JPS5943112A - Manufacture of polyvinyl alcohol synthetic fiber - Google Patents

Abstract

PURPOSE:To prepare the titled synthetic fiber having excellent alkali resistance and adhesivity to cement, and suitable as a reinforcing material for cement, by extruding a polyvinyl alcohol spinning solution containing boric acid or a copper salt into a specific coagulation bath. CONSTITUTION:A polyvinyl alcohol spinning solution added with boric acid or a copper salt such as cupric sulfate, is extruded into a coagulation bath containing sodium hydroxide, sodium sulfate, etc. wherein the concentration of the caustic alkali (Xg/l) and that of the dehydrating salt (Yg/l) satisfy the conditions of formulas I , II and III at the same time. The spun fiber is subjected to the neutralization treatment and wet-heat treatment, washed with water, dried, drawn by hot drawing in hot air, and heat treated preferably at >=200 deg.C (especially 230-250 deg.C) to obtain the objective polyvinyl alcohol synthetic fiber.

Description

【発明の詳細な説明】 本発明は，ポリビニルアルコール（以下ＰＶＡと略記す
る。）系合成繊維の製造法に関するものであり，更に詳
しく（徒セメント補強材として好適なＰＶＡ系合成繊維
の製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyvinyl alcohol (hereinafter abbreviated as PVA)-based synthetic fiber, and more specifically relates to a method for producing PVA-based synthetic fiber suitable as a reinforcing material for cement. It is something.

ＰＶＡ系合成繊維の湿式紡糸法としては，第一にＰＶＡ
系水溶液を硫酸ナトリウム（以下ボウ硝と略す。）等の
飽和水溶液の凝固浴に紡出する方法が知られている。こ
の方法で得られる繊維の横断面は馬蹄形で二重構造を有
ｌ〜てｂる。ただ，この繊維ｔま強度及びヤング率がそ
れほど高くないのでセメント等の補強材としては充分な
効果を有するものではない。第二にＰＶＡ系水溶液を濃
厚力性アルカリの凝固浴に紡出する方法が知られている
。この方法で得られる繊維は高い強度及びヤング率？有
するが，繊維の横断面は円形である。第三にＰＶＡ水溶
液にキレート架橋が成立するホウ酸や銅塩等を添加し少
量のカ性アルカリと飽和ボウ硝水溶液の凝固浴に紡出す
る方法が知られている。この方法で得られる繊維の性能
は高い強度及びヤング率を有するが，ｆＲ卸の横断面Ｉ
ｔｓＩ靖円形である。The first wet spinning method for PVA-based synthetic fibers is PVA
A method is known in which a system aqueous solution is spun into a coagulation bath of a saturated aqueous solution such as sodium sulfate (hereinafter abbreviated as sulfate). The fibers obtained by this method have a horseshoe-shaped cross section and a double structure. However, since the fiber strength and Young's modulus are not so high, it is not sufficiently effective as a reinforcing material for cement, etc. A second known method is to spin a PVA-based aqueous solution into a concentrated alkaline coagulation bath. Does the fiber obtained by this method have high strength and Young's modulus? However, the cross section of the fiber is circular. Thirdly, a method is known in which boric acid, copper salt, etc. that form chelate crosslinking are added to an aqueous PVA solution, and the resulting solution is spun into a coagulation bath of a small amount of caustic alkali and a saturated aqueous salt solution. The performance of the fiber obtained by this method is high strength and Young's modulus, but the cross section of fR wholesale I
It is a tsI circular shape.

一方，セメントをベースにした成形品，各種構築物等に
必要とされる材料特性としては曲げ強度，衝撃強度及び
ひび割れ強度等があげられ．このグこめ各種の補強材が
使用されている。すなわち，補強材として無機繊維や有
機繊維をセメントマトリックスの中に分散さすことが行
われている，．無機繊維としそは石綿を配合したスレー
ト板が代表的であり，又耐アルカリガラス繊維を配合し
たガラス繊維強化セメント成形品．ある１いは鋼繊維等
を補強材としたセメント成？形品も知られている。一方
，有機繊維としてはポリエチレン系．ＰＶＡ系あるいは
ポリプロピレン系等の合成繊維も一部補強材として使用
されている。On the other hand, material properties required for cement-based molded products and various structures include bending strength, impact strength, and cracking strength. Various reinforcing materials are used for this purpose. In other words, inorganic fibers and organic fibers are being dispersed into the cement matrix as reinforcing materials. A representative example of inorganic fibers is slate boards containing asbestos, and glass fiber-reinforced cement molded products containing alkali-resistant glass fibers. Or is it made of cement with reinforcing materials such as steel fibers? Shapes are also known. On the other hand, polyethylene is an organic fiber. Some synthetic fibers such as PVA or polypropylene are also used as reinforcing materials.

しかしながら・石！ＶＣ″Ａては発ガ７性物質と認定さ
れ健康障害の問題があり．．又供給のすべてを輸入にた
よっており不安定アあるという問題がある。又スレート
板は性能面で衝撃強度が．低いという問題がある。又，
耐：アルカリガラス繊維は耐アルカリ性がそれ程完全で
はなく，セメント成形後時間と共に曲け強度が低下する
という問題があるので，その用途はカーテンウオールや
外壁バネルＫ使用され非構造材に限定されているし，又
作業性についても皮膚障害が発生するという問題がある
。一方，合成繊維については前記ＰＶＡ系合．：成＊’
Ｍに見られる如く繊維の横断面形状が円形や．．楕円１
２．杉あるいは馬蹄形であるのでセメントとの接“’Ｉ
Ｍ種”’ＪＥ％（，又ヤング率がセメントマトリックス
より小さいためにひび割れ強度に問題を残しているジこ
れに対し，繊維横断面異形化ＰＶＡ系合成繊維として，
！Ｉ？開昭５６−１４０１１３号公報に炭酸カルシウム
等，特開昭５６−１５４５１３号公報に硫酸マグネシウ
ム等を混合紡糸する方法等が提案されて″′４が・紡調
が不安定１あり・又混合物？一部が浴中に溶出するため
湿熱浴の管理が繁雑であるという問題がある。However, stone! VC''A is recognized as a gas-causing substance and poses a health hazard.Also, all supplies are dependent on imports, resulting in instability.Also, slate boards have low impact strength in terms of performance. ．There is a problem that the value is low.Also,
Resistance: Alkali glass fiber does not have perfect alkali resistance, and its bending strength decreases over time after cement formation, so its use is limited to non-structural materials, such as curtain walls and exterior wall panels. However, there is also the problem of workability in that skin disorders occur. On the other hand, regarding synthetic fibers, the PVA-based composites mentioned above. :Nari*'
As seen in M, the cross-sectional shape of the fiber is circular. ．． Ellipse 1
2. Because it is cedar or horseshoe-shaped, there is no contact with cement.
In contrast, as a PVA-based synthetic fiber with deformed fiber cross-section,
! I? Japanese Unexamined Patent Publication No. 56-140113 proposed a method of mixing calcium carbonate, etc., and Japanese Unexamined Patent Publication No. 56-154513 proposed a method of mixing and spinning with magnesium sulfate, etc. ``'4 ・Unstable spinning 1 ・Additionally, a mixture? There is a problem in that the management of the moist heat bath is complicated because a part of it is eluted into the bath.

繊維による七メ．ント成形品等の補強に際しては．繊維
の強度及びヤング率が高く仝れば成形品の曲げ強度も高
くなることが一般に認められており，又繊維とセメント
との接着強度が高くなればなる程その補強効果がより充
分なものとなることも一般に認められている。Seven fibers. When reinforcing molded products etc. It is generally accepted that the higher the fiber strength and Young's modulus, the higher the bending strength of the molded product, and the higher the adhesive strength between the fiber and cement, the more sufficient the reinforcing effect will be. It is also generally accepted that

そこで本発明者らは，耐アルカリ性が良好で．強度及び
ヤ・ング率が高く，セメントとの接着性が良好でセメン
トの補強効果が優れ，かつ健康障害や皮膚障害がない繊
維を生産管理・も容易に製造する方法を提供することを
泪的と．・して鋭意研究の結果．ホウ酸又は銅塩を含？
有するＰ■・Ａ系紡糸原液を特定の凝固浴中に紡出し．
？繊維を・製造することによって上記の泪的が達成でき
るという事実を見い出し．本発明に．到達したもの・・
である。Therefore, the present inventors discovered that the alkali resistance is good. Our mission is to provide a method for easily manufacturing fibers with high strength and young modulus, good adhesion to cement, excellent reinforcing effect on cement, and no health or skin problems. and.・Results of intensive research. Contains boric acid or copper salts?
The P■/A-based spinning stock solution having the following properties is spun into a specific coagulation bath.
? Discovered the fact that the above aspirations can be achieved by manufacturing fibers. To the present invention. What we have reached...
It is.

すなわち本発明は・，ホウ酸又は銅塩を添加したＰＶＡ
系紡糸原液をが性アルカリ′濃度（ＸＩｌ／ｔ）及び脱
水性塩類濃度（Ｙ１１／ｔ）が下記（ａ）．（ｂ）−（
ｃ）式の条件を同時に満足する凝固浴・中に紡出し，つ
いで常法の中和，湿熱処理を行った後，水洗，乾燥し．
更Ｋ熱延伸を施すことを特徴とするＰＶＡ系合成繊維の
製造法である。That is, the present invention is based on PVA to which boric acid or copper salt has been added.
The concentration of alkali (XIl/t) and the concentration of dehydrating salt (Y11/t) of the spinning dope are as follows (a). (b)-(
c) It is spun into a coagulation bath that satisfies the conditions of formula at the same time, and then subjected to conventional neutralization and moist heat treatment, followed by washing with water and drying.
This is a method for producing PVA-based synthetic fibers, which is characterized by subjecting it to further K hot stretching.

Ｙ≦４１５−１．６８Ｘ（ａ） Ｙ≧８５０−５Ｘ（ｂ） Ｙ≧１８５−０．５８Ｘ（ｅ） 本発明によれば，従来のＰＶＡ・系合成繊維のような馬
蹄形，ｔｉｌ！円形あるい？は円形の横断面の場合忙は
見られなかった角のある横断面を有し，しかも場合によ
っては１〜３ミ久ロンの突起を有する繊維が得られる。Y≦415-1.68X (a) Y≧850-5X (b) Y≧185-0.58X (e) According to the present invention, the horseshoe-shaped, til! Is it circular? Fibers are obtained which have an angular cross section, which was not observed in the case of a circular cross section, and in some cases have protrusions of 1 to 3 μm.

本発明の方法によってＰＶＡ系合成繊維を製造するには
，紡糸原液としてホウ酸又は銅塩を添加したＰＶＡ系紡
糸原液を用いることが必要である。In order to produce PVA-based synthetic fibers by the method of the present invention, it is necessary to use a PVA-based spinning dope to which boric acid or copper salt has been added.

本発明に用いられる銅塩としては，たとえば硫酸第一？
銅，硫酸第二銅，硝酸銅などの水溶性銅塩があげられる
が．特に好ましいのは硫酸第二銅である。ホウ酸又は銅
塩の添加量はＰＶＡに対し０．３〜４重量係，好ましく
は０．６〜２重量チである。Examples of copper salts used in the present invention include sulfuric acid-1?
Examples include water-soluble copper salts such as copper, cupric sulfate, and copper nitrate. Particularly preferred is cupric sulfate. The amount of boric acid or copper salt added is 0.3 to 4 parts by weight, preferably 0.6 to 2 parts by weight, based on PVA.

本発明に用いるＰＶＡの好ましい平均重合度は１０００
〜２５００，特に１３００〜１８００である。ＰＶＡｏ
ケン化度は特に限定されないが９９．５〜９８モルチの
ものが好ましい。紡糸原液中のＰＶＡの濃度は１０〜２
５重量チ．特に１４〜２０重量チが好ましい。紡糸原液
のＰＲは原液がアルカリ性となるとゲル化が起こり，一
方，あまり低くなりすぎると装置等の腐蝕の問題が発生
するので４．０〜５４８の範囲が好ましい。The preferred average degree of polymerization of PVA used in the present invention is 1000.
~2500, especially 1300-1800. PVAo
Although the degree of saponification is not particularly limited, it is preferably 99.5 to 98 mol. The concentration of PVA in the spinning stock solution is 10-2
5 weight chi. Particularly preferred is 14 to 20 weight. The PR of the spinning dope is preferably in the range of 4.0 to 548, since gelation occurs when the dope becomes alkaline, and on the other hand, if it becomes too low, problems of corrosion of equipment etc. occur.

本発明においては，かかる紡糸原液を．カ性アルカリ濃
度（ＸＩ／ｔ＞及び脱水性塩類＃′度（Ｙ１／ｔ）が前
記（ａ）−’（ｂ）．（ｃ）式の条件を同時に満足する
・従固浴中に紡出することが必要である。In the present invention, such a spinning stock solution is used. The caustic alkali concentration (XI/t> and the degree of dehydrating salts #' degree (Y1/t) simultaneously satisfy the conditions of the above formulas (a)-'(b).(c).Spinning in a solid bath It is necessary to.

第１図は本発明の凝固浴糸件を示ずグラノであり，タテ
軸１・：ｊ−脱水性塩類（／ａＩＮＦ（Ｅ／／，），ヨ
コ軸は力性アルｌｉｌ濃度（９／／）であり，斜線で囲
まれた部分が本発明のνｆ固浴須域である。Figure 1 shows the coagulation bath properties of the present invention, but the vertical axis shows the concentration of 1. ), and the area surrounded by diagonal lines is the νf hard bath area of the present invention.

カ性アルカリとしてｖ」．たとえばカ性ソーダ．カ性カ
リが好土し〈用いらわ、る。カ性アルカリの濃度か１３
１９／ｔ未イγ４の場合・は．得られる繊テ．｛［の横
断而が１１′１円形であり．一方２０９ｇｌｔを越える
』希合は購断面が円形である。脱水性塩類と１〜て（づ
：，７’Ｃとえばボウ硝．硫酸カリウノ・，硫酸亜鉛，
値酸マグネシウム，硝酸ソーダなどが川いられるが，！
［♀に好斗しいのＣ・よボウ硝である。脱水性塩類の濃
度１４力性アルカリか１３０Ｅ／ｔの場合２００９／ｔ
でほぼ飽和に達【２．一方６４ｊｉ／Ｌ未満の場合は紡
調が悪い。（ａ．）５（．：Ｕ、！〕高’６：λ度のカ
性アルカリあるいは脱水｛’ＬｊＸＫ類ｋ・含むｊ′ｆ
固浴は脱水性塩類がほぼ飽和に達［７ていｌ）Ｌｉ’）
で作成できプｒい１−２，又（ｂ）式及び（ｅ）式より
カ性アルカリあるい（ｒま脱水性塩類が低（農度の場含
ぱ得られる繊、イｔの債助而が円形ないし楕円形とｋる
。凝固浴の温１｛（は３５−５５℃：．行に４０〜５５
℃が好一ましい。As a causative alkali v”. For example, caustic soda. Potassium is a good soil. The concentration of caustic alkali is 13
In the case of γ4 without 19/t. The resulting fiber. The cross section of {[ is 11'1 circular. On the other hand, the purchasing surface of "over 209 glt" is circular. Dehydrating salts and
Magnesium acid, sodium nitrate, etc. can be found in the river, but!
[This is C. Yobousou, who is very friendly with the male. If the concentration of dehydrating salts is 14% alkali or 130E/t, 2009/t
It reached almost saturation at [2. On the other hand, if it is less than 64 ji/L, the spinning quality is poor. (a.) 5 (.:U,!] High'6: λ degree caustic alkali or dehydration {'Lj
The solid bath is almost saturated with dehydrating salts.
1-2, and formula (b) and formula (e), the content of caustic alkali or dehydrating salts is low. The temperature of the coagulation bath is 35-55℃: 40-55℃.
℃ is preferable.

木発明Ｖこおいては。凝固浴を出た糸条を常法１（より
中和，湿熱処理を行った後．水洗．乾燥し，更に熱４！
Ｆ；伸する。熱ク１ｒ′．伸（で続いて２０旧：以十，
ｙ要すれば好才し〈は２３０〜２．５０Ｃで熱処理する
。Wood invention V here. After leaving the coagulation bath, the yarn is neutralized using the conventional method 1 (after being subjected to moist heat treatment, washed with water, dried, and further heated to 4!
F: Stretch. Heat 1r'. Shin (followed by 20 old: 10,
If necessary, heat treat at 230 to 2.50C.

本発明の方法に。しり｛！！’ｖ：ｈるＰｖ八系合成恢
肩ずは？）．水性で，酊アルカリ性なのでセメントマト
リノクスに充分・馴み．かつセメントマトリックス中で
も侵されない。又高い：：ＩＩｒＩＸリ，ヤング率を有
（７ていＺ）。従一って９このｓ：＊．ｐｘイｐで補強
さナシ／ｒ．セメント成形晶（．ｌｉ：匣Ｊ７−／辷曲
げｒｊｉａ度及びひび１１、＋ｊｈ．強度を４１′干ろ
。To the method of the invention. Shiri {! ! 'v: hru Pv 8 series synthetic combination shoulder? ). It is water-based and alkaline, so it is compatible with cement matrix. And it is not attacked even in cement matrix. It also has a high Young's modulus (7% Z). Juichi 9 this s: *. Not reinforced with px ip/r. Cement forming crystal (.li: box J7-/bending rjia degree and crack 11, +jh. strength 41' drying.

又．本発明の方ｌ，りにより得らノ１，／ζ性Ｎ１１邑
従フ１クの馬蹄形，１貰円形及び円形の横１新而と＆；
ｔｌＡなる異形化された１１゛＾断而４・有する。従一
）て．」＝メントに混和された場合，投錨効果によりセ
メントとの接着効果を発揮するものである。又，イ！！
られた慮託は１１４度な伸１７）：′７ｔ有ずるので耐
衝撃件ｄγ善にも効果がある。or. According to the method of the present invention, the horseshoe shape of the /ζ property N11 and the circular shape and the horizontal shape of the circular shape and &;
It has a deformed 11゛＾but4 called tlA. Juichi) Te. When mixed with cement, it exhibits an adhesive effect with cement due to its anchoring effect. Again, yes! !
Since the given consideration has an elongation of 114 degrees 17):'7t, it is also effective in improving the impact resistance.

本発明の方法により得らハ，た熾１ｆ．ｆ［を｛ｉｌ．
ｊ川Ｌ？５ｉ！式抄造法でセメント積層板を成形する場
合の繊維添加量０寸，セメントマトリックス中での繊糸
ｔの分散性と曲げ強度乃び衝慇強度を考慮すると，好斗
１，〈は（１３〜２５Ｍ〔惜チ，とくに０．５〜２重Ｅ
λ係が，１′｛好である。Obtained by the method of the present invention 1f. f[{il.
J river L? 5i! When forming a cement laminate using the paper-making method, considering the fiber addition amount of 0, the dispersibility of the fibers in the cement matrix, the bending strength, and the impact strength, the 25M [Sadly, especially 0.5~2 double E
The λ coefficient is 1'.

以１−゛，実ＩＸ（口ｌＪリをあげて本発明をさらに具
体的に説明する。Hereinafter, the present invention will be explained in more detail with reference to Example 1-1.

尚，繊だ１補強セメント板の作成と性能測定ｒ：ｌ：，
ＰＶＡ系合成糊λｚＩｆと（２て６ｍｍｌ）こ切断した
ものを４！・用Ｌ，以｝のとおり行った。In addition, the preparation and performance measurement of fiber 1 reinforced cement board r:l:,
PVA-based synthetic glue λzIf (2 to 6 mml) was cut into 4 pieces!・I did it as follows.

（１）曲げ強１戊，四性，衝撃強度 繊維２２＠部，バルプ３重ト」．部，スペシｒルクレイ
１０重ｔ部峻び普；ｌｊｌボノレトランドセメント８５
重Ｍ部を混合し２．湿式抄造法（ｌζてセメン｝ｆ一ｔ
層板を成形し，次いで２旧〕，湿空中で２８１１間養生
１−７セメント板を作成した。このスレート板について
ｔｉｔ口げ強度，シャルピー衝撃強度を測定した。尚靭
性Ｃ↓曲げ強度測定チヤ−１一紙より面積比で示した。(1) Bending strength: 1 x 4, impact strength: 22 parts, bulge: 3 parts. part, special clay 10 weight t part sharp; ljl Bonoretland cement 85
2. Mix the heavy M part. Wet papermaking method
The laminate was molded and then cured in humid air for 2811 hours to create a 1-7 cement board. The tit tip strength and Charpy impact strength of this slate board were measured. Toughness C ↓ Bending strength measurement chart 1 It is shown as an area ratio from a piece of paper.

（２）ひび割れ強度 ｉ．：ＲＡＪｋ．普通ボルトランドセメント，硅砂５号
及び水を０．００３対１対２対０．５の重ｈ［割合で混
合し，得られたモルタルを用いてリング拘束試験法（鋼
製リングの内径８３ｍ．モルタルリング２０ｍｍ厚さ）
により，ひび割れが発生する日数を求めた。(2) Crack strength i. :RAJk. Ordinary Boltland cement, silica sand No. 5, and water were mixed in a ratio of 0.003:1:2:0.5, and the resulting mortar was tested using the ring restraint test method (steel ring with an inner diameter of 83 m. mortar ring 20mm thick)
The number of days for cracks to occur was determined.

（３）繊維どセメントとの接着性 繊維をセメントに対し０．２重量係添加し，水とセ５メ
ントの比率全０５とし，セメントとし，ては普通ボルト
ランドセメントを用いてセメント中Ｖこｉｉｑａ；ｉを
分散させた。(3) Adhesiveness with fiber cement Add 0.2 weight of fiber to the cement, make the total ratio of water and cement 0.5, and use ordinary boltland cement as cement. iiqa;i was dispersed.

このものを２０℃，湿空中で４１１間養生し七メン｝・
仮を得，得られたセメント版を破断し．破断面の繊維の
吐出長を測宇した。（吐出畏の・℃σかい方が接イＩ′
１．が自好である。）実施例１．２．比較例１〜３ 平均重合１１３１４９０（７）ＰＶＡ肴：１６％度カ１
６．２，ｆＩ〕となるよう水に溶解し，イＵらノ１，た
浴液にＰＶＡに対＋，ｉ．：３重縫φのボウ酸を添力１
目−．ｐｕを５７に調整して紡糸原帛を作成した。この
紡糸原液を，水酸化ナトリウム１５ｔ）ｇ／ｔ，ボウ硝
１．６０１！／ｌ−で５０Ｃのアルカリ性のｊ盆類浴を
凝固浴として紡出１−２，第１ローラーと第２ローラ間
で４１８ＩＪｌ〔伸した後，ボウ硝３００１／ｔ，硫酸
２５１１／ｔ金含む酸性の塩戸浴にて４０℃で中和処理
いついでボウ硝３’６０９／／，，硫酸２０ｇ／ｔを含
む酸性の塩類浴に？で９０で＋湿熱処理を行った後水綜
？用い洗浄し，さらに油？剤処理［，．乾燥後２３５℃
の熱風中に′Ｃ４倍臓延伸口次に２４（１℃で定長熱処
理を行ってＰＶＡ系合成繊維を得た（実施例１）。This material was cured for 411 days at 20℃ in a humid atmosphere.
A temporary template was obtained, and the obtained cement slab was fractured. The discharge length of the fibers at the fracture surface was measured. (The way of discharge is ℃σ is close to I'
1. is selfish. ) Example 1.2. Comparative Examples 1 to 3 Average polymerization 1131490 (7) PVA appetizer: 16% degree strength 1
6.2, fI], and added PVA to the bath solution, i. :Add 1 boric acid of triple stitch φ
Eyes. A spinning fabric was prepared by adjusting pu to 57. This spinning stock solution was mixed with sodium hydroxide (15 t) g/t and sulfate (1.601 g/t). Spinning 1-2 using a 50C alkaline bath as a coagulation bath at /l-, after stretching 418 IJl between the first and second rollers, acid containing gold 3001/t, sulfuric acid 2511/t Neutralized at 40℃ in a Shioto bath, followed by an acidic salt bath containing 3'609//, sulfuric acid and 20g/t of sulfuric acid. So after performing + moist heat treatment at 90? Use, wash, and even oil? agent treatment [,. 235℃ after drying
A PVA-based synthetic fiber was obtained by subjecting it to constant length heat treatment at 24° C. (Example 1).

壕だ，熱延伸倍率を４倍から３．５倍に変？えた他は実
施例１と同一条件でｌ）ＶＡ系合成繊維を得？た（実施
例２）。？ 得られた繊維の性能を表−１に示す。又繊維の横断面は
第２図（実施例１）及び第３図（実施例２）雇示すとお
りであった。又，ζの繊維を用いて作成したセメント板
の性能Ｑ」．表−１に示すとおりであった。It's a moat, change the hot stretching ratio from 4x to 3.5x? l) VA-based synthetic fiber was obtained under the same conditions as in Example 1. (Example 2). ? Table 1 shows the performance of the obtained fibers. The cross section of the fiber was as shown in FIG. 2 (Example 1) and FIG. 3 (Example 2). Also, the performance Q of cement board made using ζ fibers. It was as shown in Table-1.

比較のため，凝固浴を以下の通り変えた他？は実施例１
と同一条件セ繊維を製造し．以下実施例１と同様に繊維
及びセメント板の性？能を測定し尼。For comparison, the coagulation bath was changed as shown below. is Example 1
The fibers were produced under the same conditions. Below, as in Example 1, what are the properties of fiber and cement board? Measuring ability.

その結果は表−１に示すとおりであった。反，繊比較例
１；ボウ硝ａｓＯｇ／ｔ，水酸化ナトリウム１５１１７
’ｌ−’ｍｇｌｌ１．５０Ｃ．（第”４図）■′較？例
２：水酸化ナト’Ｕ”ｔム３’５０ｇ／ｔ．温度２ｏ？
一？ｄ（麹５１鮪）？ ：゛ルｍ４ｕ？３’：ボウ硝４２ｂＩ／ｔ．温度４０℃
（第６図）但し，比較例３は熱延伸４″倍でｉ試料が採
取できな１かったので′２４８倍で繊維を製造した。The results were as shown in Table-1. Anti-fiber Comparative Example 1; AsOg/t, sodium hydroxide 15117
'l-'mgll1.50C. (Figure 4) Comparison Example 2: Sodium hydroxide 'U't 3'50g/t. Temperature 2o?
one? d (koji 51 tuna)? :゛ru m4u? 3': Bowsalt 42bI/t. Temperature 40℃
(FIG. 6) However, in Comparative Example 3, it was not possible to collect sample i at 4'' hot stretching, so a fiber was produced at 248 times hot stretching.

対照例二′石綿補強（ス？レート板） ＰＶＡ系合成繊維無添加め？セメント積層板１は，ク″
？リソタ：イル？ア亥べ支ト５Ｒ”１５１ｆＣ隈部−バ
ルプ３重量部及び普通ボルトランドセメント８２重量部
を混合し作成した。？ 実施？例１で得られた繊維は比較例１．２の繊維に比べ
若干高いヤン？グ率を示している。又，′繊維横断面は
異形化されている。★施例２で得られだ′＋ａ′維は比
較例１，２の繊維？に比べ低いヤング率，強度を示して
いる。又繊維横断？面は異形化してい１る噌この繊維を
補強材としたセメン？ト：板の性能は実施例め繊維補強
セメントの方が比較例及び対照例より優れて込た。Comparative example 2' Asbestos reinforcement (slate board) PVA-based synthetic fiber additive-free? The cement laminate 1 is
? Risota: Iru? The fibers obtained in Example 1 were slightly higher than the fibers in Comparative Example 1.2. Young's modulus is shown.Furthermore, the fiber cross section is deformed.★The '+a' fiber obtained in Example 2 has a lower Young's modulus and strength than the fibers of Comparative Examples 1 and 2. In addition, the cross-sectional surface of the fibers is irregularly shaped.Cement using this fiber as a reinforcing material: The performance of the board with the fiber-reinforced cement of the example is better than that of the comparison and control examples. Ta.

：実施例２け強度．ヤング率が若干低い繊維を使用した
ものであるが，横断面が異形化してＩＡ′るため補：強
効果が優れるもめと推察される。: Example 2 strength. Although fibers with a slightly lower Young's modulus are used, the cross section is irregularly shaped and becomes IA', so it is presumed that this is due to the excellent reinforcement effect.

突施？例３，比較例・４．５ 平均重合度１３００のＰＶＡを濃度が１８：（（’，Ｊ
ｉ（％となるよう水に溶解し・．得られたｒδ液にＰ’
ｉＶ・Ａ′に対し１．３重量チのホウ酸を添加し１）Ｈ
をｉ５．７に調・整七で紡糸：原液を作成した。この紡
糸原液を水酸化ナト？リウムｚｏａｅ７ｔ，ボウ硝ｇ’
ｏ．／Ｌで５０Ｃのアルカリ性？の塩類？浴ヲ凝固浴と
し・て紡出し，以下実施例１１と全ぐ同様にして繊鼾｛
ｆ：′製・造した３，得られた繊維の性能を表−・２・
に？示す。又，緯繊の４／７ｔｌゲ１面け第７図に示す
通りであった。・又，このｆＪｖ！ｉｆｆｔを用いて作
成したセメン）・板の性能は表−２の通りであった。・ 比較のため，凝固浴を以下の通り変えた他け実，１イｌ
ｉ［２１Ｊ２と同−条ｒトで繊維を製造し，以下実施例
２と同様に４載Ｋ４ＬＩｉ支びセメント板の性能を測定
した。Project? Example 3, Comparative Example 4.5 PVA with an average degree of polymerization of 1300 was used at a concentration of 18:((', J
P' in the resulting rδ liquid.
Add 1.3 weight of boric acid to iV・A' and
was adjusted to i5.7 and spun at i5.7 to create a stock solution. Is this spinning stock solution sodium hydroxide? lium zoae7t, bow salt g'
o. /L 50C alkaline? Salts? The bath was spun as a coagulating bath, and the following was carried out in the same manner as in Example 11.
f:' Manufactured 3, the performance of the obtained fibers is shown in Table-・2・
To? show. In addition, the 4/7 tl game of the weft was as shown in Figure 7.・Also, this fJv! The performance of the cement board created using ifft is shown in Table 2.・For comparison, one sample was prepared with the coagulation bath changed as follows.
Fibers were produced using the same strips as 21J2, and the performance of the 4-mounted K4LIi support cement board was measured in the same manner as in Example 2.

その桔泌ｄ表−２に示＃”ｉｍりであった。ヌ．繊維の
横断面Ｇ寸第８．９図に示す辿りであった。The cross section G dimension of the fiber was as shown in Figure 8.9.

比較例４：ボウ硝３５０＆／Ｌ，水酸化プｌ・リウム１
５ｙ７ｔ，温度５０℃（第８図） Ｌｔ較例５：水ｆａ化ｆ｝’）ウム３Ｅｉ０１／Ｌ．（
Ｆａ［２０℃実施例３で７ηられた！：’）！１４ｆ：
は比較例４．５の繊維Ｋ比べ性能（′．１ほとんど変ら
ないが，横断面は異形化され−Ｃいる。そのためかセメ
ント板の性能は実施例３の方が優ｆ１ていた。Comparative example 4: 350 &/L of sulfur salt, 1 liter of prium hydroxide
5y7t, temperature 50°C (Fig. 8) Lt Comparative Example 5: Water FA f}') Um3Ei01/L. (
Fa [7η was reduced in Example 3 at 20°C! :')! 14f:
Compared to the fiber K of Comparative Example 4.5, the performance ('.1 is almost unchanged, but the cross section is irregularly shaped -C).Perhaps for this reason, the performance of the cement board of Example 3 was superior f1.

実施例４．比較例６〜９ 子均重合度１６８０のＩ）ＶＡを濃度が１６．２’ｉｉ
’ｊ．−敞係となるよう水に溶解し，得られた溶液にＰ
ＶＡに”ｔｔ，１．３重量チのホウ酸を添加しｌ）Ｈを
５．７に調整してκＪｉ糸原液を作成した。この紡糸原
液を水酸化ナトリウム１７０．９／ｔ，ボウ硝１２０ｆ
ｉ／ｔで５０℃のアルカリｉｈＬの塩禎浴−を，・疑固
浴として紡出し．以下実施（ｉ’ｌＪ１と全く回様ｊで
して繊維孕製造し，た。得られた繊Ｋ『の性能を表−３
に示す。又，繊維の横断面は第１０図に示す通りであっ
た。又，この繊維を用いて作成したセメント板の性能に
表−３に示す通りであった。Example 4. Comparative Examples 6 to 9 I) VA with a molecular polymerization degree of 1680 was used at a concentration of 16.2'ii
'j. - P is dissolved in water so that it becomes a
A κJi yarn stock solution was prepared by adding 1.3 wt.
A salt bath of alkaline IHL at 50°C was spun at I/T as a pseudo-solid bath. Fiber production was carried out in the following manner (I'lJ1 and J).The performance of the obtained fiber K' is shown in Table 3.
Shown below. Further, the cross section of the fiber was as shown in FIG. Furthermore, the performance of the cement board made using this fiber was as shown in Table 3.

比較のため，比較例６，７については凝固浴を以下の通
り変えた他は実施例４と同一条件で，比較ｆｔ・り８．
９１Ｃ−）いては紡糸原液にホウ酸を加えず．かつ凝固
浴及び熱延伸倍率を以下の通り変えた他は実施例４と同
−条件で繊維を製造ｌ２，以下実施例４と同様に繊ｉｆ
Ｋｌ々びセメント板の性能を測定しＡ−。その結果は氏
−３に示す通りで子）っフコ。又，峨維の｛ｊｌ断而（
ζ１．￥ＮＩ１〜１４図に示す通りであった。For comparison, Comparative Examples 6 and 7 were made under the same conditions as Example 4 except that the coagulation bath was changed as follows.
91C-), no boric acid was added to the spinning dope. Fibers were produced under the same conditions as in Example 4, except that the coagulation bath and hot drawing ratio were changed as follows.
Measuring the performance of Klubi cement board A-. The result is as shown in Mr.-3. Also, Awei's {jl discontinuation (
ζ1. It was as shown in ¥NI1-14 figures.

比較例６：ボウ硝３５０Ｅ／ｔ，水酸化ナトリウム１５
．９／ｌ，温度５０’Ｃ（第１１図） 比較例７：水酸化ナトリウム３５０．９７／＝，温度２
０Ｃ．（第１２図） 比較例８：ホウ酸無添加ＰＶＡ原液（ＰＨ６’）．飽和
ボウ硝浴．熱延伸２８倍（第１３図） 比較例９ニホウ酸無添加ＰＶＡ原液（ＰＨ６）．水酸化
ナトリウム３５０ｇ／ｔ，温度２０℃．熱延伸倍率３．
３倍（？Ｊｆｊ１４図） 実施例４で得られた繊維は比較例６．７の繊維に比べ若
干高いヤング率を示している。又．繊維横断面は異形化
されている。セメント板の性能は朶施例４の方が優れ．
ていた。、 参考例１〜８・． 実施例１，７ｃ得られた繊維をそれぞれ０３３重ｆｔ’
ｉ％．０，５重量チ，．．１重量チ，１．５重量チ，２
重ｉ′チ．２．５重量チ，０．１重量チ，３重量．勇と
，バルブ３重量チ及びスペシャルクレイ１．ＯＭ量係を
含有し，残部が普通ボルトランドセ／ントから．，ナる
混合物より湿式抄造法にてセメント積層板全成形し，次
いで２０℃．湿空中で２８日間狡住し積層．板を得た。Comparative example 6: 350E/t of salt, sodium hydroxide 15
．． 9/l, temperature 50'C (Figure 11) Comparative example 7: Sodium hydroxide 350.97/=, temperature 2
0C. (Figure 12) Comparative Example 8: Boric acid-free PVA stock solution (PH6'). Saturated bow glass bath. Hot stretching 28 times (Figure 13) Comparative Example 9 PVA stock solution without diboric acid (PH6). Sodium hydroxide 350g/t, temperature 20℃. Hot stretching ratio 3.
3 times (?Jfj14 figure) The fiber obtained in Example 4 shows a slightly higher Young's modulus than the fiber in Comparative Example 6.7. or. The fiber cross section is deformed. The performance of the cement board was better in Example 4.
was. , Reference Examples 1 to 8. Examples 1 and 7c The obtained fibers were each 033 ft'
i%. 0.5 weight chi,. ．． 1 weight chi, 1.5 weight chi, 2
heavy i'chi. 2.5 weight, 0.1 weight, 3 weight. Isamu, Valve 3 weight chi and special clay 1. Contains OM quantity, and the rest is from normal Bolland cent. , a cement laminate was completely formed using a wet paper-making method from the mixture, and then molded at 20°C. Laminated in a humid atmosphere for 28 days. Got the board.

得られた積層板について曲げ強度及びシャルビー＠撃強
度を測定した。又，湿式抄造時の繊維の分散性を肉眼に
より観察し，良好（◎）．良（○），やや不良（△）で
評価した。それらの結果を表−４に示す。The bending strength and Charby @ impact strength of the obtained laminate were measured. In addition, the dispersibility of fibers during wet papermaking was visually observed and was good (◎). Evaluation was made as good (◯) or slightly poor (△). The results are shown in Table 4.

スレート平板を基準にすると繊維の添加ｆｋｌｄ０．３
〜２．５重量チが良く，とくに０．５〜２重量チが良好
であった。Based on slate plate, fiber addition fkld0.3
A weight of ~2.5 weight was good, and a weight of 0.5 to 2 weight was particularly good.

【図面の簡単な説明】[Brief explanation of the drawing]

第１図は本発明の凝固浴条件を示すグラフである。第２
１凶．ｔｉｆ．ａ図，第７図及び第１０図はそれぞれ実
施例１〜４で得られた繊維の横断面図を示し，第４図．
第５図，第６図，第８図，第９図，第１１図，第１２図
，第１３図及び第１４図はそれぞれ比較例１．〜９で得
られた繊維の横断回図を示す。 ６７一FIG. 1 is a graph showing the coagulation bath conditions of the present invention. Second
1 evil. tif. Figure a, Figure 7, and Figure 10 respectively show cross-sectional views of the fibers obtained in Examples 1 to 4, and Figure 4.
5, 6, 8, 9, 11, 12, 13, and 14 are Comparative Example 1, respectively. The cross-sectional diagram of the fiber obtained in ~9 is shown. 671

Claims (1)

【特許請求の範囲】[Claims] （１）ホウ酸又は銅塩を添加したポリビニルアルコール
系紡糸原液をカ性アルカリ濃度（ｘｇ／ｔ）及び脱水性
塩類濃度（ｙｇ７ｔ）が下記（ａ）−（ｂ），（ｃ）式
の条件を同時に満足する凝固浴中に紡出１．／Ｉ１つい
で常法の中和．湿熱処理を行った後，水洗，乾燥し，ジ
’ｆ−ＦＣ熱延伸を施すことを特徴とするポリビニルア
ルコール系合成繊維の製造法。 Ｙ≦４１．５−１．６８Ｘ（ａ） Ｙ≧８５０−５Ｘ（ｂ） Ｙ≧１８５−０．５８Ｘ（ｅ）(1) A polyvinyl alcohol-based spinning stock solution to which boric acid or copper salt has been added is prepared under conditions where the caustic alkali concentration (xg/t) and the dehydrating salt concentration (yg7t) are as shown in equations (a)-(b) and (c) below. Spinning into a coagulation bath that simultaneously satisfies 1. /I1 Next, neutralize the conventional method. A method for producing polyvinyl alcohol-based synthetic fibers, which comprises performing wet heat treatment, washing with water, drying, and subjecting to di'f-FC hot stretching. Y≦41.5-1.68X (a) Y≧850-5X (b) Y≧185-0.58X (e)