JPS6128014A - Production of fiber containing acrylonitrile - Google Patents

Production of fiber containing acrylonitrile

Info

Publication number
JPS6128014A
JPS6128014A JP15035784A JP15035784A JPS6128014A JP S6128014 A JPS6128014 A JP S6128014A JP 15035784 A JP15035784 A JP 15035784A JP 15035784 A JP15035784 A JP 15035784A JP S6128014 A JPS6128014 A JP S6128014A
Authority
JP
Japan
Prior art keywords
weight
acrylonitrile
temperature
wet
hot 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.)
Granted
Application number
JP15035784A
Other languages
Japanese (ja)
Other versions
JPH0130923B2 (en
Inventor
Naohiko Kakita
垣田 直彦
Satoru Harada
悟 原田
Muneto Makiyama
牧山 宗刀
Taizo Yasumoto
泰三 安本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kanegafuchi Chemical Industry Co Ltd
Original Assignee
Kanegafuchi Chemical Industry Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kanegafuchi Chemical Industry Co Ltd filed Critical Kanegafuchi Chemical Industry Co Ltd
Priority to JP15035784A priority Critical patent/JPS6128014A/en
Publication of JPS6128014A publication Critical patent/JPS6128014A/en
Publication of JPH0130923B2 publication Critical patent/JPH0130923B2/ja
Granted legal-status Critical Current

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  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

PURPOSE:To obtain hollow fibers using an ordinary spinneret, by drawing a filament yarn wet extruded from an acrylonitrile (AN) based copolymer solution in a hot water bath, drying the drawn yarn at a low temperature, and heat-treating the dried yarn to form single or plural cavities in the fiber cross section. CONSTITUTION:A spinning solution of an acrylonitrile (AN) based copolymer, preferably containing >=30wt%-<80wt% AN is wet spun, and the resultant yarn is drawn in a hot water bath to densify further the skin layer. The wet yarn in a state of binary structure having the skin layer and the core layer is dried at a low temperature and heat-treated to form single or plural cavities in the cross section of the fibers. Thus, 5-40% void content is obtained.

Description

【発明の詳細な説明】 「産業上の利用分野」 本発明はアクリロニトリルを含む繊維、特に繊維横断面
に単一又は複数個の空洞を形成せしめるアクリロニトリ
ルを含む繊維の製造法に関するものである。
DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" The present invention relates to a method for producing acrylonitrile-containing fibers, in particular acrylonitrile-containing fibers that form single or multiple cavities in the cross section of the fibers.

「従来の技術」 「発明が解決しようとする問題点」一
般に、中空繊維は腰があり、見かけ比重が小さく、崇高
であり、しかも保温性、吸水性を持つ等数多くの特徴を
有している。従来、中空繊維を製造する場合には、■複
雑な構造を有する紡糸口金を使用する方法、■発泡剤等
の添加剤を紡糸原液中に含有せしめる方法等が用いられ
ているが、■の方法では紡糸口金の構造上、微細孔を作
ることが技術的に困難であり、繊度の細いものが得られ
ないという欠点がある。またそれに伴ない、孔数を増加
させることが困難で、しかも紡糸口金が非常乙こ高価な
ものとなるため、生産性が低く且つ採算性の悪いものと
なっている。一方、■の方法では発泡剤の性質上1分散
性が不均一になり易く、紡糸操業が不安定で、繊維束中
の大部分が中空にならないなどの問題点があった。
``Prior art'' ``Problems to be solved by the invention'' In general, hollow fibers are stiff, have a low apparent specific gravity, are noble, and have many characteristics such as heat retention and water absorption. . Conventionally, when producing hollow fibers, methods such as (1) using a spinneret with a complicated structure, (2) a method of incorporating additives such as a foaming agent into the spinning solution, etc. have been used, but the method of (2) However, due to the structure of the spinneret, it is technically difficult to create fine pores, and it is difficult to obtain fine pores. In addition, it is difficult to increase the number of holes and the spinneret becomes extremely expensive, resulting in low productivity and poor profitability. On the other hand, method (2) has problems such as the dispersibility tends to be non-uniform due to the nature of the blowing agent, the spinning operation is unstable, and most of the fiber bundles are not hollow.

[問題点を解決するための手段」 本発明者らはかかる実情に鑑み、前述の如き従来法の欠
点を改善するために鋭意研究を続けた結果、本発明に到
達したものである。
[Means for Solving the Problems] In view of the above-mentioned circumstances, the inventors of the present invention have conducted intensive research to improve the drawbacks of the conventional methods as described above, and as a result they have arrived at the present invention.

即ち、本発明はアクリロニトリル系共重合体を有機溶媒
又は無機溶媒に溶解して紡糸原液とし、通常の紡糸口金
を通じて湿式紡糸し、スキン層とコア層を持つ二元構造
を形成せしめ、次に熱水浴中で延伸し前記スキン層をよ
り緻密化した湿潤糸条を二元構造を維持した状態で低温
乾燥し、更に熱処理を行うことにより繊維横断面に単一
又は複斂個の空洞を形成せしめることを特徴とするアク
リロニトリルを含む繊維の製造法を内容とするものであ
る。
That is, in the present invention, an acrylonitrile-based copolymer is dissolved in an organic or inorganic solvent to form a spinning dope, wet-spun through an ordinary spinneret to form a binary structure having a skin layer and a core layer, and then heated. Wet yarn drawn in a water bath to make the skin layer more dense is dried at low temperature while maintaining its binary structure, and then heat-treated to form single or multiple cavities in the cross section of the fiber. The subject matter is a method for producing fibers containing acrylonitrile, which is characterized in that the fibers contain acrylonitrile.

本発明で用いるアクリロニトリル系共重合体は、b7ま
しくは30重量%ツ上80重量%未尚のアクリロニトリ
ルからなる共重合体で、アクリロニトリルと1種又は2
種以上のビニル系単量体との共重合によって得られる。
The acrylonitrile copolymer used in the present invention is a copolymer consisting of b7 or 30% by weight but not more than 80% by weight of acrylonitrile.
It is obtained by copolymerization with more than one type of vinyl monomer.

より好ましくはアクリロニトリルが30重量%以上60
重量%以下よりなる共重合体が望ましい。即ち、アクリ
ロニトリルが60重量%を越えると、湿式紡糸において
目的とする二元構造が発現され難い傾向が現われる。
More preferably, the acrylonitrile content is 30% by weight or more60
A copolymer consisting of less than % by weight is desirable. That is, when the acrylonitrile content exceeds 60% by weight, it tends to be difficult to develop the desired binary structure during wet spinning.

ビニル系単量体としては、例えばアクリル酸、メタクリ
ル酸、塩化ビニル、塩化ビニルデン、酢酸ビニルのよう
なビニルエステル、ビニルピロリドン、ビニルピリジン
及びそのアルキル置換体、アクリル酸エステル、メタク
リル酸エステル、アクリル酸アミド、メタクリル酸アミ
ド又はそれらのモノ及びジアルキル置換体、スチレンス
ルホン酸、メタリルスルホン酸、又はこれらの金属塩類
及びアミン塩類等が挙げられる。本発明においては、共
重合し得る単量体については余り厳密さは要求されず、
アクリロニトリルと共重合し得る通常のビニル系単量体
はいずれも使用することができる。
Examples of vinyl monomers include acrylic acid, methacrylic acid, vinyl chloride, vinyldene chloride, vinyl esters such as vinyl acetate, vinylpyrrolidone, vinylpyridine and its alkyl substituted products, acrylic esters, methacrylic esters, and acrylic acid. Examples include amide, methacrylic acid amide, mono- and dialkyl-substituted products thereof, styrene sulfonic acid, methallyl sulfonic acid, and metal salts and amine salts thereof. In the present invention, there is no need to be very strict regarding monomers that can be copolymerized.
Any conventional vinyl monomer that can be copolymerized with acrylonitrile can be used.

このアクリロニトリル系共重合体を有機溶媒、例えばア
セトン、アセトニトリル、ジメチルホルムアミド、ンメ
チルアセタミド、ジメチルスルホキシド或いは無機溶媒
、例えば塩化亜鉛、硝酸ロダン塩等に溶解させて紡糸原
液とするが、無機又は有機の顔料或いは紡績、着色防止
、耐光性等に効果のある安定剤等と紡糸に支障をきたさ
ない限り使用することも可能である。
This acrylonitrile copolymer is dissolved in an organic solvent such as acetone, acetonitrile, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, or an inorganic solvent such as zinc chloride, rhodan nitrate, etc. to prepare a spinning stock solution. It is also possible to use organic pigments or stabilizers effective for spinning, color prevention, light resistance, etc., as long as they do not interfere with spinning.

本発明で用いられる通常の紡糸口金とは、円形又は長軸
と短軸の長さの比が5対1より小さい楕円形、或いは三
角形、六角形、菱形のような多角形等のオリフィスを有
する紡糸口金を意味するが、円形成いは楕円形に近い形
状のオリフィスが好適である。
The conventional spinneret used in the present invention has an orifice that is circular or oval with a length ratio of major axis to minor axis smaller than 5 to 1, or polygonal such as triangular, hexagonal, or rhombic. Although it refers to a spinneret, an orifice having a circular or nearly oval shape is suitable.

以上のような紡糸口金を通じて、前述の如き紡糸原液を
湿式紡糸し、その紡糸原液中に存在している有機溶媒も
しくは無機溶媒に相当する有機溶媒もしくは無機溶媒又
は両者を含存する水/8液で満たされた第1凝固浴へ導
く。ここでスキン層を形成させるためには、浴中の有機
溶媒もしくは無機溶媒又は両者の濃度は好ましくは1〜
50重量%、更に好ましくは5〜30重量%であり、ま
た温度は好ましくは一り0℃〜→−50°C1更に好ま
しくは0℃〜+30°Cする。第1凝固浴滞留時間は、
上記の濃度及び温度、更には繊度により設定されるが、
2〜80秒であることが望ましい。
The above-mentioned spinning dope is wet-spun through the spinneret as described above, and a water/8 solution containing an organic solvent or an inorganic solvent corresponding to the organic solvent or inorganic solvent present in the spinning dope, or both, is used. into a filled first coagulation bath. In order to form a skin layer, the concentration of the organic solvent, inorganic solvent, or both in the bath is preferably 1 to 1.
The amount is 50% by weight, more preferably 5 to 30% by weight, and the temperature is preferably from 0°C to -50°C, and more preferably from 0°C to +30°C. The first coagulation bath residence time is
It is set by the above concentration and temperature, as well as the fineness.
The time is preferably 2 to 80 seconds.

次いで、第2凝固浴へ繊維を導くのであるが、ここでス
キン層をより緻密化しコア層との差をより明確なものと
するためには、浴中の有機溶媒もしくは無機溶媒又は両
者の濃度は第1凝固浴と同濃度、より好ましくは第1凝
固浴よりも低い濃度であることか必要で、更に温度は第
1凝固浴と同温度、より好ましくは第1凝固浴よりも高
温度であることが望ましい。
Next, the fibers are led to a second coagulation bath, but in order to make the skin layer more dense and to make the difference from the core layer more clear, the concentration of the organic solvent, inorganic solvent, or both in the bath must be adjusted. It is necessary to have the same concentration as the first coagulation bath, more preferably a lower concentration than the first coagulation bath, and furthermore, the temperature should be the same as the first coagulation bath, more preferably a higher temperature than the first coagulation bath. It is desirable that there be.

この第2凝固浴中において繊維を延伸することも可能で
あり、延伸によっである程度の物理的性質を付与するこ
とが好ましいが、過度の延伸を行うとコアが緻密化し二
元構造を破壊する恐れがあるため避けなければならない
。第2凝固浴滞留時間は、延伸を行う場合も含めて2〜
80秒で、より好ましくは2〜40秒である。しかる後
に繊維を洗浄するのであるが、洗浄は通常10〜45℃
程度の低温水中、及び70℃以上の熱水中の2段階で行
うが、場合によっては低温水洗浄を省略してもよい。
It is also possible to draw the fiber in this second coagulation bath, and it is preferable to impart some physical properties by drawing, but excessive drawing will densify the core and destroy the binary structure. Must be avoided due to fear. The residence time in the second coagulation bath is 2 to 2, including when stretching is performed.
80 seconds, more preferably 2 to 40 seconds. After that, the fibers are washed, usually at 10-45°C.
The washing is carried out in two steps: in water at a low temperature of 70° C. and in hot water at a temperature of 70° C. or higher, but depending on the case, the low-temperature water washing may be omitted.

この洗浄浴を通した後に、目的とする二元構造を発現さ
せるためには70℃以上、好ましくは80〜100°C
以上の熱水中において1.2〜5.0倍の延伸を行うこ
とが必要であるが、より好ましくは1,5〜40倍が望
ましい。即ち、1.2倍未満の場合は繊維物性の低下が
起り、また5、0倍を越えるとコア層の空隙が緻密とな
り、目的とする二元構造が維持されない傾向が現われる
After passing through this washing bath, in order to develop the desired binary structure, the temperature should be 70°C or higher, preferably 80 to 100°C.
It is necessary to stretch the film by 1.2 to 5.0 times in hot water, more preferably from 1.5 to 40 times. That is, if it is less than 1.2 times, the physical properties of the fiber will deteriorate, and if it exceeds 5.0 times, the voids in the core layer will become dense and the desired binary structure will not be maintained.

以上のような工程を経て含水率100重量%以下且つ溶
媒含率20重量%以下の湿潤糸条をなし、緻密で強靭な
スキン層と多数の空隙を有し軟弱なコア層を持つ二層構
造を形成させることができる。
Through the above steps, a wet yarn with a water content of 100% by weight or less and a solvent content of 20% by weight or less is formed, and a two-layer structure with a dense and strong skin layer and a soft core layer with many voids is formed. can be formed.

しかしながら、この繊維の横断面に単一又は複数個の空
洞を形成させるためには熱処理が必要であるが、熱処理
前に低温乾燥、好ましくは5〜4゜°Cの低温乾燥を行
い、含水率を30重量%以下且つ溶媒含率を15重量%
以下に低下させることが望ましい。乾燥温度が40“C
を越えると、コア層の空隙が緻密になり、二層構造が維
持し難い。一方、5°C未満では乾燥効率が低下し、乾
燥時間が長くなり生産性の面で問題がある。
However, heat treatment is necessary to form single or multiple cavities in the cross section of this fiber, but before heat treatment, low temperature drying, preferably 5 to 4°C, is performed to reduce the moisture content. 30% by weight or less and the solvent content is 15% by weight
It is desirable to lower it to below. Drying temperature is 40"C
If it exceeds this, the voids in the core layer will become dense and it will be difficult to maintain the two-layer structure. On the other hand, if the temperature is lower than 5°C, the drying efficiency decreases and the drying time increases, causing problems in terms of productivity.

本発明で言う熱処理とは熱風などによる一般的な乾熱処
理、スチームなどによる湿熱処理、或いはポリエチレン
クリコール、グリセリン等のような有機化合物を利用し
た恒温浴による熱処理等のあらゆる方法を含むものであ
り、これらのいずれか1種または2種以上の方法を用い
て目的は達成される。また熱処理温度は100〜150
°Cであることが好ましく、高温度であるほど良好な空
洞が形成されるが、乾熱系では150°Cを越え、湿熱
系では130℃以上の熱処理を行うと、過度の収縮が起
こり、繊維を切断する恐れがあるので好ましくない。
The heat treatment referred to in the present invention includes all methods such as general dry heat treatment using hot air, moist heat treatment using steam, etc., or heat treatment using a constant temperature bath using organic compounds such as polyethylene glycol and glycerin. The object can be achieved using one or more of these methods. Also, the heat treatment temperature is 100 to 150
°C is preferable, and the higher the temperature, the better the cavity will be formed, but if heat treatment is performed at a temperature exceeding 150 °C in a dry heat system or 130 °C or higher in a moist heat system, excessive shrinkage will occur. This is not preferable because it may cut the fibers.

本発明方法によれば熱処理方法の種類によって形成され
る空洞の形状には違いがあるが、繊維を製造するに当た
っては熱処理方法によって得られた繊維の形状が違うの
は通常のことであり、目的に応して最も適切な方法を選
択されるべきである。
According to the method of the present invention, there are differences in the shape of the cavities formed depending on the type of heat treatment method, but when manufacturing fibers, it is normal for the shape of the fibers obtained depending on the heat treatment method to differ, and it is normal for the purpose The most appropriate method should be selected depending on the situation.

かくして繊維横断面に単一又は複数個の空洞を有する繊
維を得ることができるが、本発明方法により得られる空
洞は、単−及び複数個である場合を含めて、5〜40%
の空洞率を示している。
In this way, fibers having single or multiple cavities in the cross section of the fiber can be obtained, and the number of cavities obtained by the method of the present invention is 5 to 40%, including single and multiple cavities.
It shows the cavity ratio of .

尚、空洞率は次のような算出方法によった。Note that the void ratio was calculated using the following method.

繊維の横断面写真を均一な厚みの紙に投影し、繊維断面
の全重量(S w 十Cw)及び空洞部の重量CWの比
を次式に従って求めた。
A cross-sectional photograph of the fiber was projected onto paper of uniform thickness, and the ratio of the total weight of the fiber cross section (S w + Cw) and the weight of the cavity CW was determined according to the following formula.

空洞率〔%) = (Cw/ (Si++し))X10
0(Cw :中空部の重量、籏:非中空部の重量)また
前述の含水率及び溶媒含率は次の測定方法により算出し
た。即ち、純水中に測定する繊維を&漬し煮沸すること
により繊維中の溶媒等を溶出せしめ、ガスクロマトグラ
フィー等によりその溶液中における有機溶媒または無機
溶媒の1度を測定し、一方浸漬していた繊維を取り出し
115〜120℃で3時間乾燥したl&型重量測定した
。純水の重量をWl、浸漬前の繊維の重量をvJ2.乾
燥後の繊維の重量をW3、有機溶媒または無機溶媒の濃
度をCとすると、溶媒含率は次式により算出される。
Cavity ratio [%] = (Cw/ (Si++))X10
0 (Cw: weight of the hollow part, weight of the hollow part: weight of the non-hollow part) Moreover, the above-mentioned water content and solvent content were calculated by the following measuring method. That is, the fiber to be measured is immersed in pure water and boiled to elute the solvent, etc. in the fiber, and the amount of organic or inorganic solvent in the solution is measured by gas chromatography or the like. The fibers were taken out and dried at 115 to 120° C. for 3 hours, and the weight of the mold was measured. The weight of the pure water is Wl, and the weight of the fiber before immersion is vJ2. When the weight of the fiber after drying is W3 and the concentration of the organic solvent or inorganic solvent is C, the solvent content is calculated by the following formula.

溶媒率S (%) =(C((W1+W2)  W3)
 /JX100更に含水率は次式により算出される。
Solvent rate S (%) = (C((W1+W2) W3)
/JX100 Furthermore, the moisture content is calculated by the following formula.

含水率〔%〕−〔(匈2−誓3)/葬3) X100−
5  (%)「実施例」 以下、実施例及び比較例を挙げて本発明の詳細な説明す
るが、本考案はこれらにより何ら制■をうけるものでは
ない。
Moisture content [%] - [(匈2-匈3)/匈3) X100-
5 (%) "Examples" The present invention will be described in detail below with reference to Examples and Comparative Examples, but the present invention is not limited by these in any way.

実施例1 アクリロニトリル/スチレンスルボン酸ナトリウム/塩
化ビニル−49,5/1.0/49.5からなるアクリ
ロニトリル系共重合体をアセトン中に30重量%含有し
45〜55℃に保持された紡糸原液を、孔)そ0525
mm孔数100ホールの円形状オリフィスを有する紡糸
口金を通じて、水中にアセトンを30重量%含有し25
°Cに保持された第1凝固浴に湿式紡糸し、次いで第1
凝固浴と同様の否状態にある第2凝固浴に通し、ここで
2倍の延伸を行った。この際の第1浴滞留時間は80秒
、第2浴滞留時間は20秒であった。さらに30°Cの
水洗浴に通した後、90℃の熱水浴に通し2.5倍の延
伸を行った。この段階における含水率は74.4重量%
、アセトン含率は16.5重量%であった。次に30°
Cの低温乾燥を6分間行うことにより含水率は19.1
重量%、アセトン12,2重量%に低下せしめた。しか
る縁に145°Cの乾熱処理工程に5分間滞留させた。
Example 1 Spinning yarn containing 30% by weight of an acrylonitrile copolymer consisting of acrylonitrile/sodium styrene sulfonate/vinyl chloride-49.5/1.0/49.5 in acetone and maintained at 45 to 55°C. Add the stock solution to the hole) 0525
Acetone containing 30% by weight in water was passed through a spinneret having a circular orifice with 100 mm holes.
wet spinning into a first coagulation bath held at °C;
It passed through a second coagulation bath which was in the same state as the coagulation bath, where it was stretched twice. At this time, the first bath residence time was 80 seconds, and the second bath residence time was 20 seconds. The film was further passed through a washing bath at 30°C, and then passed through a hot water bath at 90°C to be stretched 2.5 times. Moisture content at this stage is 74.4% by weight
, the acetone content was 16.5% by weight. then 30°
By drying C at low temperature for 6 minutes, the moisture content was 19.1.
% by weight of acetone was reduced to 12.2% by weight. The edges were subjected to a dry heat treatment step at 145°C for 5 minutes.

以上の工程を経て得られた繊維は繊度が29.7デニー
ルで、単一空洞を有する中空繊維であった。この繊維の
横断面写真(走査電子顕微鏡)を第1図に示した。
The fiber obtained through the above steps had a fineness of 29.7 denier and was a hollow fiber having a single cavity. A cross-sectional photograph (scanning electron microscope) of this fiber is shown in FIG.

実施例2 実施例1と同様の紡糸原液を孔径0.14mm孔数30
0ホールの円形状オリフィスを有する紡糸口金を通じて
実施例1と同様の第1凝固浴へ湿式紡糸し、次いで水中
にアセトンを20重量%含有し25℃に保持された第2
凝固浴に通し、ここで2倍の延伸を行った。この時の第
1浴滞留時間は25秒、第2浴滞留時間は10秒であっ
た。さらに水洗浴を省略し90 ℃の熱水浴に5通じて
2.5 (i3の延伸を行った。この段階における含水
率は95重量%、アセトン含率は7.9重量%であった
。次に25°Cの低温乾燥を5分間行うことにより含水
率は28重量%、アセトン含率は5.9重量%に低下せ
しめた。しかる後に130℃に保持されたグリセリン浴
中に2分間滞留させた。以上の工程を経て得られた繊維
の繊度は6.8デニールで、その横断面写真を第2図に
示したが、構造的に実施例1のもの(第1図)とほぼ一
致している。
Example 2 The same spinning dope as in Example 1 was used with a pore diameter of 0.14 mm and a number of pores of 30.
Wet-spun into a first coagulation bath similar to Example 1 through a spinneret with a circular orifice of 0 holes, followed by a second coagulation bath containing 20% by weight of acetone in water and maintained at 25°C.
It was passed through a coagulation bath where it was stretched twice. At this time, the first bath residence time was 25 seconds, and the second bath residence time was 10 seconds. Further, the water washing bath was omitted and the film was stretched in a hot water bath at 90° C. for 2.5 (i3). At this stage, the water content was 95% by weight and the acetone content was 7.9% by weight. Next, low-temperature drying at 25°C was performed for 5 minutes to reduce the water content to 28% by weight and the acetone content to 5.9% by weight.Then, the mixture was left in a glycerin bath maintained at 130°C for 2 minutes. The fineness of the fiber obtained through the above process was 6.8 denier, and its cross-sectional photograph is shown in Figure 2, which is structurally almost the same as that of Example 1 (Figure 1). We are doing so.

実施例3 実施例1と同様の紡糸原液を孔径0.5mm、孔数50
−ルの円形状オリフィスを有する紡糸口金を通じて水中
にアセトンを40重量%含有し45°Cに保持された第
1凝固浴に湿式紡糸し、次いで水中にアセトンを30重
量%含有し、25℃に保持された第2凝固浴に通し、こ
こで1.4倍の延伸を行った。この時の第1浴扁留時間
は90秒、第2浴滞留時間は20秒であった。更に30
 ’Cの水洗浴に通した後、90℃の熱水浴に通し3.
6侶の延伸を行った。この段階における含水率は81.
8重量%、アセトン含率は16.9重量%であった。
Example 3 The same spinning dope as in Example 1 was used with a pore diameter of 0.5 mm and a number of pores of 50.
- Wet-spun into a first coagulation bath containing 40% by weight of acetone in water and held at 45°C through a spinneret with a circular orifice of 300° C.; It passed through a maintained second coagulation bath, where it was stretched 1.4 times. At this time, the first bath residence time was 90 seconds, and the second bath residence time was 20 seconds. 30 more
3. Pass through a 90°C hot water bath after passing through a water washing bath at 'C.
Six members were extended. The moisture content at this stage is 81.
The acetone content was 16.9% by weight.

次に30°Cの低温乾燥を5分間行うことにより含水率
は23,2電量%、アセトン含率は12.2重量%に低
下せしめた。しかる後に125℃の湿熱処理工程に]0
分間滞留させた。以上の工程を経て得られた繊維の繊度
は56.5デニールで、第3図に示す如く複数個の空洞
を有する中空繊維であった。
Next, by drying at a low temperature of 30° C. for 5 minutes, the water content was reduced to 23.2% by weight and the acetone content was reduced to 12.2% by weight. After that, a wet heat treatment process at 125°C]0
It was allowed to stay for a minute. The fiber obtained through the above steps had a fineness of 56.5 denier and was a hollow fiber having a plurality of cavities as shown in FIG.

比較例1 実施例Iと同様の紡糸原液を用い、孔径0,25mm孔
数100ホールの円形オリフィスを有する紡糸口金を通
じて、水中にアセトンを30重量%含有し、25°Cに
保持された第1凝固浴に湿式紡2凝固浴に通し、ここで
2倍の延伸を行った。この時の第1浴滞留時間は80秒
、第2浴滞留時間は20秒であった。更に30℃の水洗
浴に通した後90℃の熱水浴に通し25倍の延伸を行な
った。
Comparative Example 1 Using the same spinning dope as in Example I, a spinneret containing 30% by weight of acetone in water and maintained at 25°C was passed through a spinneret having a circular orifice with a hole diameter of 0.25 mm and 100 holes. Wet-spun into a coagulation bath 2 It passed through a coagulation bath, where it was stretched twice. At this time, the first bath residence time was 80 seconds, and the second bath residence time was 20 seconds. Further, the film was passed through a washing bath at 30°C and then a hot water bath at 90°C to be stretched 25 times.

次に80°Cの乾燥を6分間行なった後、145°Cの
乾熱処理工程乙こ5分間滞留させた。以上の工程を経て
得られた繊維は繊度が30デニールで、空洞は全く形成
されなかった。
Next, after drying at 80°C for 6 minutes, a dry heat treatment step at 145°C was carried out for 5 minutes. The fiber obtained through the above steps had a fineness of 30 denier, and no cavities were formed at all.

上記実施例及び比較例において得られた繊維の形4/、
特性を第1表に示した。
Fiber shape 4/ obtained in the above examples and comparative examples,
The properties are shown in Table 1.

「作用」 「発明の効果」 本発明は次の如き利点を有する; (11複雑な構造を有する紡糸口金を必要とせず、通常
のオリフィスを有する紡糸口金が使用できるため無駄な
経費を必要とせず、生産性の低下がなく、更に通常の紡
糸口金であるため、繊度の細いものが容易に得られる。
"Operation""Effects of the Invention" The present invention has the following advantages; There is no decrease in productivity, and since it uses a normal spinneret, products with fine fineness can be easily obtained.

(2)発泡剤等の添加剤を一切必要としないため安定し
た紡糸操業が維持でき、一定の制御された空洞を形成せ
しめることが可能である。(3)本発明を遂行し得るた
めに用いられる工程は繊維を製造する際には通常のもの
であり、従来となんら変わりはないため、生産性に優れ
、安価な該繊維を生産することが可能である。
(2) Since no additives such as foaming agents are required, stable spinning operation can be maintained and a certain controlled cavity can be formed. (3) The process used to carry out the present invention is a normal process for manufacturing fibers and is no different from the conventional process, so it is possible to produce the fibers with high productivity and at low cost. It is possible.

更に本発明によって得られる繊維は次の如き用途に適し
ている。即ち、適当な腰を持ちダル感があるため、パイ
ル用として好適であり、また保温性、吸水性を持つため
カーペット、ふとん綿、その他に使用しても良好な製品
が得られる。
Furthermore, the fibers obtained according to the present invention are suitable for the following uses. That is, it has a suitable stiffness and a dull feel, making it suitable for pile applications, and its heat retention and water absorption properties make it suitable for use in carpets, futons, and other applications.

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

第1図乃至第3図は、いずれも実施例1乃至実施例3で
得られた繊維の形状を示す横断面8微鏡写真である。 1(〆)μm 50μm 2001jm 手続補正書(自船 1.事件の表示 昭和59年特許願第150357号 2、発明の名称 アクリロニトリルを含む繊維の製造法 3、補正をする者 事件との関係:特許出願人 住所:大阪市北区中之島三丁目2番4号名称:  (0
94)鐘淵化学工業株式会社代表者:代表取締役 高 
1) 敞 4、代理人 住所 大阪市北区西天満3丁目2番4号明細書の「発明
の詳細な説明」の欄の記載を前記の通り補正する; (1)第5頁、第8〜9行目に「硝酸ロダン塩Jとある
を“硝酸、ロダン塩”に訂正する。 (2)同頁、第11行目に「安定剤等と」とあるを“安
定剤等を”に訂正する。 (3)第6頁、第8行目に「0℃〜+30°Cする」と
あるを“0℃〜→−30℃である”に訂正する。 (4)同頁、下から5行目の「であることか」を“であ
ることが”に訂正する。 (5)第7頁、第2行目に「コアが」とあるを“コア層
が”に訂正する。 (6)同頁、第8行目に「低温水洗浄」とあるを“どち
らか一方または両者”に訂正する。 (7)同頁、第12行目にr 1.2 Jとあるを“1
.1”に訂正する。 (8)同頁、第14行目に「1.2倍」とあるを“1.
1倍”に訂正する。 (9)第8頁、第1行目に「二層構造」とあるを“二元
構造”に訂正する。 (10)同頁、第8行目に同しく「二層構造」とあるを
“二元構造”に訂正する。 (11)同頁、第13行目に[ポリエチレンクリコール
」とあるを“ポリエチレングリコール”に訂正する。 (12)第9頁、下から4行目に「中空部」とあるを“
空洞部”に又、「非中空部」とあるを“非空洞部”に訂
正する。 (13)第10頁、第4行目に「乾燥した後重量を」と
あるを“乾燥した後、重量を”に訂正する。 (14)同頁、第9行目に「/W」とあるを“/ W3
”に訂正する。 (15)同頁下から7行目に「本考案」とあるを“本発
明”に訂正する。 (16)第11頁、第12行目の「アセトン」の次に“
含率は”を挿入する。 (17)第15頁、表中最下段にr 59. OJとあ
るを“30.0”に訂正する。 以上
1 to 3 are microphotographs of 8 cross sections showing the shapes of the fibers obtained in Examples 1 to 3. 1 (〆)μm 50μm 2001jm Procedural amendment (Own ship 1. Indication of the case 1982 Patent Application No. 150357 2, Name of the invention Method for manufacturing fibers containing acrylonitrile 3, Person making the amendment Relationship with the case: Patent Applicant address: 3-2-4 Nakanoshima, Kita-ku, Osaka Name: (0
94) Kanebuchi Chemical Industry Co., Ltd. Representative: Representative Director Takashi
1) The description in the "Detailed Description of the Invention" column of the specification of Sho 4, agent address: 3-2-4 Nishitenma, Kita-ku, Osaka, is amended as above; (1) Pages 5, 8- On the 9th line, "Nitric acid, Rodan salt J" is corrected to "nitric acid, Rodan salt." (2) On the same page, on the 11th line, "Stabilizers, etc." is corrected to "Stabilizers, etc." do. (3) On the 6th page, line 8, the phrase "0°C to +30°C" is corrected to "0°C to -30°C." (4) On the same page, in the 5th line from the bottom, ``Dere katoka'' is corrected to ``Dere ga''. (5) On page 7, in the second line, the phrase "core" is corrected to "core layer". (6) On the same page, in the 8th line, the phrase "low-temperature water cleaning" is corrected to "one or both." (7) On the same page, in the 12th line, replace r 1.2 J with “1”
.. (8) On the same page, in the 14th line, "1.2 times" should be changed to "1.
(9) On page 8, in the first line, the words "two-layer structure" are corrected to "two-layer structure." (10) On the same page, in the 8th line, the words "two-layer structure" should be corrected to "two-layer structure." (11) On the same page, in the 13th line, "polyethylene glycol" is corrected to "polyethylene glycol." (12) On page 9, the fourth line from the bottom says “hollow part”.
In addition, the words "non-hollow part" in "Cavity part" should be corrected to "non-hollow part." (13) On page 10, line 4, "weight after drying" is corrected to "weight after drying". (14) On the same page, in the 9th line, replace “/W” with “/W3
(15) In the 7th line from the bottom of the same page, the words "present invention" are corrected to "the present invention." (16) On page 11, line 12, next to “acetone” “
Insert "for the content rate." (17) On page 15, at the bottom of the table, correct "r 59. OJ" to "30.0".

Claims (1)

【特許請求の範囲】 1、アクリロニトリル系共重合体を有機溶媒又は無機溶
媒に溶解して紡糸原液とし、通常の紡糸口金を通じて湿
式紡糸し、スキン層とコア層を持つ二元構造を形成せし
め、次に熱水浴中で延伸し前記スキン層をより緻密化し
た湿潤糸条を二元構造を維持した状態で低温乾燥し、更
に熱処理を行うことにより繊維横断面に単一又は複数個
の空洞を形成せしめることを特徴とするアクリロニトリ
ルを含む繊維の製造法。 2、アクリロニトリル系共重合体がアクリロニトリルを
30重量%以上80重量%未満含有する特許請求の範囲
第1項記載の製造法。 3、湿式紡糸が第1及び第2凝固浴の溶媒濃度1〜50
重量%、温度−10〜50℃、滞留時間2〜80秒の条
件下で為される特許請求の範囲第1項記載の製造法。 4、熱水浴中での延伸が、70℃以上の熱水中において
、1.1〜5.0倍に延伸させる特許請求の範囲第1項
記載の製造法。 5、低温乾燥が温度5〜40℃で乾燥させる特許請求の
範囲第1項記載の製造法。 6、熱処理が温度100〜150℃で熱処理させる特許
請求の範囲第1項記載の製造法。
[Claims] 1. An acrylonitrile-based copolymer is dissolved in an organic or inorganic solvent to obtain a spinning dope, and wet-spun through a normal spinneret to form a binary structure having a skin layer and a core layer; Next, the wet yarn, which has been drawn in a hot water bath to make the skin layer more dense, is dried at a low temperature while maintaining the binary structure, and then heat-treated to create single or multiple cavities in the cross section of the fiber. A method for producing fibers containing acrylonitrile, characterized by forming acrylonitrile. 2. The production method according to claim 1, wherein the acrylonitrile copolymer contains 30% by weight or more and less than 80% by weight of acrylonitrile. 3. In wet spinning, the solvent concentration of the first and second coagulation baths is 1 to 50.
% by weight, a temperature of -10 to 50°C, and a residence time of 2 to 80 seconds. 4. The manufacturing method according to claim 1, wherein the stretching in a hot water bath is performed by stretching 1.1 to 5.0 times in hot water at 70°C or higher. 5. The manufacturing method according to claim 1, wherein the low-temperature drying is performed at a temperature of 5 to 40°C. 6. The manufacturing method according to claim 1, wherein the heat treatment is carried out at a temperature of 100 to 150°C.
JP15035784A 1984-07-18 1984-07-18 Production of fiber containing acrylonitrile Granted JPS6128014A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP15035784A JPS6128014A (en) 1984-07-18 1984-07-18 Production of fiber containing acrylonitrile

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP15035784A JPS6128014A (en) 1984-07-18 1984-07-18 Production of fiber containing acrylonitrile

Publications (2)

Publication Number Publication Date
JPS6128014A true JPS6128014A (en) 1986-02-07
JPH0130923B2 JPH0130923B2 (en) 1989-06-22

Family

ID=15495217

Family Applications (1)

Application Number Title Priority Date Filing Date
JP15035784A Granted JPS6128014A (en) 1984-07-18 1984-07-18 Production of fiber containing acrylonitrile

Country Status (1)

Country Link
JP (1) JPS6128014A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6485306A (en) * 1987-09-24 1989-03-30 Nikkiso Co Ltd Method for drawing with hot water and guide therefor
WO2006043661A1 (en) * 2004-10-22 2006-04-27 Kaneka Corporation Hollow acrylic synthetic fiber

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6485306A (en) * 1987-09-24 1989-03-30 Nikkiso Co Ltd Method for drawing with hot water and guide therefor
WO2006043661A1 (en) * 2004-10-22 2006-04-27 Kaneka Corporation Hollow acrylic synthetic fiber
JP5014799B2 (en) * 2004-10-22 2012-08-29 株式会社カネカ Hollow acrylic synthetic fiber

Also Published As

Publication number Publication date
JPH0130923B2 (en) 1989-06-22

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