JPH0233314A - High-tenacity polyvinyl alcohol based fiber and production thereof - Google Patents
High-tenacity polyvinyl alcohol based fiber and production thereofInfo
- Publication number
- JPH0233314A JPH0233314A JP18384288A JP18384288A JPH0233314A JP H0233314 A JPH0233314 A JP H0233314A JP 18384288 A JP18384288 A JP 18384288A JP 18384288 A JP18384288 A JP 18384288A JP H0233314 A JPH0233314 A JP H0233314A
- Authority
- JP
- Japan
- Prior art keywords
- polyvinyl alcohol
- bond
- polymerization
- less
- strength
- 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 56
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 55
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 16
- 229920000642 polymer Polymers 0.000 abstract description 10
- 238000009987 spinning Methods 0.000 abstract description 8
- 239000012770 industrial material Substances 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 2
- 238000007599 discharging Methods 0.000 abstract 1
- 238000010791 quenching Methods 0.000 abstract 1
- 230000000171 quenching effect Effects 0.000 abstract 1
- 230000002787 reinforcement Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 238000000354 decomposition reaction Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 230000015271 coagulation Effects 0.000 description 7
- 238000005345 coagulation Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 238000001891 gel spinning Methods 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000499 gel Substances 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000002166 wet spinning Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-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
- 238000001816 cooling Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000004291 polyenes Chemical class 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011240 wet gel Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- 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、高強力ポリビニルアルコール系繊維およびそ
の製造法に関するものであり、特に産業資材用および複
合材の強化用に適したポリビニルアルコール系繊維を得
ようとするものである。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a high-strength polyvinyl alcohol fiber and a method for producing the same, and in particular to a polyvinyl alcohol fiber suitable for use in industrial materials and reinforcing composite materials. It is an attempt to obtain.
(従来の技術)
従来ポリビニルアルコール系線維は、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高強力で
その主用途である産業資材用繊維としてはもちろん、最
近ではアスベスト代替橡維としてセメントの補強材にも
使用されている。(Prior technology) Conventional polyvinyl alcohol fibers have higher strength than polyamide, polyester, and polyacrylonitrile fibers, and are used not only as fibers for industrial materials, which is their main use, but also as fibers for reinforcing cement as an asbestos substitute. is also used.
しかしこれまで得られたポリビニルアルコール系繊維は
、芳香族ポリアミド(アラミド)繊維や超高分子量ポリ
エチレン繊維のような高強力を有していなかった。However, the polyvinyl alcohol fibers obtained so far have not had the high strength of aromatic polyamide (aramid) fibers or ultra-high molecular weight polyethylene fibers.
ポリビニルアルコール系繊維は通常ポリビニルアルコー
ル水溶液を紡糸原液として用い凝固性無機塩水溶液中で
湿式紡糸し、延伸、乾燥熱処理等の処理を施す方法によ
シ製造されているがこのポリビニルアルコール系繊維が
高強力を得るために各種の方法が提案されてきた。Polyvinyl alcohol fibers are usually produced by a method of wet spinning in a coagulable inorganic salt aqueous solution using a polyvinyl alcohol aqueous solution as a spinning stock solution, followed by stretching, dry heat treatment, etc. Various methods have been proposed to obtain strength.
たとえば特公昭43−16675号公報にはポリビニル
アルコールのジメチルスルホキシド溶液全紡糸原液とし
てメタノール、エタノール、ベンゼン、クロロホルム等
の有機溶媒中に湿式紡糸する方法、特開昭56−128
309号公報には湿式または乾式紡糸法によって得られ
たポリビニルアルコール系繊維を少なくとも10倍以上
に延伸し九後熱処理する方法が提案されている。また特
公昭37−14422号公報や特公昭47−32142
号公報にはホウ酸またはホウ酸塩を含有するポリビニル
アルコール水溶液を種々の塩を含むアルカリ性凝固浴中
に紡糸し、ホウ酸をポリビニルアルコールに架橋させた
後、再びホウ酸またはその架橋物をその後の中和、水洗
などの工程で除去する方法が開示されている。しかしこ
れらの方法によって得られる繊維の強度Fi12f/d
r以下であった。For example, Japanese Patent Publication No. 43-16675 describes a method of wet spinning in a dimethyl sulfoxide solution of polyvinyl alcohol in an organic solvent such as methanol, ethanol, benzene, or chloroform as the entire spinning stock solution, and JP-A No. 56-128.
No. 309 proposes a method in which polyvinyl alcohol fibers obtained by wet or dry spinning are stretched at least 10 times or more and then heat-treated. Also, Japanese Patent Publication No. 37-14422 and Japanese Patent Publication No. 47-32142
The publication discloses that a polyvinyl alcohol aqueous solution containing boric acid or a borate salt is spun into an alkaline coagulation bath containing various salts, the boric acid is crosslinked to polyvinyl alcohol, and then the boric acid or its crosslinked product is then spun. Disclosed is a method for removing it through steps such as neutralization and washing with water. However, the fiber strength Fi12f/d obtained by these methods
It was below r.
一方特開昭60−126312号公報にはポリビニルア
ルコールの重合度が約4000でジメチルスルホキシド
を溶媒とし九乾湿式紡糸方法によシ、延伸倍率約30倍
強度209/drのポリビニルアルフール繊維を得るこ
とが示されているが、容易ではない。On the other hand, JP-A-60-126312 discloses that a polyvinyl alcohol fiber having a degree of polymerization of polyvinyl alcohol of about 4000 and a nine-dry wet spinning method using dimethyl sulfoxide as a solvent is used to obtain a polyvinyl alfur fiber with a stretching ratio of about 30 times and a strength of 209/dr. This has been shown to be possible, but it is not easy.
超高分子量ポリエチレンのゲル紡糸−超延伸の考え方を
ポリビニルアルコール線維に応用した例として特開昭5
9−130314号公報があるが、辷れは重合度約ao
oooのポリビニルアルフール繊維い、グリセリンまた
はエチレングリコールを溶媒として冷却によシゲル繊維
をつくり、最高強度19P/drのポリビニルアルコー
ル系繊維を得る方法である。しかしポリビニルアルコー
ル系繊維はポリエチレン繊維と異なシ分子問および分子
内に水素結合を有し、折りたたみ分子鎮をとりにくいと
考えられておシ、高重合度ポリビニルアルコールで濃度
を低くシ、分子鎮のからみを少なくしてもいまだ満足す
べき高い延伸倍率と高強力のポリビニルアルコール系繊
維を得ることは困難であった。Gel spinning of ultra-high molecular weight polyethylene - An example of applying the concept of ultra-stretching to polyvinyl alcohol fibers was published in JP-A-5
There is a publication No. 9-130314, but the degree of polymerization is about ao.
In this method, polyvinyl alcohol fibers of ooo are produced by cooling using glycerin or ethylene glycol as a solvent to obtain polyvinyl alcohol fibers with a maximum strength of 19 P/dr. However, unlike polyethylene fibers, polyvinyl alcohol-based fibers have hydrogen bonds between and within molecules, and are thought to be difficult to fold and retain their molecular weight. Even if the entanglement is reduced, it is still difficult to obtain polyvinyl alcohol fibers with a satisfactory high draw ratio and high strength.
高強力繊維を得るには分子鎮を高度に配向する必要があ
シ、そのためには高倍率に延伸する必要がある。ポリビ
ニルアルコール系繊維の場合高倍率延伸で高強力化を行
なうためKは次の点が考えられる。To obtain high-strength fibers, it is necessary to highly orient the molecular weight, and for this purpose, it is necessary to draw at a high magnification. In the case of polyvinyl alcohol fibers, the following points can be considered for K since high strength is achieved by stretching at a high ratio.
(1)高重合度ポリビニルアルコールを用いる。(1) Highly polymerized polyvinyl alcohol is used.
(2)低濃度ポリビニルアルコール溶液を用いる。(2) Use a low concentration polyvinyl alcohol solution.
(8) ゲル紡糸を行なう。(8) Perform gel spinning.
(4)分子間の水素結合を抑制する。(4) Suppress intermolecular hydrogen bonds.
(5)分子鎮間に適度の空隙を与える。(5) Providing appropriate voids between molecules.
(6)延伸時に繊維の着色分解を抑える。(6) Suppressing color decomposition of fibers during stretching.
従来上記(1)〜(6)を満足し高倍率延伸による高強
力ポリビニルアルコール系繊維を得る方法は見出されて
いなかった。Conventionally, no method has been found that satisfies the above (1) to (6) and obtains high-strength polyvinyl alcohol fibers by high-strength stretching.
(発明が解決しようとする課題)
以上の背景をふまえて、本発明者らは高強力ポリビニル
アルコール系繊維を得るために鋭意検討した。一般に繊
維強度を高くするには、高重合度のポリマーを用いて結
晶と結晶を結ぶタイ分子を多くすると同時に、分子鎮の
配向と結晶化を高めゐために高倍率延伸が必要となる。(Problems to be Solved by the Invention) Based on the above background, the present inventors conducted extensive studies in order to obtain a high-strength polyvinyl alcohol fiber. Generally, to increase fiber strength, it is necessary to use a polymer with a high degree of polymerization to increase the number of tie molecules that connect crystals, and at the same time to increase the orientation and crystallization of molecular chains, it is necessary to draw at a high magnification.
一方繊維が高温で延伸される時に、着色分解を抑制する
ことも高強力化の方向にある。本発明者らはポリマー分
子内の1.2−グリコール結合に着目し検討した結果、
1,2−グリコール結合が1.2モルチを超えると配向
結晶化を阻害したり、あるいは1,2−グリコール結合
の縮合によシポリエン結合が生成し、分解が生じ九シ着
色したりしやすくなって高強力繊維を得ることが困難と
なることが判った。On the other hand, suppressing color decomposition when fibers are drawn at high temperatures is also a way to increase strength. The present inventors focused on and studied the 1,2-glycol bond within the polymer molecule, and found that
If the number of 1,2-glycol bonds exceeds 1.2 molar, oriented crystallization may be inhibited, or cypolyene bonds may be formed by condensation of 1,2-glycol bonds, resulting in decomposition and easy discoloration. It has been found that it is difficult to obtain high strength fibers.
すなわち1,2−グリコール結合が1.2モルチ以下の
高重合度ポリビニルアルコールが高強力繊維を得るに有
効であることを見出し本発明に到達したのである。In other words, the present invention was achieved by discovering that polyvinyl alcohol with a high degree of polymerization having a 1,2-glycol bond of 1.2 molar or less is effective for obtaining high-strength fibers.
(課題を解決するための手段)
本発明は
r(1)平均重合度12,000以下のポリビニルアル
コール系ポリマーより成り、1.2−グリコール結合が
1.2モル−以下、ポリエン結合が100 ppm以下
、単砿維引張強度が117d以上である高強力ポリビニ
ルアルコール系繊維。(Means for Solving the Problems) The present invention consists of a polyvinyl alcohol polymer having an r(1) average degree of polymerization of 12,000 or less, with a 1.2-glycol bond of 1.2 mol or less and a polyene bond of 100 ppm. The following is a high-strength polyvinyl alcohol fiber having a single fiber tensile strength of 117d or more.
(2)平均重合度が12,000以下であり、1.2−
グリコール結合が1.2モル−以下であるポリビニルア
ルコール系ポリマーを少なくとも80チ以上使用し、延
伸倍率3倍以上で湿延伸を行ない、しかる後200℃以
上で全延伸倍率17倍以上の加熱延伸を行ない、1,2
−グリコール結合が1.2モルチ以下、ポリエン結合が
i o o ppm以下、単繊維引張強度が18 f/
d以上の線維を得ることを特徴とするポリビニールアル
コール系繊維の製造法。」
に関するものである。(2) The average degree of polymerization is 12,000 or less, and 1.2-
At least 80 or more polyvinyl alcohol-based polymers having glycol bonds of 1.2 mol or less are used, wet stretching is carried out at a stretching ratio of 3 times or more, and then heated stretching is carried out at a temperature of 200° C. or higher at a total stretching ratio of 17 times or more. conduct, 1, 2
- Glycol bond is 1.2 molar or less, polyene bond is IO ppm or less, single fiber tensile strength is 18 f/
A method for producing polyvinyl alcohol fibers, characterized by obtaining fibers with a particle size of d or more. ”.
以下本発明の内容をさらに詳細に説明する。The contents of the present invention will be explained in more detail below.
本発明に言うポリビニルアルコール系ポリマーとは、3
0℃の水溶液で粘度法により求めた平均重合度が12,
000以下のものであり、好it、<’は、3000〜
8000のものである。平均重合度12000以上でも
よいが、重合温度を低くする操作が必要であるなどコス
トアップになる。ケン化度は99.5モルチ以上で、1
,2−グリコール結合が162モルチ以下好ましくは1
.0モルチ以下のものである。The polyvinyl alcohol-based polymer referred to in the present invention is 3
The average degree of polymerization determined by the viscosity method in an aqueous solution at 0°C is 12,
000 or less, preferably it, <' is 3000 or less
8000. Although the average degree of polymerization may be 12,000 or more, it requires an operation to lower the polymerization temperature, which increases costs. Saponification degree is 99.5 molti or more, 1
, 2-glycol bond is 162 or less, preferably 1
.. It is 0 molti or less.
該ポリマーを得る方法としては、例えば10℃以下の重
合温度で、ビニルエステル最も好ましくは酢酸ビニルを
重合し、蒸留により未反応ビニルエステルを除去しアル
カリを添加して加アルコール分解を行なう方法がある。A method for obtaining the polymer includes, for example, polymerizing a vinyl ester, most preferably vinyl acetate, at a polymerization temperature of 10° C. or lower, removing unreacted vinyl ester by distillation, and performing alcoholysis by adding an alkali. .
重合方法はバルク重合、溶液重合、懸濁重合、エマルジ
ョン重合などの方法で重合することができる。0℃以下
の重合温度で重合する場合、水を媒体とする懸濁重合、
エマルジョン重合では氷点降下剤としてアルコール、グ
リコール、グリセリン、ジメチルスルホキシドまたは無
機塩などを水媒体に溶解させて重合を行なうことができ
る。必要とする重合度のポリビニルアルコールを得るた
めには重合温度、重合速度、モノマー濃度などを設定し
て重合するが、必要に応じて重合度調整剤たとえば、ジ
スルフィド、メルカプタン、ジアゾチオエーテル、ノ・
ロゲン化物などを用いることもできる。The polymerization can be carried out by methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. When polymerizing at a polymerization temperature of 0°C or lower, suspension polymerization using water as a medium;
In emulsion polymerization, polymerization can be carried out by dissolving alcohol, glycol, glycerin, dimethyl sulfoxide, or an inorganic salt in an aqueous medium as a freezing point depressant. In order to obtain polyvinyl alcohol with the required polymerization degree, polymerization is carried out by setting the polymerization temperature, polymerization rate, monomer concentration, etc. If necessary, polymerization degree regulators such as disulfide, mercaptan, diazothioether, etc.
Logenides and the like can also be used.
本発明でいうポリビニルアルコールの重合度はJIS
K 6726に基づき、前述のごとく30℃における水
溶液の極限粘度〔η〕から次式により重合度PAを測定
し九値で定義する
PA=((η〕X10’、/8.29)”−613但し
〔η〕の単位: g7t
なお本発明の場合平均重合度が単一系の場合に加えて1
.2−グリコール結合が1.2モルチ以下のポリビニル
アルコール系ポリマーを少なくとモ80重量−以上好ま
しくは90重量−以上占めるような混合系であってもよ
い。80重量%未清では1゜2−グリコール結合量が多
く、前述のごとくポリマーの着色分解が促進されたり、
配向結晶化が低下したシして高強力繊維は得難くなる。The degree of polymerization of polyvinyl alcohol in the present invention is determined according to JIS
Based on K 6726, the degree of polymerization PA is measured from the limiting viscosity [η] of the aqueous solution at 30°C as described above using the following formula, and defined as nine values: PA=((η)X10',/8.29)"-613 However, the unit of [η]: g7t In the case of the present invention, the average degree of polymerization is 1 in addition to the case of a single system.
.. A mixed system may be used in which the polyvinyl alcohol polymer having 2-glycol bonds of 1.2 molar or less accounts for at least 80% by weight or more, preferably 90% by weight or more. 80% by weight unclarified has a large amount of 1゜2-glycol bonds, and as mentioned above, coloring and decomposition of the polymer is promoted,
As oriented crystallization is reduced, it becomes difficult to obtain high-strength fibers.
例えば重合度3600と重合度10000.あるいは重
合度3000と重合度5000とのポリビニルアルコー
ル系ポリマー混合物などである。For example, the degree of polymerization is 3600 and the degree of polymerization is 10000. Alternatively, it may be a polyvinyl alcohol polymer mixture with a degree of polymerization of 3,000 and 5,000.
ポリビニルアルコール系ポリ!−には3重量−以下の顔
料、酸化防止剤、紫外線吸収剤、結晶化抑制剤などを添
加したものも含まれる。特にポリビニルアルコールのO
H基と分子間架橋を起こすホウ酸またはホウ酸塩を0.
5〜5重量%添加することはポリマーの曳糸性を向上さ
せ紡糸時のビス落ちや単糸切れを減少させると共にゲル
繊維の結晶化を抑えるので好ましい。ポリビニルアルコ
ールの平均重合度が高いほど欠陥部になり易い分子鎮末
端が少なく、かつ結晶間を連結するタイ分子が多く、高
強力高弾性率繊維になシ易い。Polyvinyl alcohol poly! - also includes those to which 3 weight or less of pigments, antioxidants, ultraviolet absorbers, crystallization inhibitors, etc. are added. Especially the O of polyvinyl alcohol
Boric acid or borate that causes intermolecular crosslinking with H groups is added to 0.
It is preferable to add 5 to 5% by weight because it improves the spinnability of the polymer, reduces screw dropout and single fiber breakage during spinning, and suppresses crystallization of gel fibers. The higher the average degree of polymerization of polyvinyl alcohol, the fewer molecular terminal ends that tend to become defects, and the more tie molecules that connect crystals, making it easier to form into a high-strength, high-modulus fiber.
ポリビニルアルコール系ポリマーの溶剤としては何でも
よいが、冷却でポリビニルアルコールがゲル化するよう
な溶剤が好ましく、例えばエチレンクリコール、トリメ
チレングリコール、ジエチレングリコール、グリセリン
などの多価アルコールやそれらと水との混合溶剤、ある
いはジメチルスルホキシド、ジメチルホルムアミド、ジ
エチレントリアミンやそれらと水との混合溶剤がある。Any solvent may be used for polyvinyl alcohol-based polymers, but solvents that cause polyvinyl alcohol to gel when cooled are preferred, such as polyhydric alcohols such as ethylene glycol, trimethylene glycol, diethylene glycol, and glycerin, and mixtures thereof with water. There are solvents, dimethyl sulfoxide, dimethyl formamide, diethylene triamine, and mixed solvents of these and water.
紡糸方式としては何でもよいが本発明ではポリビニルア
ルコール系ポリマーの溶液を紡糸ノズルから吐出させ直
ちに低温のメタノールやエタノールなどアルコール類あ
るいはそれらと該溶剤との混合液さらには無機塩を含む
水溶液に浸漬し急冷することKより透明ゲル横組を得る
方式が好ましい。この場合原液温度と凝固浴温度が大き
く異なるため湿式紡糸はできず、乾湿式紡糸ま九は冷却
のみでゲル化するゲル紡糸となるが、吐出される紡糸糸
条をできる限シ均一に急冷するためにノズルから凝固浴
までの距離を短かくして凝固浴へ浸漬させる。凝固紡糸
糸条は溶剤を含んだままで3倍以上の湿延伸を行なうの
が良い。湿延伸が3倍未満では紡糸時に生成した微結晶
の破壊が少なくそれ以降の延伸倍率が低く、高強力化は
難しくなる。本発明では湿延伸後溶剤をほぼ完全に除去
し続いて200℃以上好ましくは220℃以上で総延伸
倍率17倍以上となるように加熱延伸する。Any spinning method may be used, but in the present invention, a polyvinyl alcohol polymer solution is discharged from a spinning nozzle and immediately immersed in a low-temperature alcohol such as methanol or ethanol, or a mixture of these and the solvent, or an aqueous solution containing an inorganic salt. A method of obtaining transparent gel horizontal writing is preferable to rapid cooling. In this case, wet spinning is not possible because the temperature of the stock solution and the coagulation bath temperature are greatly different, and dry-wet spinning results in gel spinning that gels only by cooling, but the spun yarn that is discharged is rapidly cooled as uniformly as possible. Therefore, the distance from the nozzle to the coagulation bath is shortened and the product is immersed in the coagulation bath. The coagulated spun yarn is preferably wet-stretched three times or more while still containing the solvent. If the wet stretching is less than 3 times, the microcrystals generated during spinning will be less likely to be broken, and the subsequent stretching ratio will be low, making it difficult to increase the strength. In the present invention, after wet stretching, the solvent is almost completely removed, and then the film is heated and stretched at 200° C. or higher, preferably 220° C. or higher, to a total stretching ratio of 17 times or higher.
200℃未満の温度では延伸倍率が低く配向結晶化が十
分でないので好ましくない。また総延伸倍率が17倍以
下では分子配向が不十分となシ高強力は得が丸い。A temperature lower than 200° C. is not preferable because the stretching ratio is low and oriented crystallization is not sufficient. Further, if the total stretching ratio is 17 times or less, the molecular orientation will be insufficient and high strength will not be obtained.
本発明は高強力な繊維を得んとするものであるので上記
のような高温度での高倍率の延伸を必須とする。しかし
ここでポリビニルアルコールポリマー分子内の1.2−
グリフール結合が1.2モル−を越えると上記高温度で
の延伸処理を行なえば繊維の着色分解が生ずる。一方こ
の着色分解を生起させないような温度に延伸温度を低下
させれば、高度な延伸が出来なくなシ、その結果として
高強度な繊維を得ることが出来かくなるのである。従っ
て本発明においては、高強度高倍率の延伸処理でも繊維
の着色分解なく高強度な繊維とするために、1,2−グ
リコール結合を1.2モルチ以下に抑えるものである。Since the present invention aims to obtain highly strong fibers, the above-mentioned stretching at high temperature and high magnification is essential. However, here the 1.2-
If the number of glyfur bonds exceeds 1.2 moles, coloring and decomposition of the fibers will occur if the above-mentioned high-temperature stretching treatment is carried out. On the other hand, if the stretching temperature is lowered to a temperature that does not cause this color decomposition, it becomes impossible to achieve a high degree of stretching, and as a result, it becomes impossible to obtain high-strength fibers. Therefore, in the present invention, the 1,2-glycol bond is suppressed to 1.2 mole or less in order to obtain a high-strength fiber without discoloration and decomposition even during high-strength, high-magnification stretching treatment.
なおポリビニルアルコールの着色分解を出来るだけ抑え
る点で加熱温度とその温度での滞留時間を調節したシあ
るいは空気浴以外KN2ガス浴やシリコンオイル浴など
を用いるのは好ましい。本発明で言う高強力ポリビニル
アルコール繊維は試料長10cIL1引張速度5m/m
inで引張試験機によシ測定した単繊維強度が1897
6以上好ましくは20f/d以上のものを意味する。In addition, in order to suppress the color decomposition of polyvinyl alcohol as much as possible, it is preferable to use a KN2 gas bath, a silicone oil bath, etc. other than a bath or air bath in which the heating temperature and residence time at that temperature are adjusted. The high-strength polyvinyl alcohol fiber referred to in the present invention has a sample length of 10 cIL and a tensile speed of 5 m/m.
The single fiber strength measured by a tensile tester was 1897.
It means 6 or more, preferably 20 f/d or more.
前述のごと<1.2−グリコール結合が多くなると加熱
工程で分解し、脱水による二重結合が生成しやすくポリ
エン結合が生成する。ポリエン結合は1100ppまで
は生成してもかまわないが、1100pp以上になると
生成糸条が黄色味を呈したシ、強度が低下したシして好
ましくない。As mentioned above, when the number of <1.2-glycol bonds increases, it decomposes during the heating process, and double bonds are likely to be formed due to dehydration, resulting in the formation of polyene bonds. Polyene bonds may be formed up to 1,100 pp, but if the amount exceeds 1,100 pp, the resulting yarn will have a yellowish tinge and its strength will decrease, which is not preferable.
次K 1.2−グリコール結合・含有量、ポリエン結合
金有量の測定法について説明する。Next K 1. The method for measuring 2-glycol bond/content and polyene bond gold content will be explained.
ポリビニルアルコール中の1,2−グリコール結合量に
ついては、ポリビニルアルコールのDMSO−ds浴溶
液5%程度のトリフロロ酢酸を添加し、500MHz
” H−NMRを測定する。そのスペクトルのδ=3.
25ppm付近に現われるピークの面積をAとし、δ=
1.2〜1.8ppmのピーク面積をBとすると次式(
1)で1.2−グリコール結合量を求めることができる
。Regarding the amount of 1,2-glycol bond in polyvinyl alcohol, add about 5% trifluoroacetic acid to a DMSO-ds bath solution of polyvinyl alcohol, and
”Measure H-NMR. δ of the spectrum is 3.
Let A be the area of the peak that appears around 25 ppm, and δ=
If the peak area of 1.2 to 1.8 ppm is B, then the following formula (
1) The amount of 1.2-glycol bond can be determined.
またポリビニルアルコール中のポリエンの量ハ1H−島
侃により定量を行なう。δ=5.8〜7.4ppmに存
在するピークの全部の面積をAとし、δ=1.2〜1、
gppmのピーク面積をBとすると次式り2)でポリエ
ン量を求めることができる。Further, the amount of polyene in polyvinyl alcohol is determined by 1H-island. Let A be the total area of the peaks present at δ = 5.8 to 7.4 ppm, and δ = 1.2 to 1,
Letting the peak area of gppm be B, the amount of polyene can be determined using the following formula 2).
以下実施例によシ本発明を具体的に説明するが、本発明
は実施例のみに限定されるものではない。The present invention will be specifically explained below using examples, but the present invention is not limited only to the examples.
実施例1および比較例1
平均重合度4500,1.2−グリコール結合0.9モ
ル−〇完全ケン化ポリビニルアルコールを9重量%にな
るようにグリセリンに170℃にて溶解せしめた。次い
で該溶液を170℃で孔径0.2u+。Example 1 and Comparative Example 1 Completely saponified polyvinyl alcohol with an average degree of polymerization of 4500 and 1.2-glycol bonds of 0.9 mol was dissolved in glycerin at 170° C. to a concentration of 9% by weight. The solution was then heated to 170° C. to a pore size of 0.2 u+.
ホール数20のノズルよシ吐出させ25w下の凝固浴に
落下せしめた。凝固浴組成はメタノール/グリセリン=
9/1であ多温度は0℃とした。乾湿式ゲル紡糸後、延
伸倍率4倍で湿延伸を行ないしかるのちメタノールで溶
剤を抽出し60”C,の熱風でメタノールを除去した。It was discharged through a nozzle with 20 holes and dropped into a coagulation bath under 25W. Coagulation bath composition is methanol/glycerin =
In 9/1, the temperature was 0°C. After dry-wet gel spinning, wet stretching was carried out at a stretching ratio of 4 times, and then the solvent was extracted with methanol and the methanol was removed with hot air at 60"C.
次いで19〜23倍の総延伸倍率となるよう248℃で
乾熱延伸を施した。得られた延伸糸の単繊維強度は22
f/dであつ九。また1、2−グリコール結合Fio
、9モルチでポリエン結合は50 ppmであった。Next, dry heat stretching was performed at 248° C. to give a total stretching ratio of 19 to 23 times. The single fiber strength of the obtained drawn yarn was 22
f/d at nine. In addition, 1,2-glycol bond Fio
, 9 molti and the polyene bond was 50 ppm.
なお比較例1として1,2−グリコール結合が1,5モ
ルチのポリビニルアルコールを使用したが得られた延伸
糸の単繊維強度は17 f/dと低下し着色分解を起し
た。In Comparative Example 1, polyvinyl alcohol having a 1,2-glycol bond of 1,5 molt was used, but the single fiber strength of the resulting drawn yarn was reduced to 17 f/d, and color decomposition occurred.
実施例2
平均重合度7000.1,2−グリコール結合0.8モ
ルチの完全ケン化ポリビニルアルコールを5重量%にな
るようにジメチルスルホキシドに95℃で溶解せしめた
。次いで該溶液を80℃で乾湿式ゲル紡糸した。凝固浴
組成はメタノール/ジメチルスルホキシド=6/4であ
り温度は10℃とした。Example 2 Completely saponified polyvinyl alcohol with an average degree of polymerization of 7000.1,2-glycol bonds of 0.8 mol was dissolved in dimethyl sulfoxide at 95°C to a concentration of 5% by weight. The solution was then wet-dry gel spun at 80°C. The coagulation bath composition was methanol/dimethyl sulfoxide = 6/4, and the temperature was 10°C.
紡糸後延伸倍率5倍で湿延伸を行なった。その後実施例
1と同様にして処理し、総延伸倍率20〜23倍となる
よう248℃で乾熱延伸した。得られた延伸糸の単繊維
強度は21 f/dであった。また1、2−グリコール
結合量0.8モルチ、ポリエン結合75ppmであった
。After spinning, wet stretching was performed at a stretching ratio of 5 times. Thereafter, it was treated in the same manner as in Example 1, and dry-heat stretched at 248° C. to a total stretching ratio of 20 to 23 times. The single fiber strength of the obtained drawn yarn was 21 f/d. Further, the amount of 1,2-glycol bond was 0.8 mol, and the polyene bond was 75 ppm.
実施例3
平均1合度2700.1,2−グリコール結合1.4モ
ルチの完全ケン化ポリビニルアルコール/平均重合度9
000,1.2−グリコール結合0.7モルチの完全ケ
ン化ポリビニルアルコール=1/9の混合物をグリセリ
ンに溶解せしめ、実施例1と同様に処理し、最終的に2
35℃で乾熱延伸を施した。Example 3 Average degree of polymerization: 2700. Completely saponified polyvinyl alcohol with 1.4 moles of 1,2-glycol bonds/average degree of polymerization: 9
000,1.2-Glycol bond A mixture of 0.7 mol of completely saponified polyvinyl alcohol = 1/9 was dissolved in glycerin, treated in the same manner as in Example 1, and finally 2
Dry heat stretching was performed at 35°C.
得られた延伸糸の単繊維強度は23 f/dであった。The single fiber strength of the obtained drawn yarn was 23 f/d.
また1、2−グリコール結合は0.75モルチ、ポリエ
ン結合45 ppmであった。Furthermore, the amount of 1,2-glycol bond was 0.75 ppm, and the amount of polyene bond was 45 ppm.
Claims (2)
ール系ポリマーより成り、1,2−グリコール結合が1
.2モル%以下、ポリエン結合が100ppm以下、単
繊維引張強度が18g/d以上である高強力ポリビニル
アルコール系繊維。(1) Made of polyvinyl alcohol polymer with an average degree of polymerization of 12,000 or less, with 1,2-glycol bond
.. A high-strength polyvinyl alcohol fiber having a polyene bond of 2 mol% or less, a polyene bond of 100 ppm or less, and a single fiber tensile strength of 18 g/d or more.
グリコール結合が1.2モル%以下であるポリビニルア
ルコール系ポリマーを少なくとも80%以上使用し、延
伸倍率3倍以上で湿延伸を行ない、しかる後200℃以
上で全延伸倍率17倍以上の加熱延伸を行ない、1,2
−グリコール結合が1.2モル%以下、ポリエン結合が
100ppm以下、単繊維引張強度が18g/d以上の
繊維を得ることを特徴とするポリビニルアルコール系繊
維の製造法。(2) The average degree of polymerization is 12,000 or less, and 1,2-
Use at least 80% or more of a polyvinyl alcohol polymer with glycol bonds of 1.2 mol% or less, perform wet stretching at a stretching ratio of 3 times or more, and then heat stretching at a total stretching ratio of 17 times or more at 200°C or higher. conduct, 1, 2
- A method for producing polyvinyl alcohol fibers, characterized by obtaining fibers having a glycol bond of 1.2 mol % or less, a polyene bond of 100 ppm or less, and a single fiber tensile strength of 18 g/d or more.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP18384288A JPH0233314A (en) | 1988-07-22 | 1988-07-22 | High-tenacity polyvinyl alcohol based fiber and production thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP18384288A JPH0233314A (en) | 1988-07-22 | 1988-07-22 | High-tenacity polyvinyl alcohol based fiber and production thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0233314A true JPH0233314A (en) | 1990-02-02 |
Family
ID=16142795
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP18384288A Pending JPH0233314A (en) | 1988-07-22 | 1988-07-22 | High-tenacity polyvinyl alcohol based fiber and production thereof |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0233314A (en) |
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---|---|---|---|---|
JP2001003249A (en) * | 1999-06-23 | 2001-01-09 | Kuraray Co Ltd | Water soluble nonwoven fabric for packing detergent |
JP2008133345A (en) * | 2006-11-28 | 2008-06-12 | Japan Vam & Poval Co Ltd | Method for polymerizing aliphatic vinyl ester and method for producing polyvinyl alcohol-based resin |
JP2013177646A (en) * | 2008-02-19 | 2013-09-09 | Kuraray Co Ltd | Vinyl alcohol-based polymer |
JPWO2012043280A1 (en) * | 2010-09-27 | 2014-02-06 | 積水化学工業株式会社 | Modified polyvinyl alcohol, modified polyvinyl acetal and ceramic slurry composition |
WO2017170938A1 (en) * | 2016-03-31 | 2017-10-05 | 株式会社クラレ | Polyvinyl alcohol |
JP2019065068A (en) * | 2017-09-28 | 2019-04-25 | 株式会社クラレ | Polyvinyl alcohol |
-
1988
- 1988-07-22 JP JP18384288A patent/JPH0233314A/en active Pending
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001003249A (en) * | 1999-06-23 | 2001-01-09 | Kuraray Co Ltd | Water soluble nonwoven fabric for packing detergent |
JP2008133345A (en) * | 2006-11-28 | 2008-06-12 | Japan Vam & Poval Co Ltd | Method for polymerizing aliphatic vinyl ester and method for producing polyvinyl alcohol-based resin |
JP2013177646A (en) * | 2008-02-19 | 2013-09-09 | Kuraray Co Ltd | Vinyl alcohol-based polymer |
JPWO2012043280A1 (en) * | 2010-09-27 | 2014-02-06 | 積水化学工業株式会社 | Modified polyvinyl alcohol, modified polyvinyl acetal and ceramic slurry composition |
JP5555718B2 (en) * | 2010-09-27 | 2014-07-23 | 積水化学工業株式会社 | Process for producing modified polyvinyl acetal |
WO2017170938A1 (en) * | 2016-03-31 | 2017-10-05 | 株式会社クラレ | Polyvinyl alcohol |
KR20180132749A (en) * | 2016-03-31 | 2018-12-12 | 주식회사 쿠라레 | Polyvinyl alcohol |
CN109071715A (en) * | 2016-03-31 | 2018-12-21 | 株式会社可乐丽 | polyvinyl alcohol |
US11111319B2 (en) | 2016-03-31 | 2021-09-07 | Kuraray Co., Ltd. | Polyvinyl alcohol |
JP2019065068A (en) * | 2017-09-28 | 2019-04-25 | 株式会社クラレ | Polyvinyl alcohol |
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