JPS6399315A - Production of high-strength and high-initial elastic modulus polyvinyl alcohol fiber - Google Patents
Production of high-strength and high-initial elastic modulus polyvinyl alcohol fiberInfo
- Publication number
- JPS6399315A JPS6399315A JP24004686A JP24004686A JPS6399315A JP S6399315 A JPS6399315 A JP S6399315A JP 24004686 A JP24004686 A JP 24004686A JP 24004686 A JP24004686 A JP 24004686A JP S6399315 A JPS6399315 A JP S6399315A
- Authority
- JP
- Japan
- Prior art keywords
- pva
- spinning
- strength
- dmso
- water
- 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 37
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims description 48
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims description 48
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 94
- 238000009987 spinning Methods 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000012046 mixed solvent Substances 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 239000011550 stock solution Substances 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 9
- LCGLNKUTAGEVQW-UHFFFAOYSA-N methyl monoether Natural products COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims 2
- 238000002166 wet spinning Methods 0.000 abstract description 13
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000004026 adhesive bonding Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 30
- 239000002904 solvent Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 11
- -1 Polyethylene Polymers 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 230000015271 coagulation Effects 0.000 description 6
- 238000005345 coagulation Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 238000000578 dry spinning Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001891 gel spinning Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- XRASRVJYOMVDNP-UHFFFAOYSA-N 4-(7-azabicyclo[4.1.0]hepta-1,3,5-triene-7-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=CC=C21 XRASRVJYOMVDNP-UHFFFAOYSA-N 0.000 description 1
- 101100049042 Arabidopsis thaliana PVA11 gene Proteins 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Artificial Filaments (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は、高強度・高初期弾性率を有するポリビニルア
ルコール(以下PVAと略記する。)繊維の製造法に関
し、さらに詳しくは、高強度・高初期弾性率を有するP
VA繊維を、紡糸時にフイラメント同士が膠着すること
なく、安定に紡糸して製造する方法に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for producing polyvinyl alcohol (hereinafter abbreviated as PVA) fibers having high strength and high initial elastic modulus. P with high initial modulus
The present invention relates to a method for stably spinning and producing VA fibers without causing filaments to stick to each other during spinning.
(従来の技術)
最近、ポリバラフェニレンテレフタルアミド(以下PP
TAと略記する。)に代表されるごとく、剛直な分子鎖
を有する重合体を用いて、硫酸等の特定溶媒に溶液が液
晶性を示すような濃度となるようにその重合体を溶解し
た後紡糸する。いわゆる液晶紡糸を行うことにより、2
0g/d以上の強度と500 g/d以上の初期弾性率
を有する高強度・高初期弾性率繊維を得ることが可能と
なり、すてにPPTA繊維は実用段階に入っている。し
かしながら、かかる繊維は原料コスト、製造コストの面
で一般糸に比べて非常にコスト高となり、不利である。(Prior art) Recently, polyvalent phenylene terephthalamide (hereinafter referred to as PP)
It is abbreviated as TA. ), a polymer with a rigid molecular chain is used, and the polymer is dissolved in a specific solvent such as sulfuric acid to a concentration such that the solution exhibits liquid crystallinity, and then spun. By performing so-called liquid crystal spinning, 2
It has become possible to obtain high strength and high initial elastic modulus fibers having a strength of 0 g/d or more and an initial elastic modulus of 500 g/d or more, and PPTA fibers have already entered the practical stage. However, such fibers are disadvantageous in that they are much more costly than ordinary yarns in terms of raw material costs and manufacturing costs.
一方、屈曲性の高分子量ポリマーから高強度・高初期弾
性率繊維を得る方法も開発され、注目を浴びている。い
わゆるゲル紡糸法である。ゲル紡糸法によるポリエチレ
ン繊維においては、PPTA繊維の約2倍、あるいはそ
れ以上の強度を有し。On the other hand, a method for obtaining high-strength, high-initial-modulus fibers from flexible high-molecular-weight polymers has also been developed and is attracting attention. This is the so-called gel spinning method. Polyethylene fibers produced using the gel spinning method have a strength that is approximately twice or more than that of PPTA fibers.
初期弾性率においても極限にかなり近い性能を有する繊
維が得られているものの、その融点の低さから耐熱性に
欠ける欠点を有している。Although fibers have been obtained that have performance that is quite close to the limit in initial elastic modulus, they have the drawback of lacking heat resistance due to their low melting points.
PVA繊維は、汎用繊維中9強度・初期弾性率の点で優
れており、耐熱性においても、ポリエチレン繊維に比べ
て優れている。したがって、 PPTAIIIi維と
同程度の強度と初期弾性率を有するPVA繊維が得られ
るならば、コスト・パフォーマンスの点で大変有利であ
り、用途の拡大が可能である。PVA fibers are superior to general-purpose fibers in terms of strength and initial elastic modulus, and are also superior to polyethylene fibers in heat resistance. Therefore, if PVA fibers having strength and initial elastic modulus comparable to those of PPTA IIIi fibers could be obtained, it would be very advantageous in terms of cost performance and the range of uses could be expanded.
従来、PVA繊維の強度と初期弾性率を改善する方法は
種々検討されており9例えば、特公昭48−32623
号公報、特公昭48−32624号公報、特公昭4B−
9210号公報、特公昭53−1368号公報等に各種
の提案がなされている。これらの提案による方法は、ホ
ウ酸水溶液にPVAを溶解して紡糸原液を調製し、硫酸
ナトリウム等の脱水性塩類を含むアルカリ性水溶液中に
湿式紡糸してゲル状の未延伸糸を一旦形成せしめ。Conventionally, various methods for improving the strength and initial elastic modulus of PVA fibers have been studied9.For example, Japanese Patent Publication No. 48-32623
Publication No. 48-32624, Special Publication No. 4B-
Various proposals have been made in Japanese Patent Publication No. 9210, Japanese Patent Publication No. 1368/1980, and the like. In the method proposed by these methods, a spinning stock solution is prepared by dissolving PVA in an aqueous boric acid solution, and wet spinning is performed in an alkaline aqueous solution containing dehydrating salts such as sodium sulfate to once form a gel-like undrawn yarn.
次いで、その未延伸糸から酸性水溶液中でホウ酸を除去
した後延伸する方法であるが、PVAの溶媒として実質
的に水を用いるものであり、また。Next, the method involves removing boric acid from the undrawn yarn in an acidic aqueous solution, and then stretching the yarn, which essentially uses water as a solvent for PVA.
得られた繊維の強度は高々17g/dにすぎない。The strength of the obtained fibers is only 17 g/d at most.
また、溶媒にジメチルスルホキシド(以下DMSOと略
記する。)を用い、凝固液にメタノール。In addition, dimethyl sulfoxide (hereinafter abbreviated as DMSO) was used as the solvent, and methanol was used as the coagulation liquid.
アセトン、トルエン等を用いたPVAの湿式紡糸法につ
いても、特公昭43−16675号公報に公知である。A wet spinning method for PVA using acetone, toluene, etc. is also known from Japanese Patent Publication No. 16675/1983.
しかし、この方法では、PVA繊維を約20倍延伸して
得たにもかかわらず、初期弾性率の向上はみられるもの
の2強度は10 g/dにすぎない。However, in this method, although the initial elastic modulus is improved, the 2 strength is only 10 g/d, even though the PVA fiber is drawn by about 20 times.
一方、PVA繊維の強度と初期弾性率を共に改善する方
法が、特開昭59−130314号公報や特開昭60−
126312号公報に提案されている。これらの方法は
、PVAの溶媒として種々の有機溶媒1例えば、DMS
O,グリセリン、エチレングリコール等を用いるか、又
は水を用いるか、あるいはこれらの混合溶媒を用いて紡
糸原液を調製し、この紡糸原液を口金から空気や窒素等
の不活性雰囲気層を通過させて凝固浴(主とじてメタノ
ール)に押し出すことにより、すなわち乾・湿式紡糸す
ることにより、高強度・高初期弾性率PVA繊維を製造
するものである。On the other hand, methods for improving both the strength and initial elastic modulus of PVA fibers are disclosed in JP-A-59-130314 and JP-A-60-
This is proposed in Japanese Patent No. 126312. These methods use various organic solvents 1, for example, DMS as a solvent for PVA.
A spinning stock solution is prepared using O, glycerin, ethylene glycol, etc., water, or a mixed solvent thereof, and this spinning stock solution is passed through a layer of inert atmosphere such as air or nitrogen through a spinneret. PVA fibers with high strength and high initial elastic modulus are produced by extrusion into a coagulation bath (mainly methanol), that is, by dry/wet spinning.
(発明が解決しようとする問題点)
以上のごとく、高強度・高初期弾性率を有するPVA繊
維の製造法が種々提案されているが、前記の実質的に水
をPVAの溶媒として用いる湿式紡糸法では、18g/
d以上の強度を有するpvA繊維は得られておらず、さ
らに、紡糸後フィラメント同士が膠着するため、温熱処
理工程を必要とするものである。(Problems to be Solved by the Invention) As described above, various methods for producing PVA fibers having high strength and high initial elastic modulus have been proposed. According to the law, 18g/
A pvA fiber having a strength of d or higher has not been obtained, and furthermore, since the filaments stick to each other after spinning, a heat treatment step is required.
また、PVAの溶媒にDMSOを用いて湿式紡糸する方
法では1強度の高いPVA1l維を得ることができなか
った。Furthermore, it was not possible to obtain PVA11 fibers with high strength using a wet spinning method using DMSO as a PVA solvent.
さらに1強度及び初期弾性率を共に改善することができ
る乾・湿式紡糸法については、上記2種類の方法よりも
優れているが、かかる方法では。Furthermore, the dry/wet spinning method, which can improve both strength and initial elastic modulus, is superior to the above two methods.
口金と凝固液(冷却液)との間に不活性雰囲気層が存在
するということが問題となる。すなわち。The problem is that there is an inert atmosphere layer between the cap and the coagulating liquid (cooling liquid). Namely.
紡糸原液が口金吐出孔から押し出された場合1口全直下
(不活性雰囲気層中)では、形状不安定で。When the spinning dope is extruded from the nozzle discharge hole, the shape is unstable directly below the first nozzle (in an inert atmosphere layer).
しかも太いゲル状フィラメントが形成されるので。Moreover, thick gel-like filaments are formed.
複数の吐出孔から紡糸原液が押し出された場合には、吐
出孔の間隔(1つの吐出孔とその隣の吐出孔との間隔)
が狭ければ、各々のゲル状フィラメントは互いに密着を
起こし、膠着糸の生成の原因になるという問題がしばし
ば生ずるのである。When the spinning dope is extruded from multiple discharge holes, the interval between the discharge holes (the distance between one discharge hole and the discharge hole next to it)
If the diameter is narrow, the respective gel-like filaments tend to adhere to each other, which often causes the formation of adhesive threads.
したがって1本発明は、紡糸時にフィラメント同士が膠
着することなく、安定に紡糸することができ、高強度・
高初期弾性率を有するPVA繊維をPPTA繊維よりも
低コストで製造する方法を提供することを目的とするも
のである。Therefore, the present invention enables stable spinning without the filaments sticking to each other during spinning, and has high strength and
It is an object of the present invention to provide a method for producing PVA fibers having a high initial modulus at a lower cost than PPTA fibers.
(問題点を解決するための手段)
本発明者等は、かかる現状に鑑み、ポリエチレンよりも
高い耐熱性を有するPVAを用いて上記目的を達成せん
と鋭意検討した結果2本発明に到達した。(Means for Solving the Problems) In view of the current situation, the present inventors conducted intensive studies to achieve the above object using PVA, which has higher heat resistance than polyethylene, and as a result, they arrived at the present invention.
すなわち9本発明は9重合度1500以上のPVAを重
量混合比が5:95〜60 : 40である水及びDM
SOの混合溶媒に溶解して紡糸原液を調製し、該紡糸原
液を湿式紡糸法により口金から。That is, 9 The present invention uses PVA with a degree of polymerization of 1500 or more in water and DM in a weight mixing ratio of 5:95 to 60:40.
A spinning stock solution is prepared by dissolving SO in a mixed solvent, and the spinning stock solution is passed through a spinneret by a wet spinning method.
重量混合比が10:90〜70 : 30であるDMS
Oとアルコールの混合溶液中に押し出し、未延伸糸を形
成せしめ、しかる後未延伸糸を一旦捲き取るか又は連続
して少なくとも15倍以上の延伸を行うことを特徴とす
る高強度・高初期弾性率PVA繊維の製造法を要旨とす
るものである。DMS with a weight mixing ratio of 10:90 to 70:30
High strength and high initial elasticity characterized by extruding into a mixed solution of O and alcohol to form an undrawn yarn, and then winding up the undrawn yarn once or continuously stretching it at least 15 times or more. The gist of this paper is a method for producing polyurethane PVA fiber.
以下1本発明をさらに詳しく説明する。The present invention will be explained in more detail below.
本発明で用いられるPVAの重合度は、得られる繊維の
物性から1500以上であり、好ましくは3000以上
、さらに好ましくは4500以上である。また、PVA
のケン化度は、99%以上のものが好ましい。The degree of polymerization of PVA used in the present invention is 1,500 or more, preferably 3,000 or more, and more preferably 4,500 or more in view of the physical properties of the resulting fiber. Also, PVA
The saponification degree of is preferably 99% or more.
このようなPVAを水及びU5MSOの混合溶媒に溶解
して紡糸原液を調製するのであるが、 PVAの重合
度が1500〜10000程度で、紡糸温度を約40〜
120℃とする場合、PVAの濃度を2〜35重量%の
範囲に調整するのが好ましい。濃度が2重量%未満の場
合は曳糸性が低下し。A spinning stock solution is prepared by dissolving such PVA in a mixed solvent of water and U5MSO.
When the temperature is 120°C, it is preferable to adjust the concentration of PVA to a range of 2 to 35% by weight. If the concentration is less than 2% by weight, the stringability will decrease.
35重量%を超える場合は粘度が高く、紡糸原液の均一
性が低下すると共に未延伸糸の延伸性も低下する傾向に
あり、好ましくない。If it exceeds 35% by weight, the viscosity is high and the uniformity of the spinning dope tends to decrease, as well as the drawability of the undrawn yarn tends to decrease, which is not preferable.
また、水及びDMSOの混合溶媒における両者の重量混
合比は、5:95〜60:40の範囲である。この範囲
外では、混合溶媒としての効果が低下し、紡糸時にフィ
ラメント同士がしばしば膠着するという現象がみられる
ようになり、好ましくない。また、最も好ましい水及び
DMSOの重量混合比は、20:80〜45 : 55
である。本発明においては、この混合溶媒にPVAの耐
熱剤。Further, the weight mixing ratio of water and DMSO in the mixed solvent is in the range of 5:95 to 60:40. Outside this range, the effectiveness as a mixed solvent is reduced and a phenomenon in which filaments often stick together during spinning is undesirable. Moreover, the most preferable weight mixing ratio of water and DMSO is 20:80 to 45:55.
It is. In the present invention, a PVA heat resistant agent is added to this mixed solvent.
顔料、架橋剤等を適宜混入して用いても差し支えない。Pigments, crosslinking agents, etc. may be appropriately mixed in and used.
本発明においては、上記の水/DMSO混合溶媒にPV
Aを溶解して調製された紡糸原液を9次いで、湿式紡糸
法により口金から液中に押し出して未延伸糸を形成させ
る。紡糸原液を口金から押し出す液としては1重量部合
比が10:90〜70:30.好ましくは10:90〜
50 : 50であるDMSOとアルコールの混合溶液
を用いる。In the present invention, PV is added to the above water/DMSO mixed solvent.
A spinning solution prepared by dissolving A is then extruded into the solution through a spinneret by a wet spinning method to form an undrawn yarn. The liquid for extruding the spinning dope from the spinneret has a 1 part weight ratio of 10:90 to 70:30. Preferably from 10:90
A mixed solution of DMSO and alcohol in a ratio of 50:50 is used.
本発明においては、この混合溶液は少量の水を含有して
いても差し支えない。例えば2本発明においては、紡糸
原液中の水が液中に持ち込まれ、その結果、液の組成が
水/DMSO/アルコールの3成分になることもあり得
るが、そのような液中の水の濃度の増加は僅かであり、
特に問題とならない。In the present invention, this mixed solution may contain a small amount of water. For example, in the present invention, water in the spinning stock solution may be brought into the solution, and as a result, the composition of the solution may become three components: water/DMSO/alcohol. The increase in concentration is small;
There is no particular problem.
ここで用いられるアルコールとしては9例えば。Examples of alcohols used here include 9.
メタノール、エタノール、プロパツール、イソプロパツ
ール、ブタノール等の脂肪族系アルコールが好ましく、
特にメタノールが好適に用いられる。Aliphatic alcohols such as methanol, ethanol, propatool, isopropanol, butanol are preferred;
In particular, methanol is preferably used.
本発明では、前記液中で形成された未延伸糸を一旦捲き
取るか又は連続して延伸工程に供給して延伸する。本発
明においては、この間、乾燥、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。In the present invention, the undrawn yarn formed in the liquid is once wound up or continuously supplied to a drawing step and drawn. In the present invention, during this time, other steps such as drying, oil treatment, etc. may be appropriately introduced if necessary.
本発明で適用できる延伸方法は種々あるが1例えば、ヒ
ートプレート等の加熱体にPVA繊維を接触させながら
延伸する方法、ヒートオーブン等の熱風浴中で延伸する
方法、熱媒中で延伸する方法、誘電加熱方式で延伸する
方法があげられる。There are various stretching methods that can be applied in the present invention. For example, a method in which the PVA fiber is stretched while being in contact with a heating body such as a heat plate, a method in which the PVA fiber is stretched in a hot air bath such as a heat oven, and a method in which it is stretched in a heating medium. , a dielectric heating method for stretching.
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1本発明においては、2段以上の多段
で延伸することが好ましい。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、油剤付与等を行ってもよい。In these methods, the stretching can be carried out in one stage or in multiple stages of two or more stages, but in the present invention, it is preferable to perform the stretching in multiple stages of two or more stages. Further, in the case of multi-stage stretching, moisture application, oil application, etc. may be performed between the n-th 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・高初期弾性率を有するPV
A繊維を得るには、紡糸延伸を含めて全延伸倍率を少な
くとも15倍以上とする必要があり、好ましくは20倍
以上とするのがよい。ここでいう紡糸延伸とは、紡糸原
液が口金から押し出される時の吐出線速度(Vo)と、
形成されたPvA未延伸糸が最初に引き取られるローラ
ーの速度(V+)の比(V+/VO)で表される紡糸ド
ラフト及び熱延伸工程での延伸を除外した。その他の工
程で行われるすべての延伸を意味しており、乾燥工程や
油剤処理工程等で行われる延伸も紡糸延伸に含まれる。PV having high strength and high initial elastic modulus which is the object of the present invention
In order to obtain fiber A, the total draw ratio including spinning and drawing needs to be at least 15 times or more, preferably 20 times or more. The spinning drawing referred to here refers to the ejection linear velocity (Vo) when the spinning dope is extruded from the spinneret,
Stretching in the spinning draft and hot drawing steps, which is expressed as the ratio (V+/VO) of the speed (V+) of the roller at which the formed PvA undrawn yarn is first taken off, was excluded. This refers to all stretching performed in other processes, and stretching performed in drying processes, oil treatment processes, etc. is also included in spinning/drawing.
したがって9本発明でいう全延伸倍率とは、前記の紡糸
ドラフトのみを除くすべての延伸から計算されたもので
ある。Therefore, the total draw ratio as used in the present invention is calculated from all drawings except for the above-mentioned spinning draft.
(作 用)
本発明によれば、紡糸時にフィラメント同士が膠着する
ことなく、安定に紡糸でき、しかも得られた未延伸糸は
高倍率に延伸できるので、高強度・高初期弾性率PVA
繊維を得ることが可能である。(Function) According to the present invention, the filaments can be stably spun without sticking to each other during spinning, and the obtained undrawn yarn can be stretched to a high ratio, resulting in a PVA with high strength and high initial elastic modulus.
It is possible to obtain fibers.
このフィラメント同士が膠着しない理由は、現時点では
十分に解明されていないのであるが、紡糸原液の溶媒に
水/DMSO混合溶媒を用い、紡糸原液を押し出す液に
DMSO/アルコール混合溶液を用いることは、上記の
従来法に比べて明らかに差が認められる。The reason why these filaments do not stick to each other is not fully understood at present, but using a water/DMSO mixed solvent as the solvent for the spinning stock solution and a DMSO/alcohol mixed solution as the liquid for extruding the spinning stock solution, There is a clear difference compared to the conventional method described above.
また、高い延伸性を有する未延伸糸が得られる理由は、
紡糸原液が口金から押し出された後、水及びDMSOの
抽出が開始されるのであるが、この抽出がほぼ終了する
までに要する時間を従来の湿式紡糸の抽出時間に比べて
長くなるよう制御することができたためと推察される。In addition, the reason why undrawn yarn with high drawability can be obtained is as follows.
After the spinning dope is extruded from the spinneret, the extraction of water and DMSO starts, but the time required for this extraction to almost complete is controlled so that it is longer than the extraction time of conventional wet spinning. It is presumed that this is due to the fact that
つまり、未延伸糸中の水及びDMSOをアルコール10
0%で抽出するのではなく、紡糸原液の1つの成分であ
るDMSOを含むアルコールで抽出することにより、そ
のような制御が可能になったものと推察される。そのた
め、抽出により凝固に至るまでの過程でPVA分子のま
わりに水及びDMSOの混合溶媒が比較的長時間残存し
くあるいは水又はDMSOのどちらか一方の溶媒が優先
的に抽出されて。In other words, water and DMSO in the undrawn yarn are mixed with 10% alcohol.
It is presumed that such control was made possible by extracting with alcohol containing DMSO, which is one of the components of the spinning solution, instead of extracting with 0%. Therefore, in the process of extraction leading to coagulation, the mixed solvent of water and DMSO remains around the PVA molecules for a relatively long time, or one of the solvents, water or DMSO, is preferentially extracted.
他方の溶媒が比較的長時間残存するのかもしれないカリ
、そのため、PVA分子の動きが比較的自由となり、P
VA分子鎖が折りたたみ構造をとりやすくなるものと推
察される。The other solvent may remain for a relatively long time, so the movement of PVA molecules is relatively free, and P
It is presumed that the VA molecular chain becomes more likely to assume a folded structure.
これに対して、PVAのホウ酸水溶液を紡糸原液として
硫酸ナトリウム等の脱水性塩類を含む凝固液中←湿式紡
糸する方法や、PVAのDMSO溶液を紡糸原液として
メタノール中に湿式紡糸する方法では、紡糸原液が口金
から押し出された後凝固するまでの時間が短時間である
ため、PVA分子の絡み合いが比較的多い状態で未延伸
糸が形成されることになり、後の延伸工程で高倍率に延
伸できないものと推察される。On the other hand, in the method of wet spinning using a boric acid aqueous solution of PVA as a spinning stock solution in a coagulating solution containing dehydrating salts such as sodium sulfate, or the method of wet spinning in methanol using a DMSO solution of PVA as a spinning stock solution, Since the time required for the spinning dope to solidify after being extruded from the spinneret is short, undrawn yarn is formed with a relatively large amount of entanglement of PVA molecules, resulting in a high drawing ratio in the subsequent drawing process. It is presumed that it cannot be stretched.
本発明者等が行った実験では、紡糸原液のPVA淵度を
15wt%として50デニール/10フイラメントの未
延伸糸を得る場合、溶媒を90%以上抽出するのに要し
た時間は1本発明の場合で3分以上であったのに対して
、紡糸原液の溶媒及び凝固液にDMSO及びメタノール
を用いた場合と。In experiments conducted by the present inventors, when obtaining an undrawn yarn of 50 denier/10 filaments by setting the PVA depth of the spinning stock solution to 15 wt%, the time required to extract 90% or more of the solvent was 1. In contrast, it took more than 3 minutes in the case where DMSO and methanol were used as the solvent for the spinning solution and the coagulation liquid.
水及び脱水性塩類を含む水溶液を用いた場合とでは、共
に1分以下という結果を得た。このことは。In both cases where an aqueous solution containing water and dehydrating salts was used, a result of less than 1 minute was obtained. About this.
上記の考えを示唆するものと思われる。This seems to suggest the above idea.
(実施例) 以下、実施例により本発明をさらに詳しく説明する。(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.
なお1例中1強度、初期弾性率とあるのは、試料長20
cm、引張速度20cm/分で引張試験を行ったときの
値である(20℃、65%RH)。In addition, 1 strength and initial elastic modulus in one example are for a sample length of 20
cm, values obtained when a tensile test was conducted at a tensile speed of 20 cm/min (20° C., 65% RH).
実施例1〜3.比較例1
重合度2300.3500及び4800(7)PVAを
9重量比20:80の水/DMSO混合溶媒に100℃
で各々溶解し、濃度15重量%の紡糸原液を調製した。Examples 1-3. Comparative Example 1 PVA with polymerization degree of 2300.3500 and 4800 (7) was added to a mixed solvent of water/DMSO at a weight ratio of 20:80 at 100°C.
Each was dissolved to prepare a spinning stock solution having a concentration of 15% by weight.
これらの紡糸原液を70℃の紡糸口金から1重量混合比
が10 : 90のDMSO7/メタノール混合溶液中
に押し出し、PVA未延伸糸を形成させ1次いで、未延
伸糸中の水及びDMS○を十分に抽出してから未延伸糸
を捲き取った。このときフィラメント同士の膠着はみら
れなかった。捲き取った未延伸糸を乾燥させた後、2段
で表1に示す倍率の熱延伸を行い、500デニール/1
00フイラメントの延伸糸を得た。ただし、このときの
延伸倍率は、最高延伸倍率の90%としたものである。These spinning stock solutions were extruded from a spinneret at 70° C. into a DMSO7/methanol mixed solution with a weight mixing ratio of 10:90 to form an undrawn PVA yarn. Next, the water and DMS in the undrawn yarn were sufficiently removed. After extraction, the undrawn yarn was wound up. At this time, no adhesion between the filaments was observed. After drying the rolled-up undrawn yarn, it was hot-stretched in two stages at the ratio shown in Table 1 to 500 denier/1
A drawn yarn of 00 filament was obtained. However, the stretching ratio at this time was 90% of the maximum stretching ratio.
比較のため、全延伸倍率を14.6倍とした以外は実施
例1と同様にして延伸糸を得た。For comparison, a drawn yarn was obtained in the same manner as in Example 1 except that the total draw ratio was 14.6 times.
表1に延伸条件及び得られた延伸糸の糸質測定結果を示
す。Table 1 shows the drawing conditions and the results of measuring the quality of the drawn yarn.
水/ D M S Oの重量混合比及びD M S O
/メタノールの重量混合比を、それぞれ20:80及び
10:90とした場合、全延伸倍率を15倍以上とする
ことにより1強度15g/d以上の高強度・窩初期弾性
率PVA繊維が得られる。Water/DMSO weight mixing ratio and DMSO
When the weight mixing ratio of /methanol is 20:80 and 10:90, respectively, a high strength PVA fiber with a single strength of 15 g/d or more and a cavity initial elastic modulus can be obtained by setting the total stretching ratio to 15 times or more. .
実施例4〜6.比較例2〜4
溶媒として、水/DMSOの重量混合比が10:90.
30ニア0,50:50あるいは70:30の混合溶媒
、DMS0100%(0:100)及び水100%(1
00:0)の6種の溶媒を用い、これらの溶媒に重合度
4800のPVAを溶解し、各々濃度12重量%の紡糸
原液を調製した。Examples 4-6. Comparative Examples 2 to 4 As a solvent, the weight mixing ratio of water/DMSO was 10:90.
30nia 0, 50:50 or 70:30 mixed solvent, DMS0 100% (0:100) and water 100% (1
PVA having a degree of polymerization of 4800 was dissolved in these solvents to prepare spinning stock solutions each having a concentration of 12% by weight.
これらの紡糸原液を80℃の紡糸口金から9重量混合比
が15=85のDMSO/メタノール混合溶液中に押し
出して(ただし、水100%の溶媒を用いた場合のみ、
硫酸ナトリウムを350 g/l含む水溶液中に押し出
した)、PVA未延伸糸を形成させ1次いで、未延伸糸
に含まれている溶媒を十分に抽出してから一旦捲き取り
、乾燥した。These spinning stock solutions were extruded from a spinneret at 80°C into a DMSO/methanol mixed solution with a weight mixing ratio of 15 = 85 (however, only when a 100% water solvent was used;
(extruded into an aqueous solution containing 350 g/l of sodium sulfate) to form an undrawn PVA yarn.Next, the solvent contained in the undrawn yarn was sufficiently extracted, and the yarn was once rolled up and dried.
これらの未延伸糸を熱風オーブン中、2段で表2に示す
倍率の熱延伸を行い、400デニール/100フイラメ
ントの延伸糸を得た。ただし、このときの全延伸倍率は
、最高延伸倍率の85%としたものである。These undrawn yarns were hot-stretched in two stages in a hot air oven at the ratio shown in Table 2 to obtain drawn yarns of 400 denier/100 filaments. However, the total stretching ratio at this time was 85% of the maximum stretching ratio.
表2に延伸条件及び得られた延伸糸の糸質測定結果を示
す。Table 2 shows the drawing conditions and the yarn quality measurement results of the obtained drawn yarn.
表 2
1千→ヨ
ニョ力
実施例7
水/DMSOの重量混合比が15 : 85である混合
溶媒に2重合度5500のPVAを溶解し。Table 2 1,000 → Yoyo force Example 7 PVA with a degree of bipolymerization of 5500 was dissolved in a mixed solvent of water/DMSO at a weight mixing ratio of 15:85.
p V A ?W度8%の紡糸原液を調製した。この紡
糸原液を80℃の紡糸口金から2重量混合比が20:8
0のDMSO/エタノール混合溶液中に押し出し、PV
A未延伸糸を形成させ1次いで、未延伸糸中の溶媒を十
分に抽出してから、PVA未延伸糸を乾燥させ、しかる
後連続して延伸した。延伸は、乾熱オーブン中、3段で
行い、全延伸倍率を25.2倍として、250デニール
/100フイラメントのPVA延伸糸を得た。得られた
延伸糸の強度は23.98/d、初期弾性率は527
g/dという高い値であった。PVA? A spinning dope having a W degree of 8% was prepared. This spinning dope was added to a spinneret at 80°C at a mixing ratio of 20:8 by weight.
Extruded into 0 DMSO/ethanol mixed solution, PV
After forming an undrawn yarn A, the solvent in the undrawn yarn was sufficiently extracted, the PVA undrawn yarn was dried, and then continuously stretched. Stretching was performed in three stages in a dry heat oven, with a total stretching ratio of 25.2 times, to obtain a PVA drawn yarn of 250 denier/100 filaments. The strength of the obtained drawn yarn was 23.98/d, and the initial elastic modulus was 527.
It was a high value of g/d.
実施例8〜10.比較例5.6
重合度4800のPVAを1重量混合比が20:80の
水/ D M S O混合溶媒に溶解L*:a1度12
%の紡糸原液を調製した。この紡糸原液を口金から9重
量混合比が0:100.20:80゜40:60.60
:40.あるいは80:20のDMSO/メタノール混
合溶液中にそれぞれ押し出し、PVA未延伸糸を形成さ
せ9次いで、未延伸糸中の水/DMSOを十分抽出して
から未延伸糸を捲き取り、しかる後2段で熱延伸し、3
00デニール/150フイラメントの延伸糸を得た。Examples 8-10. Comparative Example 5.6 PVA with a degree of polymerization of 4800 was dissolved in a water/DMSO mixed solvent with a weight mixing ratio of 20:80 L*: a1 degree 12
% spinning stock solution was prepared. This spinning stock solution was mixed from the spinneret at a weight mixing ratio of 0:100.20:80°40:60.60.
:40. Alternatively, each is extruded into a DMSO/methanol mixed solution of 80:20 to form an undrawn PVA yarn.Next, the water/DMSO in the undrawn yarn is sufficiently extracted, and the undrawn yarn is wound up. 3.
A drawn yarn of 00 denier/150 filament was obtained.
延伸条件及び得られた延伸糸の糸質測定結果を表3に示
す。Table 3 shows the drawing conditions and the yarn quality measurement results of the obtained drawn yarn.
表 3
比較例6については、凝固液中のDMSOの割合が多す
ぎて、 HA固能能力極めて低下しており。Table 3 Regarding Comparative Example 6, the proportion of DMSO in the coagulation solution was too high, and the HA solidification ability was extremely reduced.
延伸に供することのできる未延伸糸が得られなかった。An undrawn yarn that could be subjected to drawing could not be obtained.
また、実施例10においては、未延伸糸の凝固浴浸漬時
間を、実施例8や9の場合よりも長くした(10分程度
)。Furthermore, in Example 10, the immersion time of the undrawn yarn in the coagulation bath was longer than in Examples 8 and 9 (about 10 minutes).
(発明の効果)
本発明によれば、紡糸時にフィラメント同士が膠着する
ことなく、安定に紡糸することができ。(Effects of the Invention) According to the present invention, stable spinning can be performed without filaments sticking to each other during spinning.
しかもPPTA繊維に匹敵する高強度・高初期弾性率P
VA繊維を製造することが可能であり、さらに、ポリエ
チレンゲル紡糸繊維よりも優れた耐熱性を有しているた
め、用途の拡大が可能である。Moreover, it has high strength and high initial elastic modulus P comparable to PPTA fiber.
Since it is possible to produce VA fibers and has better heat resistance than polyethylene gel spun fibers, it is possible to expand the range of uses.
その上、フィラメント同士が膠着することがないので、
乾・湿式紡糸(ゲル紡糸)で用いられる口金よりも大き
さを小さくできるか、又は同じ大きさの場合、吐出孔の
数をより多くすることができるので、吐出孔間での吐出
環を少なくすることができるか又はマルチフィラメント
化ができるので、非常に有利である。Moreover, since the filaments do not stick together,
The size of the nozzle can be smaller than that used for dry/wet spinning (gel spinning), or if the size is the same, the number of discharge holes can be increased, so the number of discharge rings between the discharge holes can be reduced. It is very advantageous because it can be made into filaments or made into multifilaments.
また、従来の湿式紡糸設備を大幅に改造することなく使
用することができることも1本発明の有利な点の1つで
ある。Another advantage of the present invention is that conventional wet spinning equipment can be used without significant modification.
Claims (7)
量混合比が5:95〜60:40である水及びジメチル
スルホキシドの混合溶媒に溶解して紡糸原液を調製し、
該紡糸原液を湿式紡糸法により口金から、重量混合比が
10:90〜70:30であるジメチルスルホキシドと
アルコールの混合溶液中に押し出し、未延伸糸を形成せ
しめ、しかる後未延伸糸を一旦捲き取るか又は連続して
少なくとも15倍以上の延伸を行うことを特徴とする高
強度・高初期弾性率ポリビニルアルコール繊維の製造法
。(1) Prepare a spinning stock solution by dissolving polyvinyl alcohol with a degree of polymerization of 1500 or more in a mixed solvent of water and dimethyl sulfoxide at a weight mixing ratio of 5:95 to 60:40,
The spinning stock solution is extruded from a spinneret into a mixed solution of dimethyl sulfoxide and alcohol with a weight mixing ratio of 10:90 to 70:30 to form an undrawn yarn, and then the undrawn yarn is wound once. A method for producing high-strength, high-initial-modulus polyvinyl alcohol fibers, which comprises stretching at least 15 times or more continuously.
ある特許請求の範囲第1項記載の製造法。(2) The manufacturing method according to claim 1, wherein the polyvinyl alcohol has a degree of polymerization of 3000 or more.
重量%である特許請求の範囲第1項記載の製造法。(3) The polyvinyl alcohol concentration of the spinning stock solution is 2 to 35
% by weight.
80〜45:55である特許請求の範囲第1項記載の製
造法。(4) The weight mixing ratio of water and dimethyl sulfoxide is 20:
The manufacturing method according to claim 1, wherein the ratio is 80 to 45:55.
が10:90〜50:50である特許請求の範囲第1項
記載の製造法。(5) The manufacturing method according to claim 1, wherein the weight mixing ratio of dimethyl sulfoxide and alcohol is 10:90 to 50:50.
1項記載の製造法。(6) The production method according to claim 1, wherein the alcohol is methanol.
囲第1項記載の製造法。(7) The manufacturing method according to claim 1, which involves stretching at least 20 times or more.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP24004686A JPS6399315A (en) | 1986-10-08 | 1986-10-08 | Production of high-strength and high-initial elastic modulus polyvinyl alcohol fiber |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP24004686A JPS6399315A (en) | 1986-10-08 | 1986-10-08 | Production of high-strength and high-initial elastic modulus polyvinyl alcohol fiber |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS6399315A true JPS6399315A (en) | 1988-04-30 |
Family
ID=17053670
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP24004686A Pending JPS6399315A (en) | 1986-10-08 | 1986-10-08 | Production of high-strength and high-initial elastic modulus polyvinyl alcohol fiber |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6399315A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0268309A (en) * | 1988-09-01 | 1990-03-07 | Kuraray Co Ltd | Production of high-tenacity polyvinyl alcohol fiber |
US5264173A (en) * | 1989-05-24 | 1993-11-23 | Masatsugu Mochizuki | Polyvinyl alcohol monofilament yarns and process for producing the same |
-
1986
- 1986-10-08 JP JP24004686A patent/JPS6399315A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0268309A (en) * | 1988-09-01 | 1990-03-07 | Kuraray Co Ltd | Production of high-tenacity polyvinyl alcohol fiber |
US5264173A (en) * | 1989-05-24 | 1993-11-23 | Masatsugu Mochizuki | Polyvinyl alcohol monofilament yarns and process for producing the same |
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