓B、固化浴上から第１ゴ
デットローラーに接触するまでの大気滞留時間をＴ↓A
とするとき、０．５Ｔ↓B≦Ｔ↓A≦１０Ｔ↓Bを満足
し、かつ第１ゴデットローラー部での固化糸の溶媒残存
率を原液溶媒量に対し２５〜８０％とすることを特徴と
するＰＶＡ系繊維の製法である。[Means for Solving the Problems] That is, according to the present invention, a spinning stock solution obtained by dissolving a PVA-based polymer having a viscosity average degree of polymerization of 1500 or more in an organic solvent is placed in a bath in an organic solvent-based solidifying bath having coagulability. In the upstream wet spinning, which extruded in a state of less than draft 1 and took the formed solidified yarn at the first godet roller speed of 10 m / min or more, the residence time of the solidified yarn in the solidifying bath was T ↓ B, the solidifying bath The atmospheric residence time from the top to the contact with the first godet roller is T ↓ A
When 0.5T ↓ B ≦ T ↓ A ≦ 10T ↓ B is satisfied, and the solvent residual rate of the solidified yarn in the first godet roller portion is set to 25 to 80% with respect to the stock solution solvent amount. This is a method for producing a characteristic PVA fiber.
【０００８】本発明に用いるＰＶＡ系ポリマーは、３０
℃の水溶液で粘度法により求めた粘度平均重合度が１５
００以上のものである。平均重合度が１５００未満では
本発明の目的である高強度のＰＶＡ系繊維を得ることが
できない。平均重合度が３５００以上であるとより好ま
しく、７０００以上であるとさらに好ましい。特に平均
重合度が１５００以上であると、本発明紡糸法の効果が
より顕著となる。The PVA polymer used in the present invention is 30
The viscosity average degree of polymerization determined by the viscosity method in an aqueous solution at ℃ is 15
00 or more. If the average degree of polymerization is less than 1500, the high-strength PVA-based fiber, which is the object of the present invention, cannot be obtained. The average degree of polymerization is more preferably 3500 or more, further preferably 7,000 or more. Particularly when the average degree of polymerization is 1500 or more, the effect of the spinning method of the present invention becomes more remarkable.
【０００９】用いるＰＶＡ系ポリマーのケン化度に関し
ては特別な限定はないが、９８．５モル％以上が好まし
く、９９．７モル％以上であるとさらに好ましい。また
用いるＰＶＡ系ポリマーは、他のビニル基を有するモノ
マー、例えばエチレン、イタコン酸、ビニルピロリドン
などのモノマーを１０モル％以下、好ましくは２モル％
以下の比率で共重合したものであってもよい。The saponification degree of the PVA-based polymer used is not particularly limited, but is preferably 98.5 mol% or more, and more preferably 99.7 mol% or more. The PVA-based polymer used is 10 mol% or less, preferably 2 mol%, of another vinyl group-containing monomer such as ethylene, itaconic acid, or vinylpyrrolidone.
It may be copolymerized in the following ratio.
【００１０】本発明に用いるＰＶＡ系ポリマーの溶媒と
しては、ＰＶＡ系ポリマーを溶解することができ、メタ
ノールなどの凝固能を有する有機溶媒の浸透によってＰ
ＶＡ系ポリマーの溶液を固化させることができる有機溶
媒なら特に限定はなく、ジメチルスルホキシド（ＤＭＳ
Ｏと略記する）、ジメチルホルムアミド、ジメチルイミ
ダゾリジノンなどの極性溶媒があげられる。またこれら
の溶媒の混合物なども使用しうる。数多い溶媒の中でも
ＤＭＳＯは８０℃以下の低温で溶解することができ、Ｐ
ＶＡ系ポリマーの重合度低下を少なくすることができ、
好ましい溶媒である。As a solvent for the PVA-based polymer used in the present invention, a PVA-based polymer can be dissolved and an organic solvent having a coagulating ability, such as methanol, permeates into the PVA-based polymer.
There is no particular limitation as long as it is an organic solvent that can solidify the solution of the VA polymer, and dimethyl sulfoxide (DMS
Abbreviated as O), dimethylformamide, dimethylimidazolidinone, and other polar solvents. Also, a mixture of these solvents may be used. Among many solvents, DMSO can be dissolved at a low temperature of 80 ° C or less,
It is possible to reduce the decrease in the degree of polymerization of the VA polymer,
It is the preferred solvent.
【００１１】紡糸原液におけるＰＶＡ系ポリマーの濃度
は、ＰＶＡ系ポリマーの重合度や溶媒の種類などによっ
て異なるが、通常２〜３０重量％、好ましくは３〜２０
重量％である。特に本発明では高強度ＰＶＡ繊維を得る
ことを目的としており、このためには紡糸時の単糸切れ
や糸斑、単糸間硬着などが生じない範囲内でＰＶＡ系ポ
リマー濃度を低くした方が好ましい。The concentration of the PVA-based polymer in the spinning dope varies depending on the degree of polymerization of the PVA-based polymer and the type of solvent, but is usually 2 to 30% by weight, preferably 3 to 20%.
% By weight. In particular, the present invention aims to obtain a high-strength PVA fiber, and for this purpose, it is better to lower the concentration of the PVA-based polymer within the range in which single yarn breakage, yarn unevenness, single yarn adhesion and the like do not occur during spinning. preferable.
【００１２】また、紡糸原液にはＰＶＡ系ポリマーと溶
媒以外にも目的に応じて種々の添加剤、例えば顔料など
の着色剤、酸化防止剤、紫外線吸収剤、架橋剤、界面活
性剤、酸などのｐＨ調節剤などを所要量添加してもよ
い。さらにＤＭＳＯの如く比較的高い凍結温度を有する
溶媒に対しては、水などの溶媒やメタノールなどの凝固
作用を示すものでもＰＶＡ系ポリマーが凝固しない範囲
内で添加すると、固化浴を溶媒の凍結温度以下としても
紡糸原液が凍結しないので好ましい場合がある。In addition to the PVA-based polymer and the solvent, various additives such as colorants such as pigments, antioxidants, ultraviolet absorbers, crosslinking agents, surfactants, acids, etc. may be added to the spinning dope. You may add the required amount of the pH adjuster and the like. Furthermore, for a solvent having a relatively high freezing temperature such as DMSO, if a PVA-based polymer is added within a range that does not coagulate even a solvent such as water or a solvent that exhibits a coagulating action such as methanol, the solidifying bath freezes the solvent. The following may also be preferable because the spinning dope does not freeze.
【００１３】ＰＶＡ系ポリマー、溶媒及び添加剤を溶解
機に仕込み、例えば溶媒としてＤＭＳＯを使用する場
合、混合物を攪拌しながら、５０〜１２０℃に昇温し、
攪拌を４〜１６時間続行し、ＰＶＡ系ポリマーを溶媒に
溶解し、次いで脱泡して紡糸原液とする。この際、仕込
み後昇温前に溶解機に窒素などの不活性気体を加圧注
入、減圧排出を繰り返し不活性気体に置換し、昇温溶解
中や脱泡放置中も減圧あるいは不活性気体による加圧を
行ないＰＶＡ系ポリマーの溶液を可能な限り酸素と接触
させない方がＰＶＡ系ポリマーの分解抑制の点で好まし
い。重合度が高くなると溶解脱泡温度を高くする必要が
あり、この場合特に不活性気体による置換などにより酸
素と接触させないことが重要となる。When the PVA-based polymer, the solvent and the additives are charged into a dissolver and, for example, DMSO is used as the solvent, the temperature is raised to 50 to 120 ° C. while stirring the mixture.
Stirring is continued for 4 to 16 hours, the PVA polymer is dissolved in a solvent, and then defoamed to prepare a spinning dope. At this time, an inert gas such as nitrogen was injected under pressure into the dissolver after the charging and before the temperature was raised, and the inert gas was repeatedly discharged under reduced pressure to replace the inert gas with the reduced pressure or the inert gas during the temperature rising dissolution or the degassing. From the viewpoint of suppressing decomposition of the PVA-based polymer, it is preferable to apply pressure to prevent the solution of the PVA-based polymer from contacting with oxygen as much as possible. As the degree of polymerization becomes higher, it is necessary to raise the melting and defoaming temperature. In this case, it is particularly important not to contact with oxygen by replacement with an inert gas.
【００１４】バスドラフト（原液がノズルより吐出され
る際の吐出線速度に対する第１ゴデットローラー速度の
比で定義される。）は１．０未満としないと後工程での
延伸性が不十分となり、高強度繊維を得ることが困難と
なる。バスドラフトが０．１〜０．５の範囲がより好ま
しく、０．１５〜０．３であるとさらに好ましい。ノズ
ルの孔径をバスドラフトが適性となるよう選択すること
が重要である。If the bath draft (defined by the ratio of the first godet roller speed to the discharge linear velocity when the stock solution is discharged from the nozzle) is not less than 1.0, the stretchability in the subsequent step is insufficient. Therefore, it becomes difficult to obtain high-strength fibers. The bath draft is more preferably in the range of 0.1 to 0.5, further preferably 0.15 to 0.3. It is important to select the nozzle hole size so that the bath draft is suitable.
【００１５】本発明に用いる紡糸形態は、流上湿式紡糸
法である。ノズル面と固化浴の間に不活性気体を介在さ
せる乾湿式紡糸法では不活性気体層での単糸間硬着が起
き易く、ノズルの孔ピッチを大きくせねばならずコンパ
クト化が困難となる。ノズル面が固化浴と直接接触する
湿式紡糸法はノズル吐出直後、固化浴が浸透し、直ちに
固化するため、ノズルの孔ピッチを小さくすることがで
き、このため多ホールでもコンパクト化しうる。湿式紡
糸法の中では流上湿式紡糸法がＰＶＡ系繊維の生産で最
も一般的に行なわれており、技術蓄積が多く、工業的に
最も実施し易い紡糸法である。The spinning form used in the present invention is an upstream wet spinning method. In the dry-wet spinning method in which an inert gas is interposed between the nozzle surface and the solidifying bath, single yarn yarn sticking is likely to occur in the inert gas layer, and it is difficult to make the nozzle compact because the hole pitch of the nozzle must be increased. .. In the wet spinning method in which the nozzle surface is in direct contact with the solidifying bath, the solidifying bath permeates immediately after discharge from the nozzle and solidifies immediately, so that the hole pitch of the nozzle can be made small, and therefore, it can be made compact even with many holes. Among the wet spinning methods, the upstream wet spinning method is most commonly used for the production of PVA-based fibers, has a large amount of accumulated technology, and is the most industrially easy spinning method.
【００１６】固化浴としては、ＰＶＡ系ポリマーに対し
て凝固能のある有機溶媒を用いる。芒硝などの脱水性塩
類水溶液を固化浴に用いると、固化糸の表面が優先的に
脱水され、固化糸内部の脱水が阻害され断面方向に不均
一な構造すなわちスキン−コア構造となるため、延伸性
がわるくなり、高強度なＰＶＡ系繊維を得ることができ
ない。ＰＶＡ系ポリマーに対して凝固能を有する有機溶
媒としては、例えばメタノール、エタノールなどのアル
コール類、アセトン、メチルエチルケトンなどのケトン
類などがあり、特別な限定はないが、中でも凝固能のバ
ランス及びコストの点でメタノールが好ましい。As the solidifying bath, an organic solvent having a coagulating ability with respect to the PVA polymer is used. When an aqueous solution of dehydrating salt such as Glauber's salt is used for the solidifying bath, the surface of the solidified yarn is dehydrated preferentially, the dehydration inside the solidified yarn is inhibited, and a non-uniform structure in the cross-sectional direction, that is, a skin-core structure, is drawn. The property becomes poor and it is not possible to obtain a high-strength PVA-based fiber. Examples of the organic solvent having a coagulability with respect to the PVA-based polymer include alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, and there is no particular limitation. From the viewpoint, methanol is preferable.
【００１７】本発明においては固化浴中に原液溶媒を５
〜７０％含有することが好ましい。原液溶媒の含有量
は、固化浴として用いる有機溶媒の種類や固化浴温度な
どによって異なるが、５％未満であるとノズルより吐出
直後にあまりにも固化が急激に起こり、不均一な固化糸
となり易い。一方７０％を越えると固化速度が遅過ぎて
硬着し易くなる。固化浴中の原液溶媒の含有量が１０〜
５０重量％であるとより好ましく、１５〜４５％である
とさらに好ましい。In the present invention, the stock solution solvent is added to the solidification bath at 5%.
˜70% is preferable. The content of the stock solution solvent varies depending on the type of the organic solvent used as the solidification bath and the solidification bath temperature, but if it is less than 5%, solidification will occur too rapidly immediately after being discharged from the nozzle, and a nonuniform solidified yarn is likely to be formed. .. On the other hand, when it exceeds 70%, the solidification rate is too slow, and the material tends to be hardened. The content of the stock solution solvent in the solidification bath is 10
It is more preferably 50% by weight and even more preferably 15 to 45%.
【００１８】固化浴の温度が２０℃を越えると、固化糸
は相分離が進んだ状態となりボイドが多く、不透明化
し、不均一構造となり、高強度繊維を得ることは困難と
なる。固化浴の温度が１０℃以下であるのがより好まし
く、５℃以下であると、透明な均一構造の固化糸が得ら
れるのでさらに好ましい。但し固化浴の温度があまりに
低いとノズルより吐出される紡糸原液が凍結することが
あるので、原液に凍結防止剤を添加するなどの配慮が必
要である。When the temperature of the solidifying bath exceeds 20 ° C., the solidified yarn is in a state of advanced phase separation, has many voids, becomes opaque and has a non-uniform structure, and it becomes difficult to obtain high strength fibers. It is more preferable that the temperature of the solidifying bath is 10 ° C. or lower, and if the temperature is 5 ° C. or lower, a solidified yarn having a transparent uniform structure can be obtained, and it is further preferable. However, if the temperature of the solidification bath is too low, the spinning dope discharged from the nozzle may freeze, so it is necessary to consider adding an antifreezing agent to the dope.
【００１９】本発明においては、固化浴中で形成された
固化糸を１０ｍ／分以上の第１ゴデットローラー速度で
引き取る。１０ｍ／分未満では生産速度が小さく、工業
的生産するには高コストとなる。In the present invention, the solidified yarn formed in the solidifying bath is taken up at a first godet roller speed of 10 m / min or more. If it is less than 10 m / min, the production speed is low and the cost is high for industrial production.
【００２０】次に第１ゴデットローラー部での固化糸に
含まれる溶媒残存率を２５〜８０％とすることが本発明
のポイントの１つである。本発明にいう第１ゴデットロ
ーラーとは、原液がノズルより吐出されて固化浴中で固
化糸となり、その固化糸が初めて接触する固体であり、
所定速度で回転している駆動ローラーや、固化糸との摩
擦により回転するアリーローラー、さらには固化糸の糸
道方向を変更するために用い、それ自体は動かない棒
状、Ｔ字状、スネーク状などのガイド類が包含される。
但し、固化糸に付着する固化液を除去するためにだけ用
いる所謂液切りガイドは本発明にいう第１ゴデットロー
ラーには包含されないものとする。Next, one of the points of the present invention is to set the residual solvent ratio of the solidified yarn in the first godet roller portion to 25 to 80%. The first godet roller referred to in the present invention is a solid discharged from a nozzle to become a solidified yarn in a solidifying bath, and the solidified yarn is the first solid to come into contact with the solidified yarn.
It is used to change the direction of the driving path of the drive roller that rotates at a predetermined speed, the friction roller that rotates due to friction with the solidified yarn, and the solidified yarn, and the rod shape, T-shape, and snake shape that does not move by itself. Guides such as are included.
However, the so-called liquid draining guide used only for removing the solidified liquid adhering to the solidified yarn is not included in the first godet roller according to the present invention.
【００２１】第１ゴデットローラー部での固化糸に含ま
れる溶媒残存率を２５〜８０％と高くすることは、第１
ゴデットローラー部までの原液溶媒の抽出を、固化糸が
形成される範囲内において、抑制することにより、固化
糸の構造を出来る限り均一とするというものであり、そ
の指標として第１ゴデットローラー部での固化糸に含ま
れる溶媒残存率に着目するものである。溶媒残存率は、
固化浴の原液溶媒含有量、温度及び滞留時間などによっ
て制御しうる。すなわち溶媒残存率を大きくするには、
固化浴の原液溶媒含有量を高くしたり、固化浴の温度を
下げたり、或いは固化浴中滞留時間を短くするため、固
化浴長を短くしたり或いは第１ゴデットローラー速度を
大きくしたりすればよい。溶媒残存率が８０％を越える
と固化が不十分となり、得られた固化糸が硬着したり、
極端には例えば固化浴の原液溶媒含有量を７５％とする
と正常な紡糸が困難となる。溶媒残存率が２５％未満で
は固化浴中での溶媒抽出が大き過ぎ強度の優れたＰＶＡ
系繊維を得ることができない。溶媒残存率が３０〜６０
％であるとさらに高強度繊維が得られ易い。Increasing the residual solvent ratio of the solidified yarn in the first godet roller portion to 25 to 80% is
By suppressing the extraction of the stock solution solvent to the godet roller portion within the range where the solidified yarn is formed, the structure of the solidified yarn is made as uniform as possible, and the first godet roller is used as an index thereof. It is intended to pay attention to the residual ratio of the solvent contained in the solidified yarn in part. Solvent residual rate is
It can be controlled by the solvent content of the stock solution of the solidification bath, the temperature, the residence time, and the like. That is, to increase the solvent residual rate,
Increase the stock solution solvent content of the solidification bath, lower the temperature of the solidification bath, or shorten the solidification bath length to shorten the residence time in the solidification bath or increase the speed of the first godet roller. Good. If the solvent residual ratio exceeds 80%, the solidification becomes insufficient, and the obtained solidified yarn is hard-fixed,
In an extreme case, for example, if the concentration of the stock solution solvent in the solidification bath is 75%, normal spinning becomes difficult. If the residual solvent ratio is less than 25%, the solvent extraction in the solidification bath is too large and the strength is excellent.
No fiber can be obtained. Solvent residual rate is 30-60
%, It is easier to obtain high strength fibers.
【００２２】なお本発明にいう第１ゴデットローラー部
での凝固糸に含まれる溶媒残存率は以下のようにして測
定したものである。まず第１ゴデットローラー部での固
化糸を、表面付着液を拭きとり２つ同じ時間サンプリン
グする。１つは原液溶媒、添加剤、固化浴をソックレー
抽出し、絶乾することによりＰＶＡ系ポリマー重量（Ａ
ｇ）を求める。他の１つは水に溶解し、ガスクロ分析す
ることにより原液溶媒の重量（Ｂｇ）を求める。これよ
り固化糸の原液溶媒含有量Ｂ／Ａ×１００（％／ＰＶ
Ａ）を算出する。一方原液中のＰＶＡ系ポリマーに対す
る溶媒の重量％を原液組成より計算しＣ（％／ＰＶＡ）
とすると、第１ゴデットローラー部での固化糸に含まれ
る溶媒残存率（％）は１００Ｂ／ＡＣで求めることがで
きる。The solvent residual ratio contained in the coagulated yarn in the first godet roller portion according to the present invention is measured as follows. First, the solidified yarn at the first godet roller portion is wiped off the surface-adhering liquid, and two samples are taken for the same time. One is to use Soxhlet extraction of the stock solution solvent, additives, and solidification bath, and dry it to dryness to obtain the weight of PVA-based polymer (A
g) is calculated. The other one is dissolved in water, and the weight (Bg) of the stock solution solvent is determined by gas chromatography analysis. From this, the undiluted solvent content of the solidified yarn B / A × 100 (% / PV
Calculate A). On the other hand, the weight% of the solvent to the PVA-based polymer in the stock solution was calculated from the composition of the stock solution to obtain C (% / PVA).
Then, the residual solvent ratio (%) contained in the solidified yarn in the first godet roller portion can be calculated as 100 B / AC.
【００２３】次に本発明では、固化浴中での固化糸の滞
留時間をＴ↓B、固化浴から大気に出て第１ゴデットロ
ーラーに接触するまでの固化浴上大気滞留時間をＴ↓A
とするとき、０．５Ｔ↓B≦Ｔ↓A≦１０Ｔ↓Bを満足す
るように紡糸することが重要なポイントである。第１ゴ
デットローラー速度が比較的小さい場合は、固化糸の溶
媒残存率を２５〜８０％の範囲に制御することにより、
ほぼ安定に高強度繊維が得られるが、第１ゴデットロー
ラー速度が１０ｍ／分以上と大きくなると、溶媒残存率
を２５〜８０％の範囲に制御しても、工程通過性が今一
歩で高強度繊維を安定に得ることが困難であるという事
態に直面した。そこでこの点について種々検討した結
果、固化浴を出てから第１ゴデットローラーに接触する
までの固化浴上大気滞留時間を固化浴中滞留時間の半分
〜１０倍とすれば、第１ゴデットローラーを高速として
も工程通過性及び強度とも安定化することを見出した。
固化浴上大気滞留時間が、固化浴上滞留時間の半分より
短いと工程通過性や強度が不安定となる。固化浴滞留時
間の１０倍より長いと、メタノールなどの揮発性の固化
浴の揮散量が多くなり好ましくない。Next, in the present invention, the residence time of the solidified yarn in the solidification bath is T ↓ B, and the atmospheric residence time on the solidification bath from the solidification bath to the atmosphere until it contacts the first godet roller is T ↓ B. A
In that case, it is an important point that spinning is performed so as to satisfy 0.5T ↓ B ≦ T ↓ A ≦ 10T ↓ B. When the first godet roller speed is relatively low, by controlling the solvent residual ratio of the solidified yarn in the range of 25 to 80%,
High-strength fiber can be obtained almost stably, but when the first godet roller speed is as high as 10 m / min or more, even if the solvent residual rate is controlled within the range of 25 to 80%, the process passability is still high. I faced a situation where it was difficult to obtain strong fibers stably. Therefore, as a result of various studies on this point, if the atmospheric residence time on the solidifying bath from the leaving of the solidifying bath to the contact with the first godet roller is set to be half to 10 times the residence time in the solidifying bath, the first godet It was found that the process passability and strength are stabilized even when the roller is operated at high speed.
If the atmospheric residence time on the solidifying bath is shorter than half the residence time on the solidifying bath, the process passability and strength become unstable. If it is longer than 10 times the residence time of the solidifying bath, the amount of volatilization of a volatile solidifying bath such as methanol increases, which is not preferable.
【００２４】何故固化浴上大気滞留時間が高速の場合に
重要となるかは不明であるが、高速の場合固化浴内での
原液溶媒の抽出が単糸間でバラツキ易く、このため工程
通過性や性能が不安定化するのに対し、固化浴〜第１ゴ
デットローラー間の大気滞留中は固化浴に浸漬されてい
ないため固化糸全体としての抽出は殆んど起こらないも
のの、固化糸に付着している固化浴を通じて固化単糸間
の溶媒含有量の均一化がなされるためと推測される。こ
の固化浴上大気滞留中における単糸溶媒抽出の均一化作
用が第１ゴデットローラーが高速になった際に有効に作
用する結果と推定される。Although it is not clear why the atmospheric residence time on the solidifying bath is high at a high speed, the extraction of the stock solution solvent in the solidifying bath tends to vary among the single yarns at a high speed, and thus the process passability is high. And the performance becomes unstable, while the solidified yarn is hardly immersed in the solidifying bath during the air residence between the solidifying bath and the first godet roller, the solidified yarn is hardly extracted, but It is presumed that this is because the solvent content between the solidified single yarns is made uniform through the solidifying bath attached. It is presumed that the uniformizing action of the single yarn solvent extraction during the residence in the air on the solidifying bath effectively acts when the first godet roller becomes high speed.
【００２５】第１ゴデットローラーに引き取られた固化
糸は、以下の工程に従って繊維化される。すなわち、凝
固能を有する有機溶媒よりなる抽出浴などにより固化糸
中の原液溶媒などを抽出洗滌し、次いで乾燥する。この
際第１ゴデットローラー直後より乾燥前に至る工程にお
いて１段あるいはより好ましくは２段以上の湿延伸を施
しておくと乾燥時の硬着を防止することができ好まし
い。湿延伸はローラーとローラーの間の大気中で延伸す
るローラー延伸とローラーとローラーの間の湿延伸浴中
で延伸する浴中延伸とがあり、通常両延伸法を併用する
ことが多い。好ましい湿延伸倍率は２．５〜５．５倍で
あり、３〜５倍であるとさらに好ましい。乾燥温度は４
０〜１５０℃が好ましく、７０〜１３０℃であると乾燥
効率、性能の点でもっと好ましい。さらに乾燥温度を多
段に上げていくことが好ましい。The solidified yarn taken up by the first godet roller is made into fibers according to the following steps. That is, the undiluted solution solvent in the solidified yarn is extracted and washed with an extraction bath made of an organic solvent having a coagulating ability, and then dried. At this time, it is preferable to perform wet stretching in one step or more preferably in two steps or more in the steps from immediately after the first godet roller to before drying, because it is possible to prevent sticking during drying. Wet stretching includes roller stretching in which air is stretched between the rollers and air, and in-bath stretching in a wet stretching bath between the rollers, and both stretching methods are often used in combination. The preferable wet stretch ratio is 2.5 to 5.5 times, and more preferably 3 to 5 times. Drying temperature is 4
0 to 150 ° C. is preferable, and 70 to 130 ° C. is more preferable in terms of drying efficiency and performance. Further, it is preferable to raise the drying temperature in multiple stages.
【００２６】次いで高温で熱延伸を施し、ＰＶＡ系ポリ
マーを配向結晶化させて高強度ＰＶＡ系繊維とする。熱
延伸温度は１４０〜２７０℃とする。さらに好ましくは
１５０〜２６５℃の間で熱延伸温度を多段に制御する。
特に重要な最終段の延伸は２２５〜２５５℃で行なうの
がよい。このとき湿延伸倍率も含めた全延伸倍率は従来
法では通常１６倍以上、より好ましくは１８倍以上とす
るが、本発明方法での特徴は、１２〜１８倍という比較
的低倍率延伸でも十分な強度を得ることができることで
ある。熱延伸は、熱風や輻射炉の如く気体を熱媒体とし
て繊維を昇温してもよいし、シリコン、ウッドメタルな
ど液体を熱媒体として繊維を昇温してもよいし、さらに
熱プレートに繊維を接触させて熱伝導により繊維を昇温
してもよい。また多段で熱延伸を行なってもよい。さら
に必要に応じて熱処理や熱収縮を施してもよい。Then, hot drawing is performed at a high temperature to orient and crystallize the PVA-based polymer to obtain a high-strength PVA-based fiber. The hot stretching temperature is 140 to 270 ° C. More preferably, the hot stretching temperature is controlled in multiple stages between 150 and 265 ° C.
The particularly important final stage stretching is preferably performed at 225 to 255 ° C. At this time, the total stretching ratio including the wet stretching ratio is usually 16 times or more in the conventional method, and more preferably 18 times or more, but the characteristic of the method of the present invention is that even a relatively low stretching ratio of 12 to 18 times is sufficient. It is possible to obtain various strengths. In the hot stretching, the temperature of the fiber may be raised by using a gas as a heat medium such as hot air or a radiant furnace, the temperature of the fiber may be raised by using a liquid such as silicon or wood metal as the heat medium, and the fiber may be further placed on a heat plate. May be brought into contact with each other to heat the fiber by heat conduction. Further, hot drawing may be performed in multiple stages. Further, heat treatment or heat shrinkage may be performed if necessary.
【００２７】何故に第１ゴデットローラー部での固化糸
の溶媒残存率が繊維性能に大きな影響を与えるかは不明
であるが、溶媒が抽出される際の張力が重要な因子と推
測される。すなわち第１ゴデットローラー部までは前記
の如く、バスドラフトは１．０未満であり、いわゆるバ
ックドラフト状態にあり、極めて固化糸がうけている張
力は低い。本発明紡糸法では微結晶によるジャンクショ
ンポイントの形成により固化が惹起すると考えられる
が、固化後溶媒抽出されるが、この際微結晶の生成と成
長及び相分離が同時並行的に進行するが、固化糸の張力
が低いと相分離が優先的に進行し、不透明な固化糸とな
り易い。従って低張力の第１ゴデットローラー部までは
相分離を制御するため、固化後は溶媒抽出を抑制すべき
と考えられる。一方第１ゴデットローラー以降の工程は
少なくとも定長か延伸がかかっており、糸がうける張力
は飛躍的に高くなる。高張力下では相分離が著しく抑制
されるため溶媒抽出をうけても相分離が進行せず、固化
時に形成された均一な構造すなわちジャンクションポイ
ントが均一にしかも多く存在しているため、全延伸倍率
が低くても実効延伸が効き、ＰＶＡ系ポリマーの分子鎖
が高配向となり、高強度化につながっていると推察され
る。It is unclear why the solvent residual ratio of the solidified yarn in the first godet roller part has a great influence on the fiber performance, but it is presumed that the tension when the solvent is extracted is an important factor. .. That is, up to the first godet roller portion, the bus draft is less than 1.0, as described above, in a so-called back draft state, and the tension applied to the solidified yarn is extremely low. In the spinning method of the present invention, it is considered that solidification is caused by the formation of junction points due to the microcrystals, but it is extracted with a solvent after solidification. At this time, the formation and growth of the microcrystals and the phase separation proceed concurrently, but the solidification occurs. If the tension of the yarn is low, phase separation will proceed preferentially, and an opaque solidified yarn is likely to be formed. Therefore, since the phase separation is controlled up to the first godet roller portion having a low tension, it is considered that the solvent extraction should be suppressed after the solidification. On the other hand, the steps after the first godet roller are at least fixed length or stretched, so that the tension received by the yarn is significantly increased. Since the phase separation is significantly suppressed under high tension, the phase separation does not proceed even when subjected to solvent extraction, and the uniform structure formed at the time of solidification, that is, the number of junction points are even and many, so the total draw ratio It is presumed that effective stretching is effective even when the value is low, and the molecular chains of the PVA-based polymer are highly oriented, leading to higher strength.
【００２８】以上の如く、固化浴上大気滞留時間を特定
範囲とし、さらに第１ゴデットローラー部での固化糸の
溶媒残存率を特定範囲に制御することにより、第１ゴデ
ットローラー速度が高くても、均質な原糸を得ることが
でき、全延伸倍率が比較的低くても強度の優れたＰＶＡ
系繊維を安定にかつ再現性よく製造することが実現でき
たものである。As described above, the first godet roller speed is increased by controlling the residence time on the solidifying bath in the atmosphere to a specific range and further controlling the solvent residual ratio of the solidified yarn in the first godet roller part to a specific range. However, a uniform raw yarn can be obtained, and PVA with excellent strength even if the total draw ratio is relatively low.
It was possible to realize stable and reproducible production of system fibers.
【００２９】[0029]
【実施例】以下実施例により具体的に説明するが、本発
明はこれら実施例に限定されるものではない。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
【００３０】実施例１ 粘度平均重合度４２００、ケン化度９９．９モル％のＰ
ＶＡを９重量％となるようＤＭＳＯに添加し、さらに凍
結防止剤としてメタノールを２％添加し、８０℃にて窒
素雰囲気下８時間溶解し、孔径０．１７ｍｍ、孔数４０
０のノズルより１℃のメタノール／ＤＭＳＯ＝７５／２
５よりなる固化浴中に紡糸筒長１．０ｍ、第１ゴデット
ローラー速度１２ｍ／分、バスドラフト０．２で流上紡
糸した。この時第１ゴデットローラーを紡糸筒の１．５
ｍ上すなわちノズル面と第１ゴデットローラーの距離を
２．５ｍとして、紡糸筒上大気滞留時間Ｔ↓Aは紡糸筒
滞留時間Ｔ↓Bの１．５倍とした。またこの時の第１ゴ
デットローラー部での固化糸の溶媒残存率は４０％であ
った。Example 1 P having a viscosity average polymerization degree of 4200 and a saponification degree of 99.9 mol%
VA was added to DMSO so as to be 9% by weight, 2% of methanol was further added as an antifreezing agent, and the mixture was melted at 80 ° C. for 8 hours in a nitrogen atmosphere to have a pore diameter of 0.17 mm and a pore number of 40
Nozzle of 0 from 1 ℃ methanol / DMSO = 75/2
In a solidifying bath of No. 5, the spinning cylinder length was 1.0 m, the first godet roller speed was 12 m / min, and the up-spinning was performed at a bath draft of 0.2. At this time, set the first godet roller to 1.5 in the spinning cylinder.
m, that is, the distance between the nozzle surface and the first godet roller was 2.5 m, and the atmospheric residence time T ↓ A on the spinning cylinder was 1.5 times the residence time T ↓ B. At this time, the residual solvent ratio of the solidified yarn in the first godet roller portion was 40%.
【００３１】得られた固化糸をメタノール浴に浸漬し、
ＤＭＳＯを抽出するとともに４．２倍の湿延伸を施こ
し、１００℃熱風で乾燥した。次いで第１炉１７０℃、
第２炉２４０℃の熱風炉内で全延伸倍率が１５．５倍と
なるように熱延伸し、延伸糸２ｋｇを得た。紡糸及び延
伸を通じて断糸は全くなく、ローラー捲付きも殆んどな
く、工程安定性は良好であった。また得られた繊維のヤ
ーン強度は１９．７ｇ／ｄと優れていた。また毛羽は殆
んどなかった。The obtained solidified yarn is immersed in a methanol bath,
DMSO was extracted, wet stretched 4.2 times, and dried with hot air at 100 ° C. Then the first furnace 170 ℃,
In a hot air oven at 240 ° C. in a second furnace, hot drawing was performed so that the total draw ratio was 15.5 times, and 2 kg of drawn yarn was obtained. There was no yarn breakage during spinning and drawing, there was almost no roller winding, and the process stability was good. Further, the yarn strength of the obtained fiber was excellent at 19.7 g / d. Also, there was almost no fuzz.
【００３２】比較例１ 実施例１で用いた紡糸原液を紡糸筒長２．０ｍ、第１ゴ
デットローラー速度３ｍ／分、バスドラフト０．２で実
施例１と同様に流上紡糸した。このときの溶媒残存率は
１８％であった。なおノズル面と第１ゴデットローラー
の距離は実施例１と同様に２．５ｍとしたので、Ｔ↓A
／Ｔ↓B＝０．２５倍であった、以後、実施例１と同様
の操作を実施し、全延伸倍率は２５倍が可能であった
が、ヤーン強度は１８．５ｇ／ｄと実施例１より低かっ
た。また延伸時ローラー捲付が時折みられ、工程安定性
の面でも不十分であった。Comparative Example 1 The spinning dope used in Example 1 was subjected to up-spinning in the same manner as in Example 1 with a spinning cylinder length of 2.0 m, a first godet roller speed of 3 m / min and a bath draft of 0.2. The residual solvent ratio at this time was 18%. The distance between the nozzle surface and the first godet roller was 2.5 m as in Example 1, so T ↓ A
/T↓B=0.25 times, the same operation as in Example 1 was performed thereafter, and the total draw ratio was 25 times, but the yarn strength was 18.5 g / d. It was lower than 1. In addition, roller winding was occasionally seen during stretching, and the process stability was insufficient.
【００３３】比較例２ ノズル面と第１ゴデットローラーの距離を１．２ｍとす
る以外は全て実施例１と同様に紡糸、延伸を実施した。
この時Ｔ↓A／Ｔ↓B＝０．２倍であった。また第１ゴデ
ットローラー部での固化糸の溶媒残存率は４２％であっ
た。得られたヤーンの強度は１９．５ｇ／ｄと実施例１
と遜色なかったが、延伸時に延伸糸２ｋｇ当たり２回断
糸し、ローラー捲付きが時々みられ、従って捲き上が延
伸糸には毛羽がみられた。Comparative Example 2 Spinning and drawing were carried out in the same manner as in Example 1 except that the distance between the nozzle surface and the first godet roller was 1.2 m.
At this time, T ↓ A / T ↓ B was 0.2 times. The solvent residual rate of the solidified yarn in the first godet roller part was 42%. The strength of the obtained yarn was 19.5 g / d, and Example 1 was used.
However, the yarn was broken twice per 2 kg of the drawn yarn at the time of drawing, and roller winding was occasionally observed. Therefore, fluff was observed in the drawn yarn on the winding top.
【００３４】実施例２ 粘度平均重合度９０００、ケン化度９９．８モル％のＰ
ＶＡを６％となるようＤＭＳＯに添加し、さらに水を
１．５％添加し、９０℃にて窒素雰囲気下１２時間溶解
し、孔径０．１７ｍｍ、孔数６００のノズルより−１℃
のメタノールＤＭＳＯ＝８３／１７よりなる固化浴中に
紡糸筒長１．２ｍ、第１ゴデットローラー速度１５ｍ／
分、バスドラフト０．２で流上紡糸した。この時ノズル
面と第１ゴデットローラーの距離を３．６ｍとし、Ｔ↓
A／Ｔ↓B＝２．０倍とした。また第１ゴデットローラー
部での固化糸の溶媒残存率は５０％であった。得られた
固化糸をメタノール浴に浸漬し、ＤＭＳＯを抽出すると
ともに３．８倍の湿延伸を施こし、１００℃熱風で乾燥
した。次いで第１炉１８０℃、第２炉２４８℃の熱風炉
内で全延伸倍率が１５．８倍となるよう延伸した。得ら
れたヤーン強度は２１．７ｇ／ｄと高強度であった。ま
た延伸時の断糸はなく、ローラー捲付きや毛羽も殆どな
く、工程通過性も良好であった。Example 2 P having a viscosity average polymerization degree of 9000 and a saponification degree of 99.8 mol%
VA was added to DMSO to be 6%, water was further added to 1.5%, and the mixture was dissolved at 90 ° C. for 12 hours in a nitrogen atmosphere.
Of methanol DMSO = 83/17 in a solidifying bath with a spinning cylinder length of 1.2 m and a first godet roller speed of 15 m /
Min, and spin-up spinning was performed with a bath draft of 0.2. At this time, the distance between the nozzle surface and the first godet roller is 3.6 m, and T ↓
A / T ↓ B = 2.0 times. The solvent residual rate of the solidified yarn in the first godet roller portion was 50%. The obtained solidified yarn was dipped in a methanol bath to extract DMSO, subjected to 3.8 times wet drawing, and dried with hot air at 100 ° C. Then, it was stretched in a hot air oven at 180 ° C. in the first furnace and 248 ° C. in the second furnace so that the total stretching ratio was 15.8 times. The obtained yarn strength was as high as 21.7 g / d. In addition, there was no yarn breakage during drawing, there was almost no roller winding or fluff, and the process passability was good.
【００３５】[0035]
【発明の効果】従来の凝固紡糸による高強力ＰＶＡ繊維
の製造法では、固化浴中で急速固化、溶媒緩徐抽出が有
効と考えられてきたので、固化浴中での滞留時間が長
く、低張力で相分離が行なわれていたため、高強度ＰＶ
Ａ繊維の製造が困難であった。また第１ゴデットローラ
ー速度を大きくすると、延伸の安定性が悪化し、断糸、
捲付き、毛羽の発生がみられた。これに対し、本発明で
は紡糸筒長、第１ゴデットローラー速度、固化浴組成、
固化浴温度を制御することにより、第１ゴデットローラ
ー部での固化糸の溶媒残存率を高めに設定し、かつ紡糸
筒上がりの固化糸を大気にある程度滞留させることによ
り溶媒残存率の単糸間のバラツキを小さくすることによ
り、高強度のＰＶＡ繊維を高速でも安定に製造すること
を可能にしたものである。従って本発明により得られた
強度の優れたＰＶＡ繊維はパラ系アラミド繊維など他の
高強度繊維や従来のＰＶＡ繊維に比べてコストパーフォ
ーマンスに優れており、自動車用タイヤやホースなどの
ゴム資材分野やＦＲＣ及びＦＲＰなどの補強材分野など
に広く有効に用いることができる。In the conventional method for producing high-strength PVA fibers by coagulation spinning, rapid solidification in the solidification bath and slow solvent extraction have been considered effective, so that the residence time in the solidification bath is long and the tension is low. Since the phase separation was performed in, high strength PV
It was difficult to produce the A fiber. When the speed of the first godet roller is increased, the stability of drawing is deteriorated,
There was winding and fluffing. On the other hand, in the present invention, the spinning cylinder length, the first godet roller speed, the solidifying bath composition,
By controlling the temperature of the solidifying bath, the solvent residual ratio of the solidified yarn in the first godet roller portion is set to be high, and the solidified yarn rising from the spinning cylinder is retained in the air to some extent, so that the single yarn having the solvent residual ratio is set. By reducing the variation between them, it is possible to stably produce high-strength PVA fibers even at high speed. Therefore, the PVA fiber having excellent strength obtained by the present invention is superior in cost performance to other high-strength fibers such as para-aramid fiber and the conventional PVA fiber, and is used for rubber materials such as automobile tires and hoses. It can be widely and effectively used in the field of reinforcing materials such as and FRC and FRP.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小林 悟 岡山県倉敷市酒津1621番地 株式会社クラ レ内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satoru Kobayashi 1621 Sakata, Kurashiki City, Okayama Prefecture Kuraray Co., Ltd.
Claims (1)
ルアルコール系ポリマーを有機溶媒に溶解して得られる
紡糸原液を凝固能を有する有機溶媒系の固化浴中にバス
ドラフト１未満の状態で押し出し、形成された固化糸を
１０ｍ／分以上の第１ゴデットローラー速度で引き取る
流上湿式紡糸において、固化糸の固化浴中での滞留時間
をＴ↓B、固化浴上から第１ゴデットローラーに接触す
るまでの大気滞留時間をＴ↓Aとするとき、０．５Ｔ↓B
≦Ｔ↓A≦１０Ｔ↓Bを満足し、かつ第１ゴデットローラ
ー部での固化糸の溶媒残存率を原液溶媒量に対し２５〜
８０％とすることを特徴とするポリビニルアルコール系
繊維の製法。1. A spinning stock solution obtained by dissolving a polyvinyl alcohol polymer having a viscosity average degree of polymerization of 1500 or more in an organic solvent is extruded into a solidification bath of an organic solvent system having a coagulating ability in a state of a bath draft of less than 1. In the run-up wet spinning in which the solidified yarn is drawn at a first godet roller speed of 10 m / min or more, the residence time of the solidified yarn in the solidifying bath is T ↓ B, and the first godet roller is contacted from above the solidifying bath. Assuming that the atmospheric residence time until T is T ↓ A, 0.5T ↓ B
≦ T ↓ A ≦ 10T ↓ B is satisfied, and the solvent residual ratio of the solidified yarn at the first godet roller portion is 25 to the stock solution solvent amount.
A method for producing a polyvinyl alcohol fiber, which comprises 80%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4087984A JP3021944B2 (en) | 1992-03-11 | 1992-03-11 | Manufacturing method of polyvinyl alcohol fiber with excellent strength |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4087984A JP3021944B2 (en) | 1992-03-11 | 1992-03-11 | Manufacturing method of polyvinyl alcohol fiber with excellent strength |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05263312A true JPH05263312A (en) | 1993-10-12 |
| JP3021944B2 JP3021944B2 (en) | 2000-03-15 |
Family
ID=13930086
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4087984A Expired - Fee Related JP3021944B2 (en) | 1992-03-11 | 1992-03-11 | Manufacturing method of polyvinyl alcohol fiber with excellent strength |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3021944B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012165476A1 (en) * | 2011-06-01 | 2012-12-06 | スパイバー株式会社 | Artificial polypeptide fiber and method for producing same |
| US9689089B2 (en) | 2012-06-28 | 2017-06-27 | Spiber Inc. | Solution-dyed protein fiber and method for producing same |
| US10975206B2 (en) | 2015-04-09 | 2021-04-13 | Spiber Inc. | Polar solvent solution and production method thereof |
| US11668024B2 (en) | 2015-04-09 | 2023-06-06 | Spiber, Inc. | Polar solvent solution and production method thereof |
-
1992
- 1992-03-11 JP JP4087984A patent/JP3021944B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012165476A1 (en) * | 2011-06-01 | 2012-12-06 | スパイバー株式会社 | Artificial polypeptide fiber and method for producing same |
| JP5540154B2 (en) * | 2011-06-01 | 2014-07-02 | スパイバー株式会社 | Artificial polypeptide fiber |
| JP2014129639A (en) * | 2011-06-01 | 2014-07-10 | Spiber Inc | Method for manufacturing artificial polypeptide fiber |
| JPWO2012165476A1 (en) * | 2011-06-01 | 2015-02-23 | スパイバー株式会社 | Artificial polypeptide fiber |
| US9617315B2 (en) | 2011-06-01 | 2017-04-11 | Spiber Inc. | Artificial polypeptide fiber and method for producing the same |
| US9689089B2 (en) | 2012-06-28 | 2017-06-27 | Spiber Inc. | Solution-dyed protein fiber and method for producing same |
| US10975206B2 (en) | 2015-04-09 | 2021-04-13 | Spiber Inc. | Polar solvent solution and production method thereof |
| US11668024B2 (en) | 2015-04-09 | 2023-06-06 | Spiber, Inc. | Polar solvent solution and production method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3021944B2 (en) | 2000-03-15 |
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