JP3048448B2 - Acrylonitrile filament bundle - Google Patents
Acrylonitrile filament bundleInfo
- Publication number
- JP3048448B2 JP3048448B2 JP3296061A JP29606191A JP3048448B2 JP 3048448 B2 JP3048448 B2 JP 3048448B2 JP 3296061 A JP3296061 A JP 3296061A JP 29606191 A JP29606191 A JP 29606191A JP 3048448 B2 JP3048448 B2 JP 3048448B2
- Authority
- JP
- Japan
- Prior art keywords
- acrylonitrile
- fiber
- spinning
- bundle
- coagulated
- 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.)
- Expired - Lifetime
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- Artificial Filaments (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、低コストアクリロニト
リル系フィラメント束に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low-cost acrylonitrile filament bundle.
【0002】[0002]
【従来の技術】アクリロニトリル系繊維の歴史は古く、
用途、目的に応じた様々な特性、形態を有するものが開
発されている。その中にあって、衣料用はもちろん産業
資材用途としても一層の機能化、高付加価値化が望まれ
ており、繊維束としてフィラメント(長繊維)であるこ
との重要性が大きくなってきている。一方、素材として
のアクリロニトリル系繊維はごく限られた特殊なものを
除いて低価格であることが要求され、フィラメントにお
いても製造コストの低減を目的とした生産技術の向上が
不可欠となっている。2. Description of the Related Art Acrylonitrile fibers have a long history,
Those having various characteristics and forms according to applications and purposes have been developed. Among them, further functionalization and higher added value are desired not only for clothing but also for industrial materials, and the importance of filaments (long fibers) as fiber bundles is increasing. . On the other hand, acrylonitrile-based fibers as materials are required to be inexpensive except for very limited specialty fibers, and it is indispensable to improve production technology for filaments in order to reduce production costs.
【0003】従来、フィラメントと呼ばれるものは、そ
の繊維束内に単繊維切れ・毛羽等が混入することを避け
るため、乾式紡糸法あるいは乾−湿式紡糸法によって製
造されるものが一般的である。しかしながらこれらの紡
糸法によるものは、湿式紡糸法によるものに比べ、紡糸
方式上ノズルホールの高密度化が困難であり、また製造
設備への初期投資が大きくなること等から、現状よりさ
らに製造コストを低減させることは困難である。Conventionally, filaments are generally manufactured by a dry spinning method or a dry-wet spinning method in order to prevent single fiber breakage and fluff from being mixed into the fiber bundle. However, compared to the wet spinning method, these spinning methods make it more difficult to increase the density of nozzle holes due to the spinning method and increase the initial investment in manufacturing equipment. Is difficult to reduce.
【0004】一般に低コストアクリロニトリル系繊維の
製造には、ノズルホールの高密度化において有利であ
り、かつ製造設備への投資が比較的少なくて済むなどの
点より、紡糸方式として湿式紡糸法が採用されている。
しかし得られる繊維束は一般に単繊維切れ・毛羽が多
く、フィラメントとして扱われるものではない。特殊な
例ではあるが湿式紡糸法によるフィラメント束も知られ
ている。これらの例として、紡糸工程中に急速な変形
(延伸)や、走行する繊維束の液中抵抗を抑えるといっ
た目的で、繊維束の工程通過速度を低下させて得られる
フィラメント束、あるいは紡糸ノズル周辺の凝固浴状態
を均一に維持するため、ノズルのホール密度を低下させ
て得られるもの等がある。しかしながら、同時にこれら
は何れも紡糸生産性の低下を伴い、低コストフィラメン
ト束という観点からは未だ不十分といえる。In general, wet spinning is adopted as a spinning method for the production of low-cost acrylonitrile-based fibers, because it is advantageous in increasing the density of nozzle holes and requires relatively little investment in production equipment. Have been.
However, the obtained fiber bundle generally has many single fiber breaks and fluff, and is not treated as a filament. As a special example, a bundle of filaments formed by a wet spinning method is also known. Examples of these are filament bundles obtained by reducing the fiber bundle passing through the process, or the vicinity of the spinning nozzle, for the purpose of rapid deformation (drawing) during the spinning process and for suppressing the resistance of the running fiber bundle in the liquid. In order to maintain a uniform coagulation bath state, there are those obtained by lowering the hole density of the nozzle. However, at the same time, all of these are accompanied by a decrease in spinning productivity, and are still insufficient from the viewpoint of low cost filament bundles.
【0005】従来から多くの研究がなされているにもか
かわらず、単繊維切れ・毛羽等が抑えられたフィラメン
ト束として満足いく品質の高いものであると同時に、生
産性が高く低コストにて供給され得るものはいまだ見出
されていないのが現状である。[0005] Despite a great deal of research, a filament bundle with single fiber breakage and fluff is suppressed to a satisfactory quality, and at the same time, supplied at high productivity and at low cost. At present, what can be done has not been found yet.
【0006】[0006]
【発明が解決しようとする課題】本発明者らは、このよ
うな従来の技術に対し、湿式紡糸法によるアクリロニト
リル系繊維の単繊維切れ・毛羽の解消および繊維製造の
安定性向上について鋭意検討した結果本発明を完成する
に至った。すなわち本発明の目的は、高生産性・低コス
トであって、しかも高品質であるアクリロニトリル系フ
ィラメント束を提供することにある。SUMMARY OF THE INVENTION The present inventors have intensively studied, with respect to such a conventional technique, the elimination of broken single fibers and fluff of acrylonitrile-based fibers by wet spinning and the improvement of the stability of fiber production. As a result, the present invention has been completed. That is, an object of the present invention is to provide an acrylonitrile-based filament bundle which has high productivity, low cost, and high quality.
【0007】[0007]
【課題を解決するための手段】本発明の要旨は、アクリ
ロニトリル系重合体を湿式紡糸し、凝固繊維の引張弾性
率を約2.0〜3.0g/dとすることによって得られ
るアクリロニトリル系フィラメント束である。SUMMARY OF THE INVENTION The gist of the present invention is to provide an acrylonitrile-based filament obtained by wet spinning an acrylonitrile-based polymer and setting the tensile modulus of the coagulated fiber to about 2.0 to 3.0 g / d. A bunch.
【0008】本発明においてアクリロニトリル系重合体
はアクリロニトリル、あるいはアクリロニトリルおよび
これと共重合可能な他の単量体(コモノマー)1種類以
上からなる。ここにおいてコモノマーとしては例えば、
(メタ)アクリル酸およびそのエステル類、酢酸ビニ
ル、プロピオン酸ビニル、(メタ)アクリルアミド、ジ
アセトンアクリルアミド、N−ヒドロキシメチルアクリ
ルアミド、イタコン酸、マレイン酸、フマル酸、クロト
ン酸、無水マレイン酸、メタクリロニトリル、スチレ
ン、α−メチルスチレン等を挙げることができる。なか
でも親水性・水溶性のコモノマーが好ましい。このよう
なアクリロニトリル系重合体の重合度は極限粘度[η]
が0.8以上のものが好ましい。In the present invention, the acrylonitrile-based polymer comprises acrylonitrile or one or more kinds of acrylonitrile and another monomer (comonomer) copolymerizable therewith. Here, as the comonomer, for example,
(Meth) acrylic acid and its esters, vinyl acetate, vinyl propionate, (meth) acrylamide, diacetone acrylamide, N-hydroxymethylacrylamide, itaconic acid, maleic acid, fumaric acid, crotonic acid, maleic anhydride, methacryloyl Examples thereof include nitrile, styrene, and α-methylstyrene. Among them, hydrophilic and water-soluble comonomers are preferred. The polymerization degree of such an acrylonitrile-based polymer is the intrinsic viscosity [η].
Is preferably 0.8 or more.
【0009】本発明のフィラメント束は湿式紡糸法によ
って得られる。ここにおいて本発明者らは湿式紡糸にお
ける工程糸である凝固繊維の引張弾性率と、この繊維を
後処理して得られる最終的な繊維束の単繊維切れ・毛羽
等フィラメント束としての品質を損なう現象との関係を
見いだした。すなわち凝固繊維の引張弾性率が約2.0
〜3.0g/d(d=デニールは凝固繊維中の重合体分
の重量に基づいたもの)である場合、該凝固繊維をさら
に延伸・洗浄・乾燥等の後処理して得られる繊維束は、
単繊維切れ・毛羽が極めて少なく、湿式紡糸法によって
得られたものであるにもかかわらず安定した高品質を有
するものである。The filament bundle of the present invention is obtained by a wet spinning method. Here, the present inventors impair the tensile modulus of the coagulated fiber, which is a process yarn in wet spinning, and the quality of the final fiber bundle obtained by post-processing this fiber as a filament bundle such as a single fiber cut or a fluff. I found a relationship with the phenomenon. That is, the tensile modulus of the coagulated fiber is about 2.0
When it is g3.0 g / d (d = denier is based on the weight of the polymer component in the coagulated fiber), the fiber bundle obtained by further post-treatment such as drawing, washing and drying of the coagulated fiber is ,
It has very few single fiber breakage and fluff, and has stable high quality despite being obtained by wet spinning.
【0010】凝固繊維の引張弾性率が約2.0g/d未
満の場合、凝固液中など紡糸工程の初期段階において不
均一な伸張を招き、得られる繊維束の繊度も極めて不均
一なものとなる。さらに紡糸各工程での延伸性の変動が
顕著になり単繊維切れを誘発し、安定したフィラメント
束の連続紡糸が困難となる。一方、引張弾性率が約3.
0g/dを越えると、凝固浴中での単繊維切れおよび後
工程での延伸性低下等を招き、機械的特性、品質および
生産の安定性のすべてにおいて満足できる繊維束を得る
ことができない。凝固繊維の引張弾性率は、原料重合体
の重合度およびコモノマーを加えた場合はその種類およ
びその含有量によって、さらに紡糸原液濃度、凝固条件
(凝固液組成、温度、凝固ドラフト等)および凝固繊維
繊度等の要素によって定まる。When the tensile modulus of the coagulated fiber is less than about 2.0 g / d, uneven elongation is caused in the initial stage of the spinning process such as in a coagulating liquid, and the fineness of the obtained fiber bundle is extremely uneven. Become. Furthermore, the fluctuation of the stretchability in each spinning step becomes remarkable, which causes breakage of a single fiber and makes continuous spinning of a stable filament bundle difficult. On the other hand, the tensile modulus is about 3.
If it exceeds 0 g / d, the single fiber breakage in the coagulation bath and the drawability in the subsequent step are caused, and a fiber bundle satisfying all mechanical properties, quality and production stability cannot be obtained. The tensile modulus of the coagulated fiber depends on the degree of polymerization of the raw material polymer and the type and content of the comonomer if added, and also the spinning stock solution concentration, coagulation conditions (coagulation solution composition, temperature, coagulation draft, etc.) and coagulated fiber. It is determined by factors such as fineness.
【0011】本発明のアクリロニトリル系フィラメント
束の製造例について説明する。本発明のアクリロニトリ
ル系重合体の重合方法は溶液重合、スラリー重合等公知
の方法のいずれにも限定されない。紡糸に際して用いら
れる溶剤は有機、無機の公知のものを使用することがで
きる。A production example of the acrylonitrile filament bundle of the present invention will be described. The polymerization method of the acrylonitrile polymer of the present invention is not limited to any known method such as solution polymerization and slurry polymerization. As the solvent used in spinning, known organic and inorganic solvents can be used.
【0012】本発明においてアクリロニトリル系重合体
溶液を公知の方法にしたがって湿式紡糸法により紡出、
凝固、延伸(浴中、あるいは空気中および浴中)および
乾燥緻密化を行う。浴中延伸は凝固繊維を直接行っても
よいし、また空気中にて凝固繊維をあらかじめ延伸した
後に行ってもよい。浴中延伸は通常50〜98℃の延伸
浴中で1回あるいは2回以上の多段に分割するなどして
行われ、その前後あるいは中間に水洗を行ってもよいが
本発明はそれに限定されない。これらの操作によって凝
固繊維を浴中延伸完了時までに約3倍以上延伸されるこ
とが好ましい。In the present invention, an acrylonitrile polymer solution is spun by a wet spinning method according to a known method.
Coagulation, stretching (in bath or in air and bath) and dry densification. The drawing in the bath may be performed directly on the coagulated fiber, or may be performed after the coagulated fiber is drawn in advance in the air. Stretching in the bath is usually performed in a stretching bath at 50 to 98 ° C. once or twice or more in multiple stages, and washing may be performed before, after, or in the middle, but the present invention is not limited thereto. By these operations, it is preferable that the coagulated fiber is stretched about three times or more by the time when the stretching in the bath is completed.
【0013】浴中延伸、洗浄後の繊維は公知のいずれの
方法のよっても油剤処理、乾燥が可能であるが、例えば
乾燥は複数段の加熱ローラー(または熱ドラム)あるい
は熱風等により行ってもよいが、乾燥速度、設備の簡便
さなどを考慮した場合100〜200℃程度の加熱ロー
ラーによる方法が好ましい。また必要に応じて乾燥前あ
るいは後に、繊維をさらに高温の加熱ローラーあるいは
加圧スチームによって延伸を施してもよい。The fiber after drawing and washing in a bath can be treated with an oil agent and dried by any known method. For example, drying can be performed by using a heating roller (or hot drum) having multiple stages or hot air. Although it is good, a method using a heating roller at about 100 to 200 ° C. is preferable in consideration of the drying speed, facility of the facility, and the like. If necessary, before or after drying, the fiber may be further stretched by a hot roller or pressurized steam.
【0014】[0014]
【実施例】以下実施例により本発明を具体的に説明す
る。「%」は重量%を表す。 (イ)「凝固繊維の引張弾性率」:凝固繊維束を採取
後、速やかに温度23℃、湿度50%の雰囲気中、試料
長(掴み間隔)10cm、引張速度10cm/minに
てテンシロンによる引張試験を行う。弾性率表示は、下
式により凝固繊維束のデニール(d;凝固繊維束900
0mあたりの重合体の占める重量)を求め、g/dにて
示した。 d=9000×f×Qp/V f:フィラメント数、Qp:ノズル1ホールあたりの重
合体吐出量(g/min)、V:凝固繊維引取速度(m
/min) (ロ)「重合体の極限粘度[η]」:25℃のジメチル
ホルムアミド溶液で測定した。The present invention will be described in detail with reference to the following examples. "%" Represents% by weight. (A) "Tensile elasticity of coagulated fiber": After collecting coagulated fiber bundle, immediately pulling by Tensilon at a sample length (gripping interval) of 10 cm and a pulling speed of 10 cm / min in an atmosphere of a temperature of 23 ° C. and a humidity of 50%. Perform the test. The modulus of elasticity is expressed by the following formula: denier (d; coagulated fiber bundle 900) of the coagulated fiber bundle.
The weight occupied by the polymer per 0 m) was obtained and shown in g / d. d = 9000 × f × Qp / V f: number of filaments, Qp: discharge amount of polymer per one nozzle hole (g / min), V: coagulated fiber take-off speed (m
/ Min) (b) "Intrinsic viscosity of polymer [η]": Measured with a dimethylformamide solution at 25 ° C.
【0015】実施例1および比較例1 アクリロニトリル93%、ジアセトンアクリルアミド7
%からなり極限粘度[η]が1.3の共重合体を共重合
体濃度23%でジメチルアセトアミドに溶解して紡糸原
液とし、孔径0.08mmφ、12000ホールのノズ
ルを用いて表1に示す濃度および温度のジメチルアセト
アミド水溶液中に凝固ドラフト0.8(凝固ドラフト=
凝固繊維引取速度/紡糸原液吐出線速度)で湿式紡糸し
た。得られた凝固繊維束の引張弾性率を表1に示す。こ
の凝固繊維を沸水中で5倍延伸しながら洗浄・脱溶剤し
た後、油剤溶液中に浸漬し、約130℃の加熱ローラー
にて乾燥緻密化を行うことにより単繊維デニール2.0
d、12000フィラメントの繊維束を得た。紡糸の
際、ワインダー直前を走行する乾燥した繊維束に生じた
単繊維切れ・毛羽を目視にて計測し繊維束100m当た
りの毛羽発生数を毛羽頻度として表1に示した。Example 1 and Comparative Example 1 93% of acrylonitrile, diacetone acrylamide 7
% Of a copolymer having an intrinsic viscosity [η] of 1.3 was dissolved in dimethylacetamide at a copolymer concentration of 23% to prepare a spinning dope, and the results are shown in Table 1 using a nozzle having a hole diameter of 0.08 mmφ and a 12,000 hole. Coagulation draft 0.8 (coagulation draft =
Wet spinning was carried out at a coagulated fiber take-off speed / spun stock solution discharge linear speed). Table 1 shows the tensile modulus of the obtained coagulated fiber bundle. This coagulated fiber is washed and desolvated while being stretched 5 times in boiling water, immersed in an oil solution, and dried and densified with a heating roller at about 130 ° C. to obtain a single fiber denier of 2.0.
d, a fiber bundle of 12,000 filaments was obtained. At the time of spinning, the single fiber breakage and fluff generated in the dried fiber bundle running immediately before the winder were visually measured, and the number of fluff generated per 100 m of fiber bundle was shown in Table 1 as the fluff frequency.
【0016】[0016]
【表1】 [Table 1]
【0017】比較例2 アクリロニトリル93%、アクリル酸メチル7%からな
り極限粘度[η]が1.8の共重合体を共重合体濃度2
0%でジメチルアセトアミドに溶解して紡糸原液とし、
凝固浴条件をジメチルアセトアミド濃度65%、温度3
5℃とた以外は実施例1と同様にして紡糸を行った。こ
のときの凝固繊維束の引張弾性率は4.3g/dであっ
た。実施例と同様にして単繊維切れ、毛羽の計測を行っ
たところ毛羽頻度は8.4であった。Comparative Example 2 A copolymer consisting of 93% of acrylonitrile and 7% of methyl acrylate and having an intrinsic viscosity [η] of 1.8 was prepared at a copolymer concentration of 2
Dissolve in dimethylacetamide at 0% to make a spinning stock solution,
The coagulation bath conditions were dimethylacetamide concentration 65%, temperature 3
Spinning was performed in the same manner as in Example 1 except that the temperature was 5 ° C. At this time, the tensile elastic modulus of the coagulated fiber bundle was 4.3 g / d. When the measurement of single fiber breakage and fluff was performed in the same manner as in the example, the fluff frequency was 8.4.
【0018】実施例2 アクリロニトリル90%、メタクリル酸2−ヒドロキシ
エチルエステル10%からなり極限粘度[η]が1.8
の共重合体を共重合体濃度20%でジメチルアセトアミ
ドに溶解して紡糸原液とし、孔径0.075mmφ、1
2000ホールのノズルを用いてジメチルアセトアミド
濃度65%および温度35℃の凝固浴中に吐出して湿式
紡糸した。この際に原液吐出量を増減することで凝固ド
ラフトを変化させ、以後実施例と同様にして紡糸を行っ
た。各凝固ドラフト条件における凝固繊維束の引張弾性
率およびワインダー直前での毛羽頻度を測定し結果を表
2に示した。Example 2 A mixture of 90% acrylonitrile and 10% methacrylic acid 2-hydroxyethyl ester has an intrinsic viscosity [η] of 1.8.
Was dissolved in dimethylacetamide at a copolymer concentration of 20% to prepare a spinning dope, and the pore size was 0.075 mmφ,
Using a 2000-hole nozzle, the mixture was discharged into a coagulation bath having a dimethylacetamide concentration of 65% and a temperature of 35 ° C. to perform wet spinning. At this time, the solidification draft was changed by increasing or decreasing the discharge amount of the undiluted solution, and thereafter spinning was performed in the same manner as in the example. The tensile modulus of the coagulated fiber bundle and the fuzz frequency immediately before the winder under the respective coagulation draft conditions were measured, and the results are shown in Table 2.
【0019】[0019]
【表2】 [Table 2]
Claims (1)
し、凝固繊維の引張弾性率を約2.0〜3.0g/dと
することによって得られるアクリロニトリル系フィラメ
ント束。1. An acrylonitrile-based filament bundle obtained by wet spinning an acrylonitrile-based polymer and setting the tensile modulus of the coagulated fiber to about 2.0 to 3.0 g / d.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3296061A JP3048448B2 (en) | 1991-11-12 | 1991-11-12 | Acrylonitrile filament bundle |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3296061A JP3048448B2 (en) | 1991-11-12 | 1991-11-12 | Acrylonitrile filament bundle |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH05132814A JPH05132814A (en) | 1993-05-28 |
JP3048448B2 true JP3048448B2 (en) | 2000-06-05 |
Family
ID=17828599
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3296061A Expired - Lifetime JP3048448B2 (en) | 1991-11-12 | 1991-11-12 | Acrylonitrile filament bundle |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3048448B2 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5183329B2 (en) * | 2008-07-08 | 2013-04-17 | 三菱レイヨン株式会社 | Wet spinning method of antibacterial acrylic fiber |
-
1991
- 1991-11-12 JP JP3296061A patent/JP3048448B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPH05132814A (en) | 1993-05-28 |
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