JPH02300308A - Polyvinyl alcohol fiber and production thereof - Google Patents
Polyvinyl alcohol fiber and production thereofInfo
- Publication number
- JPH02300308A JPH02300308A JP12203089A JP12203089A JPH02300308A JP H02300308 A JPH02300308 A JP H02300308A JP 12203089 A JP12203089 A JP 12203089A JP 12203089 A JP12203089 A JP 12203089A JP H02300308 A JPH02300308 A JP H02300308A
- Authority
- JP
- Japan
- Prior art keywords
- spinning
- pva
- fibers
- spinneret
- polyvinyl alcohol
- 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.)
- Pending
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 59
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims description 55
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims description 55
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 238000009987 spinning Methods 0.000 claims abstract description 37
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 18
- 238000002166 wet spinning Methods 0.000 claims abstract description 17
- 238000000578 dry spinning Methods 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 23
- 239000011550 stock solution Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000004568 cement Substances 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000012770 industrial material Substances 0.000 description 5
- -1 Polyethylene Polymers 0.000 description 4
- 238000001891 gel spinning Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241001474374 Blennius Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- 229930091051 Arenine Natural products 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はポリビニルアルコール（以下、ＰＶＡと略記す
る。）繊維及びその製造法に係わり、さらに詳しくは高
強度・高初期弾性率を有するＰＶＡ繊維及びこのＰＶＡ
繊維を生産性よく製造する方法に関するものである。Detailed Description of the Invention (Industrial Application Field) The present invention relates to polyvinyl alcohol (hereinafter abbreviated as PVA) fibers and a method for producing the same, and more specifically relates to PVA fibers having high strength and high initial modulus. and this PVA
The present invention relates to a method for manufacturing fibers with high productivity.
（従来の技術）
最近、超高分子量ポリマー溶液をいわゆるゲル紡糸し、
得られた未延伸糸を高倍率で延伸することにより、高強
度・高初期弾性率繊維を得る方法が開発され、注目を浴
びている。(Prior art) Recently, ultra-high molecular weight polymer solutions have been subjected to so-called gel spinning.
A method for obtaining fibers with high strength and high initial elastic modulus by drawing the obtained undrawn yarn at a high magnification has been developed and is attracting attention.
ゲル紡糸技術を適用したポリエチレン繊維は。Polyethylene fibers made using gel spinning technology.
アラミド繊維を超える強度、初期弾性率を有しており、
すでに実用段階に入ろうとしている。しかしながら、ポ
リエチレン繊維は融点が低いため。It has strength and initial elastic modulus exceeding that of aramid fiber,
It is already entering the practical stage. However, since polyethylene fibers have a low melting point.
耐熱性が劣るという欠点を有しており、そのため。It has the disadvantage of poor heat resistance.
産業資材用途への拡大が阻まれている。Expansion into industrial material applications is being hindered.
ＰＶＡ繊維は汎用繊維中１強度、初期弾性率の点で優れ
ており、耐熱性においても２３０〜２４０℃以上の融点
を有しているので産業資材用途において極めて有用であ
る。PVA fibers are superior among general-purpose fibers in terms of strength and initial elastic modulus, and also have heat resistance with a melting point of 230 to 240°C or higher, making them extremely useful in industrial material applications.
従来、ＰＶＡ繊維の強度と初期弾性率を改善する方法に
関して、多くの提案がなされている。例えば、特開昭５
９−１３０３１４号公報には１分子量５０万以上の超高
重合度ＰＶＡのグリセリン溶液をゲル紡糸し、得られた
未延伸糸を２０倍程度延伸する方法が開示されている。Conventionally, many proposals have been made regarding methods for improving the strength and initial elastic modulus of PVA fibers. For example,
No. 9-130314 discloses a method in which a glycerin solution of ultra-high polymerization degree PVA having a molecular weight of 500,000 or more is gel-spun, and the resulting undrawn yarn is stretched approximately 20 times.
しかしながら、この方法では、超高重合度ＰＶＡの商業
的な入手が困難であるばかりか、このような超高重合度
ＰＶＡは、溶媒に溶解した場合の溶液粘度が高くなりす
ぎるので紡糸性が悪く、紡糸性をよくするためにはポリ
マー濃度を低くする必要があるので、生産性が低・とい
う欠点がある。However, with this method, not only is it difficult to commercially obtain ultra-high polymerization degree PVA, but also such ultra-high polymerization degree PVA has poor spinnability because the solution viscosity becomes too high when dissolved in a solvent. However, in order to improve spinnability, it is necessary to lower the polymer concentration, which has the disadvantage of low productivity.
また、特開昭６０−１２６３１２号公報や特開昭６１−
１０８７１１号公報、特開昭６１−２１５７１１号公報
には９重合度１５００以上のＰＶＡをジメチルスルホキ
シド（以下、ＤＭＳＯと略記する。）、あるいはグリセ
リンに溶解した紡糸原液を、下式で定義される紡糸ドラ
フトが０．０５〜１．０となるように乾・湿式紡糸、あ
るいはゲル紡糸し、得られた未延伸糸を２０倍以上延伸
する方法が開示されている。Also, JP-A-60-126312 and JP-A-61-
No. 108711 and Japanese Unexamined Patent Publication No. 61-215711 disclose that a spinning stock solution in which PVA with a degree of polymerization of 1500 or more is dissolved in dimethyl sulfoxide (hereinafter abbreviated as DMSO) or glycerin is used for spinning defined by the following formula. A method is disclosed in which dry/wet spinning or gel spinning is performed so that the draft is 0.05 to 1.0, and the resulting undrawn yarn is stretched 20 times or more.
紡糸ドラフト＝ＶＩ／Ｖ。Spinning draft = VI/V.
（ただし、Ｖｏは紡糸口金から吐出されるときの吐出糸
条の線速度＋ Ｖ ｌは紡糸引取り速度である。）しか
しながら、これらの方法では、吐出線速度を上げて紡糸
ドラフトを１以下とするために吐出孔の直径を０．０８
ｍｍというような極めて細いものとしなければならず、
紡糸口金の製作が難しいばかりか、単糸繊度が１０デニ
ール以下の細デニールの繊維しか得られない。事実、上
記公報（特開昭６１−２１５７１１号公報）に記載され
ているように、高強度・高初期弾性率ＰＶＡ繊維とする
ためには単糸繊度を５デニール以下にとどめることが必
須と考えられており、商業的に人手可能な重合度を有す
るＰＶＡから製造された。単糸繊度が１０デニール以上
の高強度・高初期弾性率ＰＶＡ繊維は、従来全く知られ
ていない。(However, Vo is the linear velocity of the discharged yarn when it is discharged from the spinneret + V l is the spinning take-off speed.) However, in these methods, the spinning draft cannot be reduced to 1 or less by increasing the discharge linear velocity. The diameter of the discharge hole is set to 0.08
It must be extremely thin, such as mm.
Not only is it difficult to manufacture a spinneret, but only fine denier fibers with a single filament fineness of 10 denier or less can be obtained. In fact, as stated in the above publication (Japanese Unexamined Patent Publication No. 61-215711), it is considered essential to keep the single yarn fineness to 5 denier or less in order to obtain a PVA fiber with high strength and high initial elastic modulus. manufactured from PVA with a commercially acceptable degree of polymerization. High-strength, high-initial-modulus PVA fibers with a single fiber fineness of 10 deniers or more have never been known.
しかしながら、単糸繊度が１０デニール以上の高強度・
高初期弾性率ＰＶＡ繊維は、特に次の理由で市場から強
く要望されている。However, high strength fibers with single yarn fineness of 10 denier or more
High initial modulus PVA fibers are strongly desired by the market, particularly for the following reasons.
すなわち、セメントやコンクリート補強用として従来使
用されていたアスベストは発ガン性があることが判った
ため９代わりにＰＶＡ繊維が使用されるようになってき
た。しかしながら、現在使用されている単糸繊度がｌＯ
デニール未満の繊維は糸径が小さいため、そのままでは
分散性が悪く。That is, asbestos, which was conventionally used for reinforcing cement and concrete, was found to be carcinogenic, so PVA fibers began to be used instead. However, the single yarn fineness currently used is 1O
Fibers with a diameter less than denier have a small diameter, so they have poor dispersibility as they are.
このため、フィラメントを集束してカットすることによ
り２分散性をよくしているが、セメントやコンクリート
と調合する際の分散性は依然として悪いという欠点があ
る。For this reason, the two-dispersibility is improved by cutting the filaments in a bundle, but there is still a drawback that the dispersibility when mixed with cement or concrete is still poor.
単糸繊度が１０デニール以上であれば、そのままでもセ
メント等と調合する際の分散性がよいので集束処理が不
要であり１分散性の向上と低コスト化を図ることが可能
となるからである。If the single fiber fineness is 10 denier or more, the dispersibility is good when blended with cement etc. even as it is, so no bundling treatment is necessary, making it possible to improve the dispersibility and reduce costs. .
（発明が解決しようとする課題）
上述したように、高強度・高初期弾性率を有するＰＶＡ
繊維の製造法は種々提案されているが。(Problem to be solved by the invention) As mentioned above, PVA having high strength and high initial elastic modulus
Various methods for producing fibers have been proposed.
前記の超高重合度ＰＶＡポリマーを用いる方法では、ポ
リマーの商業的な入手が困難であり、コスト的にも不利
である。In the method using the ultra-high polymerization degree PVA polymer, it is difficult to obtain the polymer commercially, and it is disadvantageous in terms of cost.
また、前記の特開昭６０−１２６３１２号公報等で開示
された。ＰＶＡ−ＤＭＳＯ溶液、あるいはＰＶＡ−グリ
セリン溶液を乾・湿式紡糸、あるいはゲル紡糸し、得ら
れた未延伸糸を２０倍以上延伸する方法では、１０デニ
ール未満の細デニールの繊維しか得られず、市場の要望
が多い単糸繊度が１０デニール以上の高強度・高初期弾
性率ＰＶＡ繊維を提供することができなかった。It was also disclosed in the above-mentioned Japanese Patent Application Laid-open No. 126312/1983. In the method of dry/wet spinning or gel spinning a PVA-DMSO solution or PVA-glycerin solution and stretching the resulting undrawn yarn by 20 times or more, only fine denier fibers of less than 10 denier can be obtained, which is difficult to obtain on the market. It has not been possible to provide high strength and high initial elastic modulus PVA fibers with a single filament fineness of 10 denier or more, which is in high demand.
本発明の第１の課題は、商業的に入手可能な重合度を有
するＰＶＡからなり、高強度、高初期弾性率で、かつ、
単糸繊度が大きく、セメント等の補強用や耐候性を要求
される産業資材用途に好適なＰＶＡ繊維を提供すること
であり、また９本発明の第２の課題は、上記のＰＶＡ繊
維を生産性よく低コストで製造する方法を提供すること
である。The first object of the present invention is to be made of PVA having a commercially available degree of polymerization, with high strength and high initial modulus, and
It is an object of the present invention to provide a PVA fiber which has a large single yarn fineness and is suitable for reinforcing cement etc. and for industrial material applications requiring weather resistance. The object of the present invention is to provide a method for manufacturing the product efficiently and at low cost.
（課題を解決するための手段）
本発明者等はこのような現状に鑑み、商業的に入手可能
な重合度を有するＰＶＡを用いて上記課題を解決するた
めに鋭意検討した結果１本発明に到達した。(Means for Solving the Problems) In view of the current situation, the present inventors have conducted intensive studies to solve the above problems using commercially available PVA having a degree of polymerization, and as a result, they have developed the present invention. Reached.
すなわち２本発明は９次の構成を要旨とするものである
。In other words, the gist of the present invention is a nine-order configuration.
（１）重合度１５００以上、 ７０００以下のポリビニ
ルアルコールからなり、引張り強度が１３ｇ／ｄ以上、
初期弾性率が３００ｇ／ｄ以上であり、かつ、単糸繊度
が１０デニール以上、１００デニール未満であることを
特徴とするポリビニルアルコール繊維。(1) Made of polyvinyl alcohol with a degree of polymerization of 1500 or more and 7000 or less, with a tensile strength of 13 g/d or more,
A polyvinyl alcohol fiber having an initial elastic modulus of 300 g/d or more and a single fiber fineness of 10 denier or more and less than 100 denier.
（２）重合度１５００以上、 ７０００以下のポリビニ
ルアルコールを溶媒に溶解して調製した紡糸原液を、単
数又は複数の吐出孔を有する紡糸口金を用いて乾・湿式
紡糸し、得られた未延伸糸を延伸してポリビニルアルコ
ール繊維を製造するに際し、紡糸原液出口側に突出する
形状の吐出孔を有する紡糸口金を用いて乾・湿式紡糸す
ることを特徴とするポリビニルアルコール繊維の製造法
。(2) Undrawn yarn obtained by dry/wet spinning a spinning stock solution prepared by dissolving polyvinyl alcohol with a degree of polymerization of 1,500 or more and 7,000 or less in a solvent using a spinneret having one or more discharge holes. 1. A method for producing polyvinyl alcohol fibers, which comprises performing dry/wet spinning using a spinneret having a discharge hole protruding from the outlet side of a spinning solution when producing polyvinyl alcohol fibers by drawing the fibers.
以下１本発明の詳細な説明する。The present invention will be explained in detail below.
本発明の製造法で用いるＰＶＡの重合度は１５００以上
が必要であり、好ましくは３０００以上、さらに好まし
くは４５００以上であるが、上限としてはポリマーコス
トの面から、 ７０００以下である。重合度が１５００
よりも小さいと、得られる繊維の強度が１３ｇ／ｄより
小さくなり１本発明の目的を達成することができない。The degree of polymerization of PVA used in the production method of the present invention is required to be 1,500 or more, preferably 3,000 or more, more preferably 4,500 or more, but the upper limit is 7,000 or less from the viewpoint of polymer cost. Degree of polymerization is 1500
If it is smaller than 13g/d, the strength of the obtained fiber will be smaller than 13g/d, making it impossible to achieve the object of the present invention.
また、ＰＶＡのケン化度は９９％以上のものが好ましい
。Moreover, the degree of saponification of PVA is preferably 99% or more.
このようなＰＶＡを溶媒に溶解して紡糸原液を調製する
のであるが、溶媒としてはグリセリン。A spinning stock solution is prepared by dissolving such PVA in a solvent, and the solvent used is glycerin.
エチレングリコール、プロピレングリコール等の飽和脂
肪族多価アルコール、又はＤＭＳＯ，ジメチルホルムア
ミド、ジメチルイミダゾリジノン。Saturated aliphatic polyhydric alcohols such as ethylene glycol and propylene glycol, or DMSO, dimethylformamide, dimethylimidazolidinone.
水等及びこれらの混合物から選択すればよく、その内で
も特にＤＭＳＯ，水又はこれらの混合物が好適に用いら
れる。本発明においては、この溶媒にＰＶＡの耐熱剤、
顔料、架橋剤等を適宜混入して用いてもよい。It may be selected from water, etc. and mixtures thereof, and among these, DMSO, water, or mixtures thereof are particularly preferably used. In the present invention, this solvent includes a PVA heat resistant agent,
Pigments, crosslinking agents, etc. may be mixed in as appropriate.
紡糸原液中のＰＶＡ濃度は、２〜３５重量％の範囲に調
製するのが好ましい。濃度が２重量％未満になると曳糸
性が低下し、一方、３５重量％を超えると、未延伸糸の
延伸性が低下する傾向を示すので好ましくない。The PVA concentration in the spinning stock solution is preferably adjusted to a range of 2 to 35% by weight. If the concentration is less than 2% by weight, the spinnability will decrease, while if it exceeds 35% by weight, the drawability of the undrawn yarn will tend to decrease, which is not preferable.
本発明においては、上記の溶媒にＰＶＡを溶解して調整
した紡糸原液を単数、又は複数の吐出孔を有する紡糸口
金を用いて乾・湿式紡糸して未延伸糸を形成させるので
あるが、その際、第１図で示したように９例えば筒状細
管を埋め込んで、紡糸原液出口側に突出するように形成
した吐出孔１を有する紡糸口金を用いることが９本発明
の目的を達成するＬで極めて重要であり、吐出孔の突出
長は１〜２０ｍｍが好ましい。In the present invention, a spinning stock solution prepared by dissolving PVA in the above solvent is dry/wet-spun using a spinneret having one or more discharge holes to form an undrawn yarn. In this case, as shown in FIG. 1, it is possible to achieve the object of the present invention by using a spinneret having a discharge hole 1 in which, for example, a cylindrical thin tube is embedded and is formed to protrude toward the outlet side of the spinning dope. This is extremely important, and the protrusion length of the discharge hole is preferably 1 to 20 mm.
すなわち９通常の乾式紡糸あるいは湿式紡糸で用いられ
ている。第２図で示したような、吐出孔２が紡糸原液出
口側に突出しない紡糸口金を用いると、吐出孔出口で紡
糸原液が半球状となって紡糸口金に付着する現象が生じ
る。このような状態では紡糸の開始が困難であり、もし
仮に紡糸を開始できたとしても、得られる繊維は繊度斑
の大きいものとなり、側底実用に耐えるものではない。That is, it is used in normal dry spinning or wet spinning. When a spinneret as shown in FIG. 2 in which the discharge hole 2 does not protrude toward the spinning dope exit side is used, a phenomenon occurs in which the spinning dope becomes hemispherical at the outlet of the discharge hole and adheres to the spinneret. In such a state, it is difficult to start spinning, and even if spinning could be started, the resulting fibers would have large unevenness in fineness and would not be suitable for practical use on the sole.
このような現象は、紡糸孔の孔径を小さくして吐出線速
度を上げることによって防ぐことができるものの、ＰＶ
Ａの乾・湿式紡糸においては、溶媒の抽出が他の溶媒中
にゲル化糸条を通すことによって行なわれるので１通糸
速度を上げると糸条の受ける抵抗が大きくなることから
通糸速度は高々数１０ｍ／分迄しか上げられない。した
がって、ドラフトを小さくするために吐出線速度を上げ
ることにも一定の限界がある。また、吐出孔の孔径を小
さくすることは紡糸口金製作上の困難を増大させ、生産
設備のコストアップにもつながり不利である。さらに重
要なことは、吐出孔の孔径が小さくなるために、当然の
ことながら得られる繊維の繊度が小さくなることであり
、事実このような紡糸口金を用いる方法においては、単
糸繊度がｌＯデニール以上で、高強度・高初期弾性率を
有するＰＶＡｍ維は得られていない。Although this phenomenon can be prevented by reducing the diameter of the spinning hole and increasing the linear discharge speed,
In dry/wet spinning (A), the solvent is extracted by passing the gelled yarn through another solvent, so increasing the thread speed increases the resistance that the yarn receives, so the thread speed is It can only go up to several tens of meters per minute at most. Therefore, there is a certain limit to increasing the ejection linear velocity in order to reduce the draft. Further, reducing the diameter of the discharge hole is disadvantageous because it increases the difficulty in manufacturing the spinneret and increases the cost of production equipment. What is more important is that as the diameter of the discharge hole becomes smaller, the fineness of the resulting fibers naturally becomes smaller.In fact, in a method using such a spinneret, the single fiber fineness is 10 As described above, PVAm fibers having high strength and high initial elastic modulus have not been obtained.
ところが驚くべきことに、紡糸原液出口側に突出する形
状の吐出孔を有する紡糸口金を用いると。However, surprisingly, when a spinneret having a discharge hole protruding from the spinning dope exit side was used.
吐出線速度を下げても、吐出孔出口で紡糸原液が半球状
となって紡糸口金に付着することがなく。Even if the linear discharge speed is lowered, the spinning stock solution does not become hemispherical at the outlet of the discharge hole and adhere to the spinneret.
安定した紡糸が可能となるばかりか、従来実現しえなか
った単糸繊度が１０デニール以上で、高強度・高初期弾
性率を有するＰＶΔ繊維を得ることができるのである。Not only is it possible to perform stable spinning, but it is also possible to obtain PVΔ fibers with a single fiber fineness of 10 deniers or more, high strength, and high initial elastic modulus, which was previously unachievable.
なお１本発明で使用する紡糸口金としては、吐出孔が紡
糸原液出口側に突出するものであれば。Note that the spinneret used in the present invention is one in which a discharge hole projects toward the spinning dope exit side.
吐出孔を一体として形成したもの、筒状細管を埋め込ん
で形成したもの等いずれでもよいが、後者の方が次の理
由で−好ましい。Although the discharge hole may be formed integrally or the discharge hole may be formed by embedding a cylindrical thin tube, the latter is preferable for the following reason.
すなわち、吐出孔を筒状細管で形成すれば、長さ／直径
の値が大きい吐出孔が容易に得られ、前記の値が大きい
吐出孔を有する紡糸口金を用いれば、吐出孔中で紡糸原
液中のＰＶＡ分子鎖に十分な剪断力が与えられ、この剪
断力によりＰＶＡ分子鎖の絡み合いが解きほぐされ、絡
み合いの少ない未延伸系構造を形成することができるか
らである。That is, if the discharge hole is formed of a cylindrical thin tube, a discharge hole with a large length/diameter value can be easily obtained, and if a spinneret having a discharge hole with the above-mentioned large value is used, the spinning dope can be formed in the discharge hole. This is because sufficient shearing force is applied to the PVA molecular chains inside, and the shearing force disentangles the PVA molecular chains, forming an unstretched structure with less entanglement.
吐出された紡糸原液は、不活性雰囲気層を経て凝固浴中
に導かれ、凝固糸条が形成される。本発明においては、
糸条の均斉度を高めるために紡糸ドラフトは１〜ＩＯと
するのが好ましい。また、凝固浴としては、メタノール
、エタノール等のアルコールや、アセトン等のケトンを
用いることができるが、とりわけメタノールが好適に用
いられる。The discharged spinning stock solution is introduced into a coagulation bath through an inert atmosphere layer, and a coagulated thread is formed. In the present invention,
In order to improve the uniformity of the yarn, the spinning draft is preferably 1 to IO. Further, as the coagulation bath, alcohols such as methanol and ethanol, and ketones such as acetone can be used, and methanol is particularly preferably used.
乾・湿式紡糸して得られた未延伸糸は、一旦捲取るか又
は連続して延伸工程に供給し、延伸する。The undrawn yarn obtained by dry/wet spinning is once wound up or continuously supplied to a drawing step and drawn.
なお１本発明においては、乾・湿式紡糸工程と延伸工程
との間に、乾煙、油剤処理等必要ならばその他の工程を
適宜導入してもよい。Note that in the present invention, other processes such as dry smoke treatment, oil treatment, etc. may be appropriately introduced between the dry/wet spinning process and the stretching process, if necessary.
延伸方法としては９種々の方法を適用することができる
が１例えば、ヒートプレート等の加熱体に未延伸糸を接
触させながら延伸する方法、熱媒中で延伸する方法、誘
電加熱方式で延伸する方法等があげられる。これらの方
法では１段又は２段以上の多段で延伸することができる
が、２段取Ｊ−の多段で延伸するのが好ましい。また、
多段延伸する場合は、第ｎ段延伸と、第（ｎ＋１）段延
伸（ｎは１以上の整数）との間で水分付与、油剤付与等
を行なってもよい。There are nine different stretching methods that can be applied; for example, a method of stretching the undrawn yarn while it is in contact with a heating body such as a heat plate, a method of stretching in a heating medium, and a method of stretching using a dielectric heating method. Examples include methods. In these methods, stretching can be carried out in one stage or in multiple stages of two or more stages, but it is preferable to stretch in multiple stages of two stages J-. Also,
In the case of multistage stretching, moisture application, oil application, etc. may be performed between the nth stage stretching and the (n+1)th stage stretching (n is an integer of 1 or more).
本発明の目的である。高強度、高初期弾性率であり、か
つ、単糸が太繊度のＰＶＡ繊維を得るには、全延伸倍率
を１０倍以上とするのが好ましく。This is the object of the present invention. In order to obtain PVA fibers with high strength, high initial elastic modulus, and thick single yarns, the total stretching ratio is preferably 10 times or more.
より好ましくは１５倍以上にするのがよい。More preferably, it is 15 times or more.
本発明によれば、商業的に人手可能な重合度のＰＶＡを
用いて、高強度・高初期弾性率を有する。According to the present invention, PVA with a commercially acceptable degree of polymerization is used and has high strength and high initial modulus.
単糸が大繊度のＰＶＡａｌ維を、低コストで生産性よく
製造することが可能である。It is possible to manufacture PVAal fibers having a large single filament density at low cost and with good productivity.
このようにして得られる本発明のＰＶＡ繊維は。The PVA fiber of the present invention obtained in this way is as follows.
１３ｇ／ｄ以にの引張り強度と３００ｇ／ｄ以上の初期
弾性率を有し、かつ、単糸繊度が１０デニール以上、１
００デニール未満という従来にない大繊度であるので、
セメント補強用として使用する際の分散性がよく、この
ため、糸径が小さい場合のような。It has a tensile strength of 13 g/d or more, an initial elastic modulus of 300 g/d or more, and a single yarn fineness of 10 denier or more, 1
Because it has an unprecedented fineness of less than 0.00 denier,
It has good dispersibility when used as cement reinforcement, and for this reason, such as when the thread diameter is small.
フィラメントを集束してカットすることにより分散性を
向上させる必要がなく、工程の合理化や。There is no need to improve dispersion by focusing the filament and cutting it, streamlining the process.
セメント、コンクリートの補強効果を向上させることが
可能となる。It becomes possible to improve the reinforcing effect of cement and concrete.
また、単糸繊度が大きいため、従来のＰＶＡ繊維よりも
耐候性が著しく向上し、ローブや漁網。In addition, due to the large single yarn fineness, weather resistance is significantly improved compared to traditional PVA fibers, making it suitable for use in robes and fishing nets.
海苔網等、耐候性を要求される産業資材用途にも好適な
ものである。It is also suitable for use in industrial materials that require weather resistance, such as seaweed nets.
（作用）
本発明の製造法において、単糸繊度が１０デニール以七
、１００デニール未満でありながら、引張り強度が１３
ｇ／（１以上、初期弾性率が３００ｇ／ｄ以上という高
強度・高初期弾性率を有するＰＶＡＩａ維が得られる理
由は９次のように考えられる。(Function) In the production method of the present invention, the single yarn fineness is 10 deniers or more and less than 100 deniers, yet the tensile strength is 13 deniers.
The reason why PVAIa fibers having high strength and high initial elastic modulus of 300 g/d or higher can be obtained is considered to be as follows.
すなわち、紡糸原液量ｌ」側に突出する形状の吐出孔を
有する紡糸口金を用いて乾・湿式紡糸することにより、
吐出線速度を下げても、吐出孔で紡糸原液が半球状とな
って紡糸口金に付着することがなく、安定した紡糸がｐ
Ｊ能となるからである。That is, by performing dry/wet spinning using a spinneret having a discharge hole protruding toward the spinning stock solution amount l'' side,
Even if the discharge linear speed is lowered, the spinning stock solution does not become hemispherical in the discharge hole and adhere to the spinneret, and stable spinning can be achieved.
This is because it becomes J-Noh.
なお１本発明における引張り強度と初期弾性率は、 Ｊ
ＩＳ−Ｌ−１０１３に準じて、つかみ間隔２５ｃｍ、引
張り速度３０ｃｍ／分で測定するものである。Note that the tensile strength and initial elastic modulus in the present invention are J
In accordance with IS-L-1013, the measurement is performed at a gripping interval of 25 cm and a pulling speed of 30 cm/min.
（実施例） 次に１本発明を実施例により具体的に説明する。(Example) Next, one embodiment of the present invention will be specifically explained using examples.
実施例１〜２．比較例１
重合度１３００．１７００及び３０００のＰＶＡのＤＭ
ＳＯ溶液を調製し９次いで第１図で示したような、紡糸
原液の出口側の内径が０．７ｍｍのステンレス製円筒状
細管５０本を紡糸口金から３ｍｍの突起を形成するよう
に埋め込んだ紡糸１］１金を用いてメタノール中に乾・
湿式紡糸し、未延伸系を得た。この時。Examples 1-2. Comparative Example 1 DM of PVA with polymerization degree of 1300, 1700 and 3000
An SO solution was prepared, and 50 stainless steel cylindrical tubes with an inner diameter of 0.7 mm were embedded on the exit side of the spinning dope to form a 3 mm protrusion from the spinneret, as shown in Figure 1. 1] Dry and dry in methanol using 1 gold.
Wet spinning was performed to obtain an unstretched system. At this time.
吐出線速度及び紡糸ドラフトはそれぞれ４ｍ／分及び５
．０で一定とした。The discharge linear velocity and spinning draft were 4 m/min and 5 m/min, respectively.
．． It was set constant at 0.
次いで、得られた未延伸系を第１段延伸温度１８０℃、
第２段延伸温度２５０℃で延伸し、ＰＶＡ繊維を得た。Next, the obtained unstretched system was subjected to a first stage stretching temperature of 180°C.
The PVA fiber was obtained by drawing at a second stage drawing temperature of 250°C.
第１表に製造条件及び得られたＰＶＡ繊維の糸質を示す
。Table 1 shows the manufacturing conditions and the quality of the obtained PVA fibers.
また、比較のために、第２図に示したような。Also, for comparison, as shown in FIG.
吐出孔が突出していない紡糸１０金を用いる以外は実施
例１〜２と同様の条件で乾・湿式紡糸したところ、いず
れの場合も紡糸口金面に紡糸原液が半球状に付着する現
象が起こり、安定した紡糸が困難であり、延伸に供する
だけの未延伸糸が採取できなかった。When dry and wet spinning was carried out under the same conditions as in Examples 1 and 2 except that 10-karat gold spinning material with no protruding discharge holes was used, a phenomenon in which the spinning stock solution adhered to the spinneret surface in a hemispherical shape occurred in each case. Stable spinning was difficult, and it was not possible to collect enough undrawn yarn for drawing.
第１表から明らかなように１本発明のＰＶＡ繊維は、従
来のＰＶＡ繊維では得られなかった単糸磯度であり、か
つ、高強度・高初期弾性率を有していた。As is clear from Table 1, the PVA fiber of the present invention had a single fiber stiffness that could not be obtained with conventional PVA fibers, and also had high strength and high initial elastic modulus.
実施例３〜５．比較例２
重合度５１００のＰＶＡの１２重量％ＤＭＳＯ溶液を調
製し、紡糸原液の出口側の内径が０．７．１．２．２．
１゜２．４ｍｍのステンレス製円筒状細管を紡糸口金か
ら３ｍｍの突起を形成するように、各々１００．１？、
６゜４本埋め込んだ紡糸口金を用いて乾・湿式紡糸
し。Examples 3-5. Comparative Example 2 A 12% by weight DMSO solution of PVA with a degree of polymerization of 5100 was prepared, and the inner diameter on the outlet side of the spinning dope was 0.7.1.2.2.
A 1° 2.4 mm stainless steel cylindrical capillary was inserted into the spinneret to form a 3 mm protrusion, each 100.1 mm. ,
Dry and wet spinning using four 6° spinnerets.
未延伸系を？Ｓまた。An unstretched system? S again.
次いで、得られた未延伸糸を実施例１〜２と同様に延伸
し、ＰＶＡ繊維を得た。Next, the obtained undrawn yarn was drawn in the same manner as in Examples 1 and 2 to obtain PVA fibers.
第１表に製造条件及び得られたＰＶＡ繊維の糸質を示す
。Table 1 shows the manufacturing conditions and the quality of the obtained PVA fibers.
（発明の効果）
本発明の１） ￥ Ａ繊維は、１３ｇ／ｄ以上の強度と
３００ｇ／ｄ以上の初期弾性率を有し、かつ、単糸磯度
がｌＯデニール以上、１００デニール未満という従来に
ない大繊度であるので、セメント、コンクリート等の補
強用とし用いた場合の分散性がよく。(Effects of the Invention) 1) A fiber of the present invention has a strength of 13 g/d or more and an initial elastic modulus of 300 g/d or more, and has a single yarn roughness of 10 denier or more and less than 100 denier. Because it has a high fineness that is not found in other countries, it has good dispersibility when used for reinforcing cement, concrete, etc.
補強効果を向上させることが可能であり、さらに。It is possible to improve the reinforcement effect and further.
従来のＰＶＡ繊維よりも耐候性が著しく向上するので、
ローブや漁網、海苔網等、耐候性を要求される産業資材
用途にも好適なものである。Weather resistance is significantly improved compared to conventional PVA fibers,
It is also suitable for industrial materials that require weather resistance, such as robes, fishing nets, and seaweed nets.
また９本発明のＰＶＡｍ維の製造法によれ°ば。Further, according to the method for producing PVAm fiber of the present invention.
上記の利点を有するＰＶＡ繊維を生産性よく、低コスト
で製造することが可能となる。It becomes possible to manufacture PVA fibers having the above advantages with good productivity and at low cost.
第１図は１本発明のＰＶＡ繊維を製造する際に用いる紡
糸口金の一実施態様を示す断面図、第２図は、従来の乾
式紡糸あるいは湿式紡糸で用いられる紡糸口金の断面図
である。FIG. 1 is a sectional view showing an embodiment of a spinneret used in producing the PVA fiber of the present invention, and FIG. 2 is a sectional view of a spinneret used in conventional dry spinning or wet spinning.
Claims (2)
アルコールからなり、引張り強度が１３ｇ／ｄ以上、初
期弾性率が３００ｇ／ｄ以上であり、かつ、単糸繊度が
１０デニール以上、１００デニール未満であることを特
徴とするポリビニルアルコール繊維。(1) It is made of polyvinyl alcohol with a degree of polymerization of 1500 or more and 7000 or less, has a tensile strength of 13 g/d or more, an initial elastic modulus of 300 g/d or more, and a single yarn fineness of 10 denier or more and less than 100 denier. A polyvinyl alcohol fiber characterized by:
アルコールを溶媒に溶解して調製した紡糸原液を、単数
又は複数の吐出孔を有する紡糸口金を用いて乾・湿式紡
糸し、得られた未延伸糸を延伸してポリビニルアルコー
ル繊維を製造するに際し、紡糸原液出口側に突出する形
状の吐出孔を有する紡糸口金を用いて乾・湿式紡糸する
ことを特徴とするポリビニルアルコール繊維の製造法。(2) Undrawn yarn obtained by dry/wet spinning a spinning dope prepared by dissolving polyvinyl alcohol with a degree of polymerization of 1,500 or more and 7,000 or less in a solvent using a spinneret having one or more discharge holes. 1. A method for producing polyvinyl alcohol fibers, which comprises performing dry/wet spinning using a spinneret having a discharge hole protruding from the outlet side of a spinning solution when producing polyvinyl alcohol fibers by drawing the fibers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12203089A JPH02300308A (en) | 1989-05-15 | 1989-05-15 | Polyvinyl alcohol fiber and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12203089A JPH02300308A (en) | 1989-05-15 | 1989-05-15 | Polyvinyl alcohol fiber and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02300308A true JPH02300308A (en) | 1990-12-12 |
Family
ID=14825857
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12203089A Pending JPH02300308A (en) | 1989-05-15 | 1989-05-15 | Polyvinyl alcohol fiber and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02300308A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0496376A2 (en) * | 1991-01-22 | 1992-07-29 | Unitika Ltd. | Polyvinyl alcohol fiber and process for preparation thereof |
| KR20030058376A (en) * | 2001-12-31 | 2003-07-07 | 주식회사 효성 | Spinneret for spinning synthetic fibers |
| KR100808092B1 (en) * | 2006-10-10 | 2008-02-28 | (주)동국가연 | Apparatus for manufacturing polypropylene filaments for clothes |
-
1989
- 1989-05-15 JP JP12203089A patent/JPH02300308A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0496376A2 (en) * | 1991-01-22 | 1992-07-29 | Unitika Ltd. | Polyvinyl alcohol fiber and process for preparation thereof |
| KR20030058376A (en) * | 2001-12-31 | 2003-07-07 | 주식회사 효성 | Spinneret for spinning synthetic fibers |
| KR100808092B1 (en) * | 2006-10-10 | 2008-02-28 | (주)동국가연 | Apparatus for manufacturing polypropylene filaments for clothes |
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