JPH09137387A - Solvent-spun cellulose fiber excellent in pill resistance and peach-skin processability, its fiber structure and its production - Google Patents

Solvent-spun cellulose fiber excellent in pill resistance and peach-skin processability, its fiber structure and its production

Info

Publication number
JPH09137387A
JPH09137387A JP8220661A JP22066196A JPH09137387A JP H09137387 A JPH09137387 A JP H09137387A JP 8220661 A JP8220661 A JP 8220661A JP 22066196 A JP22066196 A JP 22066196A JP H09137387 A JPH09137387 A JP H09137387A
Authority
JP
Japan
Prior art keywords
fiber
cellulase
pilling
tencel
processing
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
Application number
JP8220661A
Other languages
Japanese (ja)
Inventor
Kiyoshi Otoi
清 音居
Sumio Abe
純夫 阿部
Masaru Kitamura
優 北村
Shohei Miyata
昌平 宮田
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.)
KANEBO SILK EREGANSU KK
OMORI KIKAKU KK
OOMORI KIKAKU KK
Kanebo Ltd
Original Assignee
KANEBO SILK EREGANSU KK
OMORI KIKAKU KK
OOMORI KIKAKU KK
Kanebo 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 KANEBO SILK EREGANSU KK, OMORI KIKAKU KK, OOMORI KIKAKU KK, Kanebo Ltd filed Critical KANEBO SILK EREGANSU KK
Priority to JP8220661A priority Critical patent/JPH09137387A/en
Publication of JPH09137387A publication Critical patent/JPH09137387A/en
Pending legal-status Critical Current

Links

Landscapes

  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

PROBLEM TO BE SOLVED: To produce a modified Tencel(R) raw stock having high pill resistance and excellent peach-skin processability in a compatible manner and capable of, especially, performing spinning to obtain excellent yarn quality under ordinary spinning conditions, without using a rubbing-beating process which usually has troubles of unevenness in the points of productivity and cloth strength, etc. SOLUTION: In a modification process of Tencel(R) fiber and its fiber structure, especially raw stock using cellulase, the amount of an anionic surfactant attached on the fiber is reduced to 0.05wt.% or bellow by washing with hot water in advance, and a linear velocity of a liquid flow of cellulase processing is controlled at <=5m/sec. These enable the cellulase processing at extremely mild conditions with total enzyme potencies of <=25000 unit, so that a single-fiber strength variation is suppressed to a narrow range of <=10% at the average single fiber strength of 3.0-4.3g/d. Further, the combination of the cross-linking modification using a glycidyl compound with the above process enables the production of a Tencel(R) fiber having high pill resistance and excellent peach-skin processability in a compatible manner and especially the production of a Tencel(R) raw stock having excellent spinnability.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】本発明は改質された溶剤紡糸
セルロース系繊維、該繊維からなる繊維構造物及びその
製造法に係わり、特に限定された処理条件での該繊維の
原綿のセルラーゼ加工による改質とエポキシ化合物によ
る架橋改質の組み合わせにより、該繊維の布帛加工に常
用されている前処理としての揉み叩き加工を実施しなく
て、高度の抗ピリング性と良好なピーチスキン加工性を
合わせ持った溶剤紡糸セルロース系繊維、該繊維からな
る繊維構造物及びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified solvent-spun cellulosic fiber, a fiber structure comprising the fiber and a method for producing the same, which is obtained by subjecting the raw cotton of the fiber to cellulase processing under particularly limited processing conditions. By combining modification and cross-linking modification with an epoxy compound, high anti-pilling property and good peach skin processability are combined without performing the rubbing and tapping process as a pretreatment that is commonly used for fabric processing of the fiber. The present invention relates to a solvent-spun cellulosic fiber, a fiber structure made of the fiber, and a method for producing the same.

【０００２】[0002]

【従来の技術】溶剤紡糸セルロース系繊維とは、精製パ
ルプを誘導体に化学反応せしめることなく、特殊な有機
溶媒、例えばＮ−メチルモルホリン−Ｎ−オキシド等に
加圧、加温下に溶解し、湿式紡糸したもので、英国コー
トルズ社の「テンセル」（商品名）が知られている。2. Description of the Related Art Solvent-spun cellulosic fibers are dissolved in a special organic solvent, such as N-methylmorpholine-N-oxide, under pressure and with heating, without chemically reacting the purified pulp with a derivative. “TENCEL” (trade name) manufactured by Courtesle of the UK is known as a wet-spun product.

【０００３】この溶剤紡糸セルロース系繊維（以下テン
セル繊維）は綿糸やレーヨンに比べて、強度が非常に強
く、張りが有りながらレーヨン特有の柔らかい風合を持
っていることが特徴で、さらに湿潤時の繊維強度がレー
ヨンと違って強く、さらに湿潤で縮みにくいといった優
れた特性を有している。[0003] This solvent-spun cellulosic fiber (hereinafter referred to as Tencel fiber) is characterized by having a very high strength compared to cotton yarn and rayon, and having a soft feel peculiar to rayon while having tension. Has excellent properties such as high fiber strength unlike rayon, and furthermore, it is hard to shrink when wet.

【０００４】テンセル繊維はＮ−メチルモルホリン−Ｎ
−オキシドを溶剤とし紡糸されたものであるが、上述の
優れた特性を持つ一方で、単繊維の構造が、スキン−コ
ア構造を持ち、このスキン層が家庭洗濯等の湿潤摩擦や
衝撃で非常にフィブリル化し易く、さらに該フィブリル
が絡んでピリングし易いという欠点を持っている。そし
て、最近のテンセル繊維に関する技術開発は、ほとんど
がピリング化を効率良く、効果的に防止しうる抗ピリン
グ技術に集中していると言っても過言では無い。例え
ば、「ニューレーヨンの実際知識」（繊維社）２８０〜
２８３頁には該繊維のピリング発現機構及びセルラーゼ
によるピリングの分解除去手法が理論的に解説されてい
る。該解説に記述されているように、現在、テンセル繊
維の抗ピリング対策としては、該繊維からなる布帛をロ
ータリーワッシャー等で揉み叩き加工を施すことで敢え
て単繊維のスキン層をフィブリル化さらにはピリング化
させ、発生したフィブリル及びピリングをさらに揉み叩
き加工しながら、セルラーゼで溶解除去する、いわゆる
バイオ加工が実施されている。従来、上述の揉み叩き加
工、セルラーゼ加工は布帛で実施されて来たが、絡み防
止対策を施した糸での揉み叩き加工やセルラーゼ加工の
研究も着手されている（特開平６−３２２６６７号公
報、特開平７−３６２６号公報参照）。The Tencel fiber is N-methylmorpholine-N
-Although spun using an oxide as a solvent, it has the above-mentioned excellent properties, but the structure of a single fiber has a skin-core structure, and this skin layer is extremely susceptible to wet friction and impact such as laundry at home. However, it has the disadvantage that the fibrils are easily entangled and easily pilled. It is no exaggeration to say that most of the recent technological developments related to TENCEL fibers are focused on anti-pilling technology that can efficiently and effectively prevent pilling. For example, "Actual knowledge of New Rayon" (Textile) 280-
On page 283, the mechanism of pilling expression of the fiber and the method of decomposing and removing pilling by cellulase are theoretically described. As described in the commentary, at present, as an anti-pilling measure against Tencel fiber, a fabric layer made of the fiber is rubbed and beaten with a rotary washer or the like so that the skin layer of the single fiber is intentionally fibrillated and further pilled. So-called bio-processing, in which fibrils and pillings generated are dissolved and removed with cellulase while rubbing and beating the generated fibrils and pilling, has been carried out. Conventionally, the above-mentioned kneading and tapping processing and cellulase processing have been carried out on fabrics, but research on kneading and tapping processing with a yarn and a cellulase processing with measures against entanglement has also been started (Japanese Patent Application Laid-Open No. Hei 6-322667). And JP-A-7-3626.

【０００５】繊維のフィブリル化現象は、一般的には、
糸や布帛への摩擦や衝撃で単繊維がさらに割繊され、割
繊されて発生したミクロ繊維が毛羽状に立ち上がる状態
である。さらに、ピリング化の機構は未だ完全に解明さ
れていない面もあるが、フィブリル化した布帛にさらに
摩擦や衝撃を加えて行った場合、ミクロ繊維同志及びミ
クロ繊維と単繊維が複雑に絡んで毛玉になり発現すると
言われている。フィブリル化は絹繊維の染色時や着用時
に白化現象として良く見られるものであるが、絹繊維の
場合は単繊維の強度が適度なものであるため、発生した
フィブリルは摩擦や衝撃で引きちぎられピリングが発生
することは無い。絹繊維の場合、フィブリル化は普通は
好ましい現象ではないが、時には布帛のピーチスキン加
工として利用される。[0005] The fibrillation phenomenon of fibers is generally
The single fiber is further split by friction or impact on the yarn or the cloth, and the microfibers generated by splitting stand up in a fluffy state. Furthermore, although the mechanism of pilling has not yet been fully elucidated, if the fibrillated fabric is further subjected to friction or impact, the microfibers and the microfibers and single fibers become complicatedly entangled with each other. It is said to be expressed as a ball. Fibrillation is often seen as a whitening phenomenon when dyeing or wearing silk fibers, but in the case of silk fibers, the strength of single fibers is moderate, so the generated fibrils are torn off by friction and impact and pilling Does not occur. In the case of silk fibers, fibrillation is usually not a preferred phenomenon, but is sometimes used as a peach skinning of fabrics.

【０００６】これに対してテンセル繊維の場合、前述の
ように単繊維強度が非常に強いため、発生したフィブリ
ルを摩擦や衝撃で引きちぎることが困難なため、著しく
ピリングし易い。そのためテンセル繊維の場合、前述の
ように揉み叩き加工で敢えてフィブリル及びピリングを
発生させ、これをセルラーゼ加工で溶解除去する加工手
段を採っている。一旦、表皮層をフィブリル化それに続
くセルラーゼ加工で溶解除去したテンセル繊維はもはや
摩擦や衝撃でピリングが発生することは無い。On the other hand, in the case of Tencel fiber, since the strength of the single fiber is very high as described above, it is difficult to tear off the generated fibrils by friction or impact, and therefore, the pilling is remarkably easy. Therefore, in the case of Tencel fiber, a processing means is used in which fibrils and pillings are intentionally generated by rubbing and tapping as described above, and are dissolved and removed by cellulase processing. Once the skin layer is fibrillated and then dissolved and removed by cellulase processing, the Tencel fiber no longer causes pilling due to friction or impact.

【０００７】しかしながら、揉み叩き加工、及びセルラ
ーゼ加工は対象が布帛であれ糸であれ、それぞれが小ロ
ット生産で、処理時間も全体として数時間〜１０数時間
掛かり、大規模な生産手法としては問題があった。[0007] However, the kneading and tapping process and the cellulase process, whether they are fabrics or yarns, are each produced in small lots and require several hours to several tens of hours as a whole, which is a problem as a large-scale production method. was there.

【０００８】一方、揉み叩き加工、セルラーゼ加工を施
したテンセル布帛の表面は、いわゆるピーチスキン調布
帛の風合を呈し、ファッション性のある繊維素材として
確固たる評価を得ている。従って、現在のところ、テン
セル繊維には感性の高いピーチスキン加工が必須の条件
であると言える。この意味で、テンセル繊維の、より大
規模、より短時間で高度な抗ピリング性加工と良好なピ
ーチスキン加工が両立する手法の開発が要望されていた
が、これまでの技術ではこれは不可能であった。On the other hand, the surface of the tencel cloth which has been beaten and cellulase processed has the texture of a so-called peach-skin-like cloth, which has been firmly evaluated as a fashionable fiber material. Therefore, at present, it can be said that the peach skin processing with high sensitivity is an essential condition for tencel fiber. In this sense, there has been a demand for the development of a method that enables both high-scale anti-pilling property processing and good peach skin processing on a larger scale and in a shorter time for TENCEL fibers, but this is impossible with conventional technology. Met.

【０００９】特に、大規模生産と短時間処理で経済性を
改善し、しかも加工の均一性の改善が期待できる点、さ
らには揉み叩き加工やセルラーゼ加工が困難な他素材と
テンセル繊維との混紡を実施する要望から、テンセル繊
維の原綿での改質加工が望まれていたが、テンセル原綿
の場合、揉み叩き加工は後の紡績を不可能にするほど綿
を損傷するため、さらに一段と困難な課題であった。In particular, it is possible to improve economic efficiency by large-scale production and short-time processing, and further, it is expected that processing uniformity can be improved. Further, tencel fiber is blended with other materials which are difficult to be beaten or cellulase processed. From the request to carry out, the modification processing of TENCEL fiber with raw cotton has been desired, but in the case of TENCEL raw cotton, the rubbing and beating process damages the cotton so as to make subsequent spinning impossible, and thus it is even more difficult. It was a challenge.

【００１０】繊維間をエポキシ化、特にグリシジル化合
物でセルロース分子間を架橋する方法で、防しわ性や耐
洗濯性を向上させる手法は公知である（例えば、続絹糸
の構造 信州大学繊維学部発行 ６３８頁 （１９８
０）、特開昭５０−１１２５９９号公報、特開昭５１−
３２８９８号公報、特開平６−２９９４６９号公報）。
又、同じ架橋機構で絹繊維のフィブリル化防止技術とし
てグリシジル化合物による架橋改質も行われている（特
開昭６４−２６７８４号公報）。しかしながら該架橋結
合をテンセル繊維に生成させた場合、抗ピリング性を改
善するには効果があるが、一方でテンセル繊維を差別化
繊維素材たらしめている、ピーチスキン加工にさらに長
時間の揉み加工が必要になり実用手法としては採用でき
ない。A method for improving wrinkle resistance and washing resistance by a method of epoxidizing fibers, particularly by cross-linking cellulose molecules with a glycidyl compound is known (for example, the structure of continuous silk thread, Shinshu University, Faculty of Textiles, 638). Page (198
0), JP-A-50-112599, JP-A-51-
No. 32898, JP-A-6-299469).
Further, cross-linking modification with a glycidyl compound has been carried out as a technique for preventing fibrillation of silk fibers by the same cross-linking mechanism (Japanese Patent Laid-Open No. 64-26784). However, when the cross-linking is generated in the tencel fiber, it is effective in improving the anti-pilling property, but on the other hand, the tencel fiber is a differentiated fiber material. It is necessary and cannot be adopted as a practical method.

【００１１】ところで、繊維のピリングは単繊維強度の
高い場合に発生するものであることは前述の通りである
が、一般に抗ピリング加工としては、単繊維強度を実用
強度として問題の無い適度なレベルまで低下調整させる
技術手段が公知である。例えば、ポリエステルの紡績糸
に用いられる抗ピリング加工は、重合度を下げたり、低
重合度ポリエステルをブレンドする手法が通常の手段で
ある。By the way, as described above, fiber pilling occurs when the strength of single fiber is high. Generally, as the anti-pilling process, the strength of single fiber is regarded as a practical strength and there is no problem. The technical means for adjusting the level to the low level are known. For example, in the anti-pilling process used for polyester spun yarn, a method of lowering the degree of polymerization or blending a low degree of polymerization polyester is a usual means.

【００１２】この手法をテンセル繊維に導入する場合、
原料が天然物であり手段は制約されるが、酸又はアルカ
リ或いはセルラーゼで、セルロースのβ−１．４グルコ
シド結合を加水分解する方法は実用可能な方法として当
然考えられる。綿糸やレーヨンの場合にも該加水分解が
実施される場合があるが、この場合は単繊維強度がそれ
ほど高くないため目的は、主として風合改良である（特
公昭４９−３８９４６号公報、特開昭５１−１４９９９
５号公報、特開昭５８−３６２１７号公報、特開昭５８
−５４０８２号公報等参照）。この場合にも見られるよ
うに、酸やアルカリを使用すると繊維が過度に加水分解
されて実用強度以下に極端に脆化したり、分解生成物に
起因する着色が惹起されるため問題があり、実用的なセ
ルロースの加水分解手段にはもつぱらセルラーゼが使用
されている。When this method is introduced into Tencel fiber,
Although the raw material is a natural product and the means is limited, a method of hydrolyzing the β-1.4 glucoside bond of cellulose with an acid, an alkali or cellulase is naturally considered as a practical method. The hydrolysis may be carried out also in the case of cotton yarn or rayon, but in this case, the purpose is mainly to improve the feeling because the strength of the single fiber is not so high (Japanese Patent Publication No. 49-38946, JP-A-2003-39946). 51-14999
5, JP-A-58-36217, JP-A-58
-54082 gazette etc.). As seen in this case, when an acid or an alkali is used, the fiber is excessively hydrolyzed and becomes extremely brittle below a practical strength, or there is a problem because coloring due to a decomposition product is caused. Paracellulase is used as a means for the conventional hydrolysis of cellulose.

【００１３】本発明者等は、先にテンセル繊維の抗ピリ
ング加工に関して、改良された物及びその製造法を提案
した。該発明は単繊維の表面が揉み叩き加工によるフィ
ブリル化又はミクロフィブリル化構造を呈しておらず、
繊維構造として完全なセルロース構造のみから成るにも
関わらず抗ピリング性に改質されている溶剤紡糸セルロ
ース系繊維、特に平均単繊維強度が３．５ｇ／ｄ以下に
改質されていて、しかも単繊維強度変動率が２０％以下
に均一に改質されているために、該繊維からなる織編物
の家庭洗濯機法での抗ピリング試験にＪＩＳ Ｌ−１０
７６法のピリング判定写真を準用しての判定で４級以上
の抗ピリング性であり、しかも該繊維から成る織編物強
度の均一性が良好に改質されていることを特徴とする抗
ピリング性溶剤紡糸セルロース系繊維に関し、その製造
法は溶剤紡糸セルロース系繊維の原綿、スライバー、紡
績糸或いは織編物のセルラーゼによる改質加工におい
て、予め該繊維に付着している紡糸油剤としてのアニオ
ン界面活性剤又はカチオン界面活性剤の付着量を０．０
５重量％以下となるように熱水で洗い落とし、かつセル
ラーゼ加工の総酵素力価（酵素力価（単位／ｇ）×酵素
濃度（％ｏｗｓ）×酵素加工時間（分））を５００００
単位以下に規制することを特徴とするものである。The present inventors have previously proposed an improved product and a method for producing the same regarding anti-pilling processing of tencel fiber. The invention does not exhibit a fibrillated or microfibrillated structure by rubbing and striking the surface of a single fiber,
Solvent-spun cellulosic fibers that have been modified to have anti-pilling properties even though they have only a complete cellulosic structure as the fiber structure, especially those that have been modified to have an average single fiber strength of 3.5 g / d or less. Since the variation rate of fiber strength is uniformly modified to 20% or less, JIS L-10 is used for the anti-pilling test of the woven and knitted fabric made of the fibers in the domestic washing machine method.
Anti-pilling property of 4 or more as judged by applying the pilling judgment photograph of Method 76, and that the uniformity of the strength of the woven or knitted fabric made of the fiber is well modified. Regarding solvent-spun cellulosic fibers, a method for producing the same is as an anionic surfactant as a spinning oil agent, which is attached in advance to solvent-spun cellulosic fibers in the modification process of raw cotton, sliver, spun yarn or woven or knitted fabric with cellulase. Alternatively, the amount of the cationic surfactant deposited is 0.0
Wash off with hot water to 5% by weight or less and total cell titer of cellulase processing (enzyme titer (unit / g) x enzyme concentration (% ows) x enzyme processing time (min)) is 50000
It is characterized by being regulated below the unit.

【００１４】該発明は、セルラーゼ加工を受けていない
テンセル繊維の平均単繊維強度が４．８ｇ／ｄ程度なの
に対して、３．５ｇ／ｄ以下に調整されているが、単繊
維強度変動率が２０％以下に均一に改質されているた
め、該発明からなるテンセル布帛は実用強度を保ちなが
ら、高度の抗ピリング性と良好なピーチスキン性を両立
させるものである。しかしながら該発明は、実施例にも
見られるように平均単繊維強度が３．０ｇ／ｄ以上にな
ると抗ピリング性が４級になり、このことから、さらに
細番手紡績糸による薄地織物の場合に、高度の抗ピリン
グ性を保ちながら実用強度を満足させるためには平均単
繊維強度が３．０ｇ〜４．０ｇ／ｄにおいても５級を満
足する抗ピリング性のテンセル繊維の開発が望まれた。According to the invention, the average single fiber strength of the tencel fibers not subjected to the cellulase treatment is about 4.8 g / d, while the average single fiber strength is adjusted to 3.5 g / d or less. Since it has been uniformly modified to 20% or less, the tencel fabric of the present invention has both high anti-pilling properties and good peach skin properties while maintaining practical strength. However, in the invention, as seen in the examples, when the average single fiber strength is 3.0 g / d or more, the anti-pilling property becomes grade 4, and therefore, in the case of a thin fabric made of fine count spun yarn, In order to satisfy practical strength while maintaining a high degree of anti-pilling property, development of anti-pilling tencel fiber satisfying Class 5 is desired even when the average single fiber strength is 3.0 g to 4.0 g / d. .

【００１５】さらに、該発明では、平均単繊維強度を
３．０ｇ／ｄ以下に調整した場合、通常のテンセル繊維
の紡績条件、特にカード条件で糸質、例えばＩＰＩ値で
かなり劣るという問題点があり、この面で平均単繊維強
度が３．０ｇ／ｄ以上で抗ピリング性がさらに改良さ
れ、しかもピーチスキン加工性を良好に保持することが
可能で、その上で紡績性を犠牲にしないテンセル原綿で
の改質が望まれていた。Further, in the present invention, when the average single fiber strength is adjusted to 3.0 g / d or less, there is a problem that the yarn quality, for example, the IPI value is considerably inferior under ordinary tencel fiber spinning conditions, particularly card conditions. In this respect, the average single fiber strength is 3.0 g / d or more, the anti-pilling property is further improved, and the peach skin processability can be maintained satisfactorily, and the spinning property is not sacrificed. Modification with raw cotton was desired.

【００１６】又、該発明の単繊維強度変動率は実施例に
も見られるように１０％以上であり、セルラーゼ加工前
の原綿の該変動率が１０％以下であるのに比較して、よ
り一層の均質なセルラーゼ加工の方法が望まれた。この
ことも上記の平均単繊維強度と同じく、細番手紡績糸に
よる布帛の実用強度を保持する上で肝要な要素である。Further, the variation rate of the single fiber strength of the present invention is 10% or more as seen in Examples, and the variation rate of the raw cotton before cellulase processing is 10% or less. A more homogeneous method of cellulase processing was desired. This is also an important factor for maintaining the practical strength of the fabric made of the fine count spun yarn, like the above average single fiber strength.

【００１７】[0017]

【発明が解決しようとする課題】本発明者等はテンセル
繊維の抗ピリング性改質及びピーチスキン加工性につい
て鋭意研究した結果、本発明を完成したものである。本
発明の目的とするところは、上述したような、テンセル
繊維を差別化繊維素材たらしめている良好なピーチスキ
ン加工性を低下させることなく改質し、しかも高度な抗
ピリング性を持ったテンセル繊維及び該繊維からなる繊
維構造物を提供するにあり、特に、本発明者等が先に提
案した発明で、抗ピリング性を改善するためにセルラー
ゼ加工を実施した場合、単繊維強度変動率が該加工前に
比して大きくなり糸品質が低下する問題点、さらにセル
ラーゼ加工の度合を強めるにつれて、通常のテンセル繊
維の紡績条件、特にカード条件で糸質がかなり劣るとい
う問題点等があり、これを改良して抗ピリング加工を施
すために、特に平均単繊維強度が３．０ｇ／ｄ以上のテ
ンセル繊維からなる繊維構造物に、高度な抗ピリング性
と良好なピーチスキン加工性を付与するテンセル原綿を
提供するにある。さらに他の目的はかかる改質を工業的
に有利に製造する方法を提供するにある。The present inventors have completed the present invention as a result of earnest studies on the anti-pilling property modification and peach skin processability of tencel fiber. The object of the present invention is to modify the tencel fiber as described above without lowering the good peach skin processability that makes the tencel fiber a differentiated fiber material, and yet has a high anti-pilling property. And a fiber structure comprising the fibers, and in particular, in the invention previously proposed by the present inventors, when cellulase processing is performed to improve the anti-pilling property, the single fiber strength variation rate is There is a problem that the yarn quality becomes larger than before processing and the yarn quality deteriorates, and as the degree of cellulase processing is strengthened, the yarn quality is considerably inferior under the usual tencel fiber spinning conditions, especially card conditions. In order to improve anti-pilling and improve anti-pilling properties, especially for fiber structures composed of tencel fibers having an average single fiber strength of 3.0 g / d or more, high anti-pilling properties and good peach To provide a Tencel cotton wool to impart Kin processability. Still another object is to provide a method for industrially producing such a modification.

【００１８】[0018]

【課題を解決するための手段】本発明は上記課題を解決
するために次の構成からなる。即ち、第１発明は、溶剤
紡糸セルロース系繊維において、単繊維の表面が揉み叩
き加工によるフィブリル化又はミクロフィブリル化構造
を呈しておらず、しかも該繊維からなる織編物の家庭用
洗濯機法での抗ピリング試験にＪＩＳ Ｌ−１０７６法
のピリング判定標準写真を準用しての判定で４級以上の
抗ピリング性に架橋改質されていながら、ピーチスキン
加工性が改質前と同等或いは改質前より良好であり、さ
らに反応染料による染色性及び染色堅牢度が改質前より
改善されていることを特徴とする溶剤紡糸セルロース系
繊維及び該繊維からなる繊維構造物であり、第２発明は
溶剤紡糸セルロース系繊維において、単繊維の表面が揉
み叩き加工によるフィブリル化又はミクロフィブリル化
構造を呈しておらず、しかも平均単繊維強度が３．０ｇ
／ｄ以上、４．３ｇ／ｄ以下、単繊維強度変動率が１０
％以下に調整されていて、さらに、ジグリシジルエーテ
ル又はポリグリシジルエーテル或いはグリシジルアクリ
レート化合物により架橋改質されていることを特徴とす
る、該繊維からなる織編物の家庭用洗濯機法での抗ピリ
ング試験にＪＩＳ Ｌ−１０７６法のピリング判定標準
写真を準用しての判定で４級以上の抗ピリング性であり
ながら、該繊維からなる織編物のピーチスキン加工性が
架橋改質前と同等或いは架橋改質前より良好であり、さ
らに反応染料による染色性及び染色堅牢度が改質前より
改善されている溶剤紡糸セルロース系繊維及び該繊維か
らなる繊維構造物である。さらに、第３発明は、溶剤紡
糸セルロース系繊維の原綿、スライバー、紡績糸或いは
織編物の改質において、紡糸油剤として残留付着してい
るアニオン界面活性剤又はカチオン界面活性剤の付着量
を０．０５重量％以下となるように熱水で洗い落とした
該繊維についてセルラーゼ加工を実施し、その際、該セ
ルラーゼ加工の総酵素力価（酵素力価（単位／ｇ）×酵
素濃度（％ｏｗｓ）×酵素加工時間（分））を１２５０
０単位以下、且つ、該セルラーゼ加工液の液流線速度を
最高部で５ｍ／秒以下に規制して該加工を実施し、さら
に、ジグリシジルエーテル又はポリグリシジルエーテル
或いはグリシジルアクリレート化合物により架橋改質す
ることを特徴とする請求項１の溶剤紡糸セルロース系繊
維及び該繊維からなる繊維構造物の製造方法である。The present invention has the following arrangement to solve the above-mentioned problems. That is, the first invention is a solvent-spun cellulosic fiber, wherein the surface of the single fiber does not exhibit a fibrillated or microfibrillated structure by rubbing and beating, and is a method for household washing of a woven or knitted fabric made of the fiber. In the anti-pilling test of JIS L-1076 method, the pilling judgment standard photo was applied correspondingly, and it was cross-linked and modified to have anti-pilling property of grade 4 or higher, but the peach skin workability was the same as or before modification. A solvent-spun cellulosic fiber and a fiber structure comprising the fiber, which are better than before and are improved in dyeing property and dyeing fastness with a reactive dye as compared with before modification. In the solvent-spun cellulosic fiber, the surface of the single fiber does not exhibit a fibrillated or microfibrillated structure by rubbing and beating, and the average single fiber strength is 3. 0g
/ D or more, 4.3 g / d or less, single fiber strength fluctuation rate is 10
% Or less and further cross-linked and modified with a diglycidyl ether or a polyglycidyl ether or a glycidyl acrylate compound, the anti-pilling of a woven or knitted fabric made of the fiber in a domestic washing machine method. In the test, the pilling judgment standard photograph of JIS L-1076 method was applied mutatis mutandis and the peach and knitting processability of the woven or knitted fabric made of the fibers was the same as that before the cross-linking modification or the cross-linking even though it had the anti-pilling property of 4 or higher. It is a solvent-spun cellulosic fiber which is better than before modification and has improved dyeing properties and dyeing fastness with a reactive dye as compared with before modification, and a fiber structure comprising the fiber. Furthermore, in the third invention, in the modification of raw cotton, sliver, spun yarn or woven or knitted solvent-spun cellulosic fibers, the amount of anionic surfactant or cationic surfactant remaining as a spinning oil agent is set to 0. Cellulase processing was performed on the fiber washed off with hot water so as to be not more than 05% by weight, in which case the total enzyme titer of the cellulase processing (enzyme titer (unit / g) x enzyme concentration (% ows) x Enzyme processing time (min) 1250
0 unit or less, and the liquid stream linear velocity of the cellulase processing liquid is regulated to 5 m / sec or less at the highest portion to carry out the processing, and further cross-linking modified with a diglycidyl ether or polyglycidyl ether or a glycidyl acrylate compound. The method for producing a solvent-spun cellulosic fiber and a fiber structure comprising the fiber according to claim 1.

【００１９】本発明は、第１に、先に本発明者等が提案
した発明の基本的技術、即ち、テンセル繊維の紡糸油剤
として常用されるアニオン界面活性剤又は希に使用され
るカチオン界面活性剤がセルラーゼの触媒毒であり、該
触媒毒作用はアニオン界面活性剤又はカチオン界面活性
剤の繊維への付着量を０．０５重量％以下に規制した場
合劇的に低減され、その結果、該繊維及び繊維構造物の
セルラーゼ加工による抗ピリング加工が、従来、該繊維
の抗ピリング加工の前処理として常用されている揉み叩
き加工を実施しなくても充分可能であり、しかも、該活
性剤の付着量の規制により該セルラーゼ加工を従来より
はるかに穏やかな、即ち、総酵素力価が著しく小さい条
件で可能になったこと、第２に、セルラーゼが該セルラ
ーゼ加工液の攪拌による剪断力で徐々に失活するが、該
失活は該加工液の液流線速度を最高部で５ｍ／秒以下に
規制することで防止でき、さらに小さな総酵素力価でセ
ルラーゼ加工が可能になること、第３に、先の本発明者
等による発明でも課題であった平均単繊維強度が３．０
ｇ／ｄ以上での抗ピリング性をより改善するべく、グリ
シジル化合物で架橋改質すること、以上３点の改善を組
み合わせることにより、通常の紡績条件、特にカード条
件で糸質が低下しない範囲、具体的には３．０ｇ／ｄ以
上に平均単繊維強度の調整を留めるセルラーゼ加工及び
架橋改質において、テンセル繊維の単繊維強度変動率が
従来のセルラーゼ加工は勿論、本発明者による先の発明
での該変動率と比しても大幅に改善され、均一性の顕著
に良好な実用繊維強度を持ち、高度の抗ピリング性と良
好なピーチスキン加工性が両立したテンセル繊維及び該
繊維構造物の製造を可能ならしめるものである。この意
味で、本発明はテンセル原綿の改質加工に特に有用であ
るが、これに限定されるものでは無く、紡績糸及び織編
物にも、抗ピリング性や布帛強度をより改善すること
や、染色性、染色堅牢度の改善を目的にして処理設備の
形態を若干変えるだけでそのまま適用できる。The present invention is, firstly, the basic technique of the invention previously proposed by the present inventors, that is, an anionic surfactant commonly used as a spinning oil for Tencel fiber or a rarely used cationic surfactant. The agent is a cellulase catalyst poison, and the catalyst poisoning effect is dramatically reduced when the amount of the anionic or cationic surfactant deposited on the fiber is controlled to 0.05% by weight or less. The anti-pilling process by cellulase process of the fiber and the fiber structure is sufficiently possible without performing the hitting process which is conventionally used as a pretreatment of the anti-pilling process of the fiber, and moreover, the active agent The cellulase processing was made possible by controlling the amount of attachment much more gently than before, that is, the total enzyme titer was extremely small. Secondly, the cellulase was stirred in the cellulase processing solution. Although it gradually deactivates due to shearing force, the deactivation can be prevented by limiting the stream velocity of the processing liquid to 5 m / sec or less at the maximum, and cellulase processing can be performed with a smaller total enzyme titer. Thirdly, the average single fiber strength, which was also a problem in the invention by the present inventors, was 3.0.
In order to further improve the anti-pilling property at g / d or more, cross-linking modification with a glycidyl compound, and by combining the above three improvements, a range in which the yarn quality does not deteriorate under normal spinning conditions, particularly curd conditions, Specifically, in the cellulase processing and cross-linking modification in which the adjustment of the average single fiber strength is kept to 3.0 g / d or more, the single fiber strength variation rate of the tencel fiber is not limited to the conventional cellulase processing, but the invention of the present invention was also used. The tencel fiber and the fibrous structure have a significantly improved practical fiber strength with significantly improved homogeneity and have a high degree of pilling resistance and good peach skin processability. Will be made possible. In this sense, the present invention is particularly useful for modification processing of TENCEL raw cotton, but is not limited to this, and for spun yarn and woven and knitted fabric, further improving anti-pilling property and fabric strength, and It can be applied as it is by slightly changing the form of the processing equipment for the purpose of improving the dyeability and dye fastness.

【００２０】逆の観点から説明すると、セルラーゼ加工
を施してない通常のテンセル繊維を架橋改質することで
高度の抗ピリング性に改質することができることは、前
記の文献からも、当業者ならば容易に予想できることで
ある。しかしながら、通常のテンセル繊維に該架橋改質
を施した場合、該改質を受けていないテンセルでも数時
間〜十数時間の処理時間を要したピーチスキン加工性が
さらに長時間を要するように悪化すると思われる。従っ
て、経済性を考慮した場合、実態として、架橋改質した
通常のテンセル繊維のピーチスキン加工は不可能であ
る。Explaining from the opposite point of view, it can be understood by those skilled in the art from the above-mentioned literature that it is possible to modify a normal tencel fiber which has not been subjected to cellulase processing to a cross-linking modification to obtain a high anti-pilling property. This is easily predictable. However, when the ordinary Tencel fiber is subjected to the cross-linking modification, the peach skin processability, which requires a processing time of several hours to several tens of hours, is deteriorated so that a longer time is required even in the Tencel that has not been modified. I think so. Therefore, in consideration of economic efficiency, it is practically impossible to process the peach skin of the ordinary crosslinked modified tencel fiber.

【００２１】これに対して、本発明者等はセルラーゼ加
工によりテンセル繊維の平均単繊維強度の調整を行い、
その際、アニオン界面活性剤又はカチオン界面活性剤の
繊維への付着量を０．０５重量％以下に規制し、さら
に、該セルラーゼ加工液の液流線速度を最高部で５ｍ／
秒以下に規制した上で総酵素力価が１２５００単位以下
の非常に穏やかな条件での該加工を実施した場合、その
効果として単繊維維強度変動率が１０％以下の該加工を
可能にし、これと架橋度をコントロールしたグリシジル
化合物による改質を組み合わせた場合、通常の紡績条
件、特にカード条件で糸質が低下しない範囲、具体的に
は３．０ｇ／ｄ以上の平均単繊維強度の範囲において
も、高度の抗ピリング性と良好なピーチスキン加工性を
合わせ持ったテンセル綿、ひいてはテンセル繊維構造物
の製造を可能にした。この場合、セルラーゼ加工での繊
維強度変動率を１０％以下に規制することは肝要な条件
であって、平均単繊維強度が３．０ｇ／ｄ以上でも、単
繊維強度変動率が１０％を越えた場合、単繊維強度の範
囲が広くなるため、これだけでも紡績工程での糸質維
持、高度の抗ピリング性それに良好なピーチスキン加工
性を阻害することは本発明者等の先の発明等で説明した
が、さらにこれにグリシジル化合物による架橋改質を組
合わせた場合、その架橋改質が不均一に進み、前記の不
均一性との相乗作用により各問題点はさらに拡大する。On the other hand, the present inventors adjusted the average single fiber strength of tencel fiber by cellulase processing,
At that time, the amount of the anionic surfactant or cationic surfactant adhering to the fiber was regulated to 0.05% by weight or less, and the liquid stream linear velocity of the cellulase working liquid was 5 m / m at the maximum.
When the processing is carried out under a very mild condition such that the total enzyme titer is 12,500 units or less after being restricted to not more than 2 seconds, the effect is that the processing rate of the single fiber strength variation is 10% or less, When this is combined with modification with a glycidyl compound whose degree of cross-linking is controlled, the range is such that the yarn quality does not deteriorate under normal spinning conditions, especially card conditions, and specifically, the range of average single fiber strength of 3.0 g / d or more. In this case, it was possible to produce TENCEL cotton, which has a high degree of pilling resistance and good peach skin processability, and thus TENCEL fiber structure. In this case, it is an essential condition to regulate the fiber strength variation rate during cellulase processing to 10% or less, and even if the average single fiber strength is 3.0 g / d or more, the single fiber strength variation rate exceeds 10%. In this case, since the range of the single fiber strength is widened, it is possible to prevent the yarn quality maintenance in the spinning process, the high anti-pilling property and the good peach-skin processability by this alone. As described above, when a crosslinking modification with a glycidyl compound is further combined therewith, the crosslinking modification proceeds nonuniformly, and each problem is further magnified by the synergistic effect with the above-mentioned nonuniformity.

【００２２】アニオン界面活性剤及びカチオン界面活性
剤のセルラーゼに対する触媒毒については先に本発明者
等が提案した発明で説明した。即ち、従来、溶剤紡糸セ
ルロース系繊維及び該繊維からなる繊維構造物に前処理
として実施されていた揉み叩き加工は、フィブリル化以
外にセルラーゼの触媒毒である紡糸油剤としてのアニオ
ン界面活性剤又はカチオン界面活性剤を不充分ながらも
繊維から剥離させることに潜在的な意味があったが、現
実には該意味は認識されておらず、ましてやアニオン界
面活性剤又はカチオン界面活性剤を０．０５重量％以下
に規制する必要性が均一なセルラーゼ加工に必要である
ことは全くと言っても過言で無く意識されていなかっ
た。その為、前処理としての揉み叩き加工で無意識で熱
水洗されていた以外、紡糸油剤としてのアニオン界面活
性剤又はカチオン界面活性剤の上記規制に対して無策で
あり、その為、揉み叩き加工をしない単なるセルラーゼ
加工のみで、効果的な抗ピリング加工及び均一な実用繊
維強度を持った抗ピリング加工が出来ず、これは不可能
と考えられていた。The catalyst poisons of anionic surfactants and cationic surfactants for cellulase have been described in the invention previously proposed by the present inventors. That is, conventionally, the beating process, which has been carried out as a pretreatment on a solvent-spun cellulosic fiber and a fiber structure composed of the fiber, is an anionic surfactant or a cation as a spinning oil agent which is a catalyst poison of cellulase other than fibrillation. Although there was a latent meaning in stripping the fiber from the fiber even though the surfactant was insufficient, the meaning was not recognized in reality, and it was even less than 0.05% by weight of the anionic surfactant or the cationic surfactant. It was no exaggeration to say that the need to regulate to less than 100% is necessary for uniform cellulase processing, and it was not recognized. Therefore, except that it was unintentionally washed with hot water in the beating process as a pretreatment, it is ineffective for the above regulation of the anionic surfactant or the cationic surfactant as a spinning oil agent, and therefore the beating process is performed. It was thought that this was not possible because effective anti-pilling processing and anti-pilling processing with uniform practical fiber strength could not be achieved by only simple cellulase processing.

【００２３】即ち、通常、テンセル繊維はアニオン界面
活性剤を主成分とするアニオン界面活性剤、時には、カ
チオン界面活性剤が０．３〜０．６重量％付着してい
る。従来、揉み叩き加工を実施しないで該繊維の抗ピリ
ングを目的にしたセルラーゼ加工に於いて、アニオン界
面活性剤又はカチオン界面活性剤が触媒毒であり、該触
媒毒の付着量を０．０５重量％以下に規制する必要性が
認識されていなかった為、これをこのまま水洗せずに、
或いは１回程度熱水洗してセルラーゼ加工を実施するの
が通例であった。１回程度の熱水洗では、繊維に付着し
ている紡糸油剤はせいぜい３分の１程度にしか減少して
おらず０．１０〜０．２０重量％残留付着している。That is, usually, the tencel fiber has 0.3 to 0.6% by weight of an anionic surfactant containing an anionic surfactant as a main component, and sometimes a cationic surfactant. Conventionally, in cellulase processing for the purpose of anti-pilling of the fiber without performing rubbing and tapping processing, an anionic surfactant or a cationic surfactant is a catalyst poison, and the amount of the catalyst poison deposited is 0.05% by weight. Since it was not recognized that it was necessary to regulate the amount below%, do not wash it as it is,
Alternatively, it was customary to carry out cellulase processing by washing with hot water about once. In about once washing with hot water, the spinning oil agent adhering to the fiber is reduced to about one third at most, and 0.10 to 0.20% by weight remains adhering.

【００２４】これをセルラーゼ加工で抗ピリングに改質
するには、触媒毒に打ち勝つ為、酵素力価１５００〜１
８００単位／ｇを持つ通常のセルラーゼの場合、酵素初
期濃度５ｇ〜１０ｇ／ l、酵素反応時間２〜３時間の処
理が必要で、この場合、総酵素力価としては少なくとも
１５００（単位／ｇ）×０．５（％ｏｗｓ）×１２０
（分）＝９００００単位の作用が必要であった。これは
セルラーゼ加工の総酵素力価としては非常に激しいもの
であり、その為、紡糸油剤の付着ムラに応じて、該油剤
の付着量が少ない部分で局部的にセルラーゼ加工が進み
過ぎ、結果的にセルラーゼ加工後の溶剤紡糸セルロース
系繊維及び該繊維からなる繊維構造物の単繊維強度変動
率は４０％を越え、部分的に極度に単繊維強度が弱い箇
所が発生し、溶剤紡糸セルロース系繊維で構成される布
帛は実用強度を満足しないことになる。To modify this into anti-pilling by cellulase processing, the enzyme titer is 1500 to 1 in order to overcome the catalyst poison.
In the case of a normal cellulase having 800 units / g, it is necessary to treat the enzyme with an initial concentration of 5 g to 10 g / l and an enzyme reaction time of 2 to 3 hours. In this case, the total enzyme titer is at least 1500 (unit / g). X 0.5 (% ows) x 120
(Min) = 90,000 units of action required. This is extremely severe as the total enzyme titer of cellulase processing, and therefore, depending on the adhesion unevenness of the spinning oil agent, the cellulase processing excessively progresses locally at a portion where the oil agent adhesion amount is small, resulting in In the solvent-spun cellulosic fiber after cellulase processing, the single fiber strength variation rate of the fiber structure comprising the fiber exceeds 40%, and there are some places where the single fiber strength is extremely weak. The fabric composed of does not satisfy the practical strength.

【００２５】これに対して、先に本発明者等が提案した
発明ではセルラーゼ加工前の熱水洗を３回以上実施し最
後に遠心脱水を実施するとか、各回の脱液に遠心脱水を
する熱水洗を２回以上実施するとかで、目標意識を持っ
て徹底的に熱水洗し残留する紡糸油剤としてのアニオン
界面活性剤又はカチオン界面活性剤を０．０５重量％以
下、好ましくは０．０２５重量％以下に落とした場合、
触媒毒の紡糸油剤としてのアニオン界面活性剤又はカチ
オン界面活性剤が少なく、且つ該界面活性剤の付着の濃
淡の差が小さいため、総酵素力価の非常に小さい条件で
均一なバイオ加工が可能になり、例えば、酵素力価１５
００〜１８００単位／ｇの酵素の場合、酵素濃度１ｇ／
l、酵素反応時間２時間のセルラーゼ加工で均一性の良
い抗ピリング性に改質された溶剤紡糸セルロース系繊維
及び該繊維からなる繊維構造物が得られた。即ち、この
場合、総酵素力価は最大でも１８００（単位／ｇ）×
０．１（％ｏｗｓ）×１２０（分）＝２１６００単位と
非常に穏やかなものであり、その為セルラーゼ加工後の
平均単繊維強度が３．５ｇ／ｄ以下でありながら単繊維
強度変動率が２０％以下に均一に改質され、その結果と
して、該繊維から成る織編物の家庭洗濯機法での抗ピリ
ング試験にＪＩＳ Ｌ−１０７６法のピリング判定標準
写真を準用しての判定で４級以上の抗ピリング性であ
り、しかも該繊維からなる織物強度の均一性が良好に改
質された抗ピリング性溶剤紡糸セルロース系繊維及び該
繊維からなる繊維構造物が得られた。On the other hand, in the invention previously proposed by the present inventors, hot water washing before cellulase processing is carried out three times or more, and centrifugal dehydration is finally carried out. Washing with water twice or more, and thoroughly rinsing with hot water with the goal in mind, and remaining 0.05% by weight or less, preferably 0.025% by weight of anionic or cationic surfactant as a spinning oil remaining. If dropped below%,
Since there are few anionic or cationic surfactants as catalyst poison spinning oils, and the difference in the density of adhesion of these surfactants is small, uniform bioprocessing is possible under conditions where the total enzyme titer is extremely small. , For example, an enzyme titer of 15
In the case of enzyme of 0 to 1800 units / g, the enzyme concentration is 1 g /
By the cellulase processing with an enzyme reaction time of 2 hours, solvent-spun cellulosic fibers modified to have good uniformity and anti-pilling properties, and a fiber structure composed of the fibers were obtained. That is, in this case, the total enzyme titer is at most 1800 (unit / g) ×
0.1 (% ows) × 120 (min) = 21600 units, which is very gentle, and therefore the average single fiber strength after cellulase processing is 3.5 g / d or less, but the single fiber strength variation rate is It is uniformly modified to 20% or less, and as a result, it is grade 4 by judgment by applying the pilling judgment standard photograph of JIS L-1076 method to the anti-pilling test in the domestic washing machine method of the woven and knitted fabric made of the fibers. An anti-pilling solvent-spun cellulosic fiber having the above-mentioned anti-pilling property and improved woven fabric uniformity in good condition, and a fiber structure comprising the fiber were obtained.

【００２６】本発明は、先に本発明者等が提案した前記
の発明の改良に関するもので、これにより、先の発明の
アニオン界面活性剤又はカチオン界面活性剤の規制下で
のセルラーゼ加工に加えて、該セルラーゼ加工液の液流
線速度に規制を加えることにより単繊維強度変動率が１
０％以下と、該加工を施さないテンセル繊維と同程度に
なり、さらにこれにグリシジル化合物による架橋改質を
組み合わせることにより、先の発明の平均単繊維強度が
３．０ｇ／ｄ以上のテンセル繊維の抗ピリング性を改善
するとともに良好なピーチスキン加工性を両立させたこ
と、及び同じく３．０ｇ／ｄ以上の平均単繊維強度のテ
ンセル繊維及び該繊維構造物に高度な抗ピリング性と良
好なピーチスキン加工性を付与できる、高品位の糸質の
紡績を可能ならしめる該繊維の原綿の改質加工を提案す
ることに新規性と進歩性がある。The present invention relates to an improvement of the above-mentioned invention previously proposed by the present inventors, which enables the cellulase processing under the control of the anionic surfactant or cationic surfactant of the previous invention to be added. Then, the rate of fluctuation of the single fiber strength is reduced to 1 by controlling the flow velocity of the cellulase processing liquid.
The content of 0% or less is similar to that of the unprocessed TENCEL fiber, and by combining this with a crosslinking modification with a glycidyl compound, the TENCEL fiber having an average single fiber strength of the above invention of 3.0 g / d or more. Has good anti-pilling properties and good peach skin processability, and also has high anti-pilling properties for Tencel fiber having an average single fiber strength of 3.0 g / d or more and the fiber structure. There is novelty and an inventive step in proposing a modified process of raw cotton of the fiber which enables the spinning of high quality yarn quality capable of imparting peach skin processability.

【００２７】[0027]

【発明の実施の形態】以下、本発明の構成要件を具体的
に説明する。本発明の溶剤紡糸セルロース系繊維とは、
具体的には、現在のところ商業的に実用化されているテ
ンセル（商品名）が唯一該当する。そして本発明はテン
セル原綿、スライバー、紡績糸、或いは織編物等の全て
に適用できるが、特に原綿に適用した場合の効果が生産
性及び経済性及び他素材との複合性の面で大きい。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The components of the present invention will be specifically described below. With the solvent-spun cellulosic fiber of the present invention,
Specifically, only Tencel (trade name) that is commercially practically used at present is applicable. The present invention can be applied to all of Tencel raw cotton, sliver, spun yarn, woven or knitted fabric, etc., but the effect when applied to raw cotton is particularly large in terms of productivity, economic efficiency, and compoundability with other materials.

【００２８】本発明においては、現在テンセル繊維のセ
ルラーゼ加工の前処理として必ず実施されている揉み叩
き加工を行わないのが大きな特徴である。その理由は前
記したが、大規模生産と短時間処理でのセルラーゼ加工
で経済性を改善し、しかも加工の均一性の改善が期待で
きる点、さらには揉み叩き加工やセルラーゼ加工が困難
な他素材とテンセル繊維との混紡を実施する要望から、
テンセル原綿でのセルラーゼ加工が望まれていたが、テ
ンセル原綿の場合、揉み叩き加工は後の紡績を不可能に
するほど綿を損傷するからである。本発明でピーチスキ
ン調の布帛を製造する場合は、テンセル繊維を布帛に製
編織した後揉み叩き加工のみを実施する。本発明の場
合、単繊維強度が適度に調整されいて、その上で架橋改
質されているため、短時間の揉み叩き加工のみで良好な
ピーチスキン加工と高度な抗ピリング性が両立する。A major feature of the present invention is that the beating process, which is always performed as a pretreatment for the cellulase process of tencel fibers, is not performed. The reason is as described above, but it is possible to improve the economic efficiency by cellulase processing in large-scale production and short time processing, and further, it is possible to expect improvement in uniformity of processing, and further it is difficult to beat other materials or cellulase processing other materials From the request to carry out a blended spinning with Tencel fiber,
This is because the cellulase process using the TENCEL raw cotton has been desired, but in the case of the TENCEL raw cotton, the rubbing and beating process damages the cotton so that the subsequent spinning is impossible. In the case of producing a peach-skin-like cloth according to the present invention, only tencel fibers are woven and knitted into a cloth, and then only a rubbing and tapping process is performed. In the case of the present invention, since the strength of the single fiber is appropriately adjusted and then the cross-linking is modified, good peach skin processing and high anti-pilling property can be achieved by only rubbing for a short time.

【００２９】本発明のテンセル繊維の平均単繊維強度は
３．０ｇ／ｄ以上、好ましくは３．５ｇ／ｄ以上、４．
３ｇ／ｄ以下である。平均単繊維強度が小さくなるほど
抗ピリング性は良好になるが、３．０ｇ／ｄ以下の該強
度の場合、セルラーゼ加工だけで高度な抗ピリング加工
が可能であるから効果としては小さい。但し、３．０ｇ
／ｄ以下でもグリシジル化合物による改質は反応染料に
よる染色性及び染色堅牢度を改質前より顕著に改善する
ため、この観点では３．０ｇ／ｄ以下でもグリシジル化
合物による改質の意味はある。The average single fiber strength of the tencel fiber of the present invention is 3.0 g / d or more, preferably 3.5 g / d or more,
It is 3 g / d or less. The smaller the average single fiber strength is, the better the anti-pilling property is. However, when the strength is 3.0 g / d or less, the effect is small because the advanced anti-pilling process can be performed only by the cellulase process. However, 3.0g
/ D or less, the modification with the glycidyl compound remarkably improves the dyeing property and the dyeing fastness with the reactive dye before the modification. From this viewpoint, the modification with the glycidyl compound is significant even at 3.0 g / d or less.

【００３０】本発明によつて得られるテンセル繊維の単
繊維強度変動率は１０％以下、好ましくは８％以下であ
る。これはセルラーゼ加工前に紡糸油剤としてのアニオ
ン界面活性剤又はカチオン界面活性剤を徹底的に洗い落
とし、残留アニオン界面活性又はカチオン界面活性剤を
平均で０．０５重量％以下、好ましくは０．０２５重量
％以下に規制することと、該セルラーゼ加工液の攪拌に
よる液流線速度を最高部で５ｍ／秒以下に規制し、攪拌
による剪断力でセルラーゼが失活するのを抑制すること
で可能になる。The tencel fiber obtained according to the present invention has a single fiber strength variation rate of 10% or less, preferably 8% or less. This is because the anionic or cationic surfactant as a spinning oil is thoroughly washed off before cellulase processing, and the residual anionic or cationic surfactant is 0.05% by weight or less on average, preferably 0.025% by weight. % Or less, and the liquid stream linear velocity due to stirring of the cellulase processing liquid is regulated to 5 m / sec or less at the highest part to suppress cellulase deactivation due to shearing force due to stirring. .

【００３１】本発明のセルラーゼ加工において、残留ア
ニオン界面活性剤又はカチオン界面活性剤が０．０２５
重量％以下で単繊維強度変動率は概ね８％以下、０．０
５重量％以下で該変動率は概ね１０％以下である。残留
アニオン又はカチオン界面活性剤が０．１０重量％以上
の場合は、所定の水準に繊維強度を調整するためには、
相対的に総酵素力価の大きいセルラーゼ加工が必要にな
り、この場合、セルラーゼ加工が残留活性剤の付着ムラ
に応じて、不均一しかも局部的に過剰に進み、セルラー
ゼ加工及び架橋改質後のテンセル繊維の平均単繊維強度
を３．０ｇ／ｄ程度に調整した場合、単繊維強度変動率
は場合によっては４０％以上になる場合があり、該繊維
からなる繊維構造物は部分的に強度不足の箇所が発生し
実用繊維としては採用できない。しかも、本発明の場
合、単繊維強度変動率の大きさに応じて架橋改質反応が
不均一に進むため、抗ピリング性及びピーチスキン加工
性も布帛表面上に不均一に発現するので好ましくない。In the cellulase processing of the present invention, the residual anionic surfactant or cationic surfactant is 0.025%.
If the weight% or less, the fluctuation rate of the single fiber strength is generally 8% or less,
When the content is 5% by weight or less, the variation rate is generally 10% or less. When the residual anionic or cationic surfactant is 0.10% by weight or more, in order to adjust the fiber strength to a predetermined level,
Cellulase processing with a relatively large total enzyme titer is required. In this case, cellulase processing proceeds unevenly and locally excessively depending on the adhesion unevenness of the residual active agent, and cellulase processing When the average single fiber strength of TENCEL fiber is adjusted to about 3.0 g / d, the single fiber strength variation rate may be 40% or more in some cases, and the fiber structure composed of the fibers is partially insufficient in strength. Is not possible to use as a practical fiber. Moreover, in the case of the present invention, the cross-linking modification reaction proceeds non-uniformly according to the magnitude of the single fiber strength variation rate, and therefore the anti-pilling property and the peach skin processability are also non-uniformly expressed on the fabric surface, which is not preferable. .

【００３２】本発明のテンセル繊維はグリシジル化合物
により架橋改質されている。該グリシジル化合物として
は、エチレングリコール、ポリエチレングリコール、プ
ロピレングリコール、ポリプロピレングリコール、グリ
セリン、ソルビトール、ポリグリセロール、ペンタエリ
スリトール等のジ、及びポリグリシジルエーテル或いグ
リシジルアクリレートであるが、エチレングリコール、
ポリエチレングリコール、プロピレングリコール及びポ
リプロピレングリコールのジグリシジルエーテルが効果
及び経済性の面で好ましい。The tencel fiber of the present invention is crosslinked and modified with a glycidyl compound. Examples of the glycidyl compound include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, glycerin, sorbitol, polyglycerol, pentaerythritol, and other di- and polyglycidyl ethers or glycidyl acrylates.
Diglycidyl ethers of polyethylene glycol, propylene glycol and polypropylene glycol are preferred from the viewpoint of effect and economy.

【００３３】本発明のグリシジル化合物による架橋度
は、これを重量増加率で表した場合、１〜２０重量％、
好ましくは２〜１５重量％が望ましい。１重量％以下で
は抗ピリング性が３級以下であるし、２０重量％を越え
た場合ピーチスキン加工性が不良になる。The degree of crosslinking by the glycidyl compound of the present invention is 1 to 20% by weight when expressed in terms of weight increase rate,
It is preferably 2 to 15% by weight. If it is less than 1% by weight, the anti-pilling property is below grade 3, and if it exceeds 20% by weight, the workability of peach skin becomes poor.

【００３４】本発明のセルラーゼ加工及び架橋改質によ
って、テンセル繊維は平均単維強度が３．０ｇ／ｄ以上
でも高度な抗ピリング性と良好なピーチスキン加工性を
合わせ持った繊維に改質される。そして、該繊維からな
る織編物の家庭用洗濯機法での抗ピリング試験にＪＩＳ
Ｌ−１０７６法のピリング判定標準写真を準用しての
判定は、平均単繊維強度が３．０〜４．０ｇ／ｄで５
級、４．０ｇ／ｄ以上で４級以上である。本発明によっ
て平均単繊維強度が３．０ｇ／ｄ以上でも高度な抗ピリ
ング性と良好なピーチスキン加工性を合わせ持つた繊維
にテンセル繊維を改質できたことは、細番手紡績糸によ
る薄地織編物に抗ピリング性と充分な実用強度を付与す
るに極めて効果的である。By the cellulase processing and cross-linking modification of the present invention, the tencel fiber is modified into a fiber having high anti-pilling property and good peach skin processability even if the average fiber strength is 3.0 g / d or more. It Then, the woven and knitted fabric made of the fiber is subjected to the JIS anti-pilling test in the domestic washing machine method.
The pilling judgment of the L-1076 method was applied mutatis mutandis, and the judgment was 5 when the average single fiber strength was 3.0 to 4.0 g / d.
Grade 4 or higher at 4.0 g / d or higher. According to the present invention, the tencel fiber can be modified into a fiber having a high anti-pilling property and a good peach skin processability even if the average single fiber strength is 3.0 g / d or more. It is extremely effective in imparting anti-pilling properties and sufficient practical strength to a knitted fabric.

【００３５】本発明の家庭用洗濯機法での抗ピリング試
験は、ＪＩＳ Ｌ−０２１７の１０３法に準拠した方法
で、家庭用洗濯機（ＪＩＳ Ｌ−０２１７の１０３号の
規定するもの）を使用し、衣料用合成洗剤２ｇ／ｌを含
む液温４０℃の洗濯機、浴比１：３０で、試験片３枚と
負荷布２枚（計５枚）を５分間洗濯した後脱液し、次に
常温の水で２分間すすぎ洗いと脱液を各々２回行い、試
験片と負荷布を取り出しタンブル乾燥機で乾燥する（吹
き出し温度約７０℃）。この操作を５回くり返し、得ら
れた試験片をＪＩＳ Ｌ−１０７６法のピリング判定標
準写真を準用して試験片の抗ピリング性を判定する。The anti-pilling test in the domestic washing machine method of the present invention is a method in conformity with JIS L-0217 method 103, and uses a domestic washing machine (specified in JIS L-0217 No. 103). Then, wash 3 pieces of test pieces and 2 pieces of load cloth (5 pieces in total) for 5 minutes in a washing machine containing a synthetic detergent for clothes at a liquid temperature of 40 ° C. at a bath temperature of 1:30, and then drain the liquid, Next, rinsing with water at room temperature for 2 minutes and deliquoring are each performed twice, and the test piece and the load cloth are taken out and dried with a tumble dryer (blowing temperature about 70 ° C.). This operation is repeated five times, and the obtained test piece is evaluated for the anti-pilling property of the test piece according to the standard pilling judgment standard photograph of JIS L-1076 method.

【００３６】本発明方法に於いては、溶剤紡糸セルロー
ス系繊維に付着している紡糸油剤として常用されるアニ
オン界面活性剤、或いは時に配合されるカチオン界面活
性剤を０．０５重量％以下、好ましくは０．０２５重量
％以下に削減すべく、揉み叩き加工に代わって、セルラ
ーゼ加工前に徹底的に熱水洗する必要がある。この為に
は、熱水洗を３回以上実施し最後に遠心脱水するとか、
熱水洗後に毎回遠心脱水する熱水洗を２回以上実施する
とかの方策が必要である。この際、助剤として、酸性亜
硫酸ナトリウム、硫酸ナトリウム等の無機塩や水酸化ナ
トリウム、炭酸ナトリウム等のアルカリ、或いはノニオ
ン界面活性剤系の洗浄剤や膨潤剤を添加した方が、アニ
オン界面活性剤又はカチオン界面活性剤を洗い落としや
すくなるので好ましい。In the method of the present invention, the anionic surfactant, which is usually used as a spinning oil agent adhering to the solvent-spun cellulosic fibers, or the cationic surfactant, which is sometimes mixed, is preferably 0.05% by weight or less. In order to reduce the content to 0.025% by weight or less, it is necessary to thoroughly perform hot water washing before cellulase processing instead of kneading and beating processing. For this purpose, washing with hot water three times or more and centrifugal dehydration at the end,
It is necessary to take measures such that hot water washing is performed twice or more by centrifugal dewatering each time after hot water washing. At this time, it is preferable to add an inorganic salt such as acidic sodium sulfite or sodium sulfate, an alkali such as sodium hydroxide or sodium carbonate, or a nonionic surfactant-based detergent or swelling agent as an anionic surfactant. Alternatively, it is preferable because the cationic surfactant is easily washed off.

【００３７】一方、このような処理で、アニオン界面活
性剤又はカチオン界面活性剤を０．０５重量％以下に規
制する目標意識がない場合は、熱水洗無しでセルラーゼ
加工を実施するか、最良でも１回水洗後、自然脱液して
含水５００〜６００％のままセルラーゼ加工液に投入す
る程度が通例であるが、この程度の熱水洗ではアニオン
界面活性剤又はカチオン界面活性剤を０．０５重量％以
下に規制することは不可能である。On the other hand, in such a treatment, if there is no target consciousness to regulate the anionic surfactant or the cationic surfactant to 0.05% by weight or less, cellulase processing is carried out without hot water washing, or at best, After washing once with water, it is customary to naturally deliquorate and add to the cellulase processing solution with a water content of 500 to 600%, but with this degree of hot water washing, 0.05 weight of anionic surfactant or cationic surfactant is added. It is impossible to regulate below%.

【００３８】本発明方法のセルラーゼとしては、セルロ
ース繊維の減量処理用として一般に市販されているセル
ラーゼが全て適用され、例えば、エンチロンＣＭ−４０
Ｌ（洛東化成工業（株））、セルクラスト１．５Ｌ（ノ
ボノルディスク（株））、酵素ＯＰ−８８００（ＧＥＮ
ＥＮＣＯＲ社）、セルラーゼＸＰ−４２５（長瀬生化学
（株））等である。これらのセルラーゼの酵素力価は通
常１５００〜３０００単位／ｇである。尚、この場合の
セルラーゼの酵素力価の１単位は、カルボキシメチルセ
ルロース（ＣＭＣ）を基質とし、４０℃、ｐＨ４．５に
於いて１分間に１μｍｏｌのブドウ糖を生成する活性で
ある。As the cellulase of the method of the present invention, all commercially available cellulases for weight loss treatment of cellulose fibers are applied, for example, Entilon CM-40.
L (Rakuto Kasei Kogyo Co., Ltd.), Cell Crust 1.5L (Novo Nordisk Co., Ltd.), Enzyme OP-8800 (GEN)
ENCOR), Cellulase XP-425 (Nagase Biochemical Co., Ltd.) and the like. The enzyme titer of these cellulases is usually 1500 to 3000 units / g. Incidentally, one unit of the enzyme titer of cellulase in this case is the activity of using carboxymethylcellulose (CMC) as a substrate and producing 1 μmol of glucose per minute at 40 ° C. and pH 4.5.

【００３９】本発明方法のセルラーゼ加工の最適温度
は、酵素の種類により若干異なるが、一般には５０〜６
０℃である。５０℃以下でも反応は進むが遅く、特別の
理由がないかぎりこれより低温で処理する意味はない。
本発明方法の処理中のｐＨは３．５〜６．５、好ましく
は４．５〜５．５に維持される。この際ｐＨ緩衝剤とし
て酢酸緩衝剤、クエン酸緩衝剤、リン酸緩衝剤を適宜使
用する。The optimum temperature for cellulase processing in the method of the present invention varies depending on the kind of enzyme, but is generally 50-6.
0 ° C. The reaction proceeds slowly even at 50 ° C or lower, and there is no point in treating at a temperature lower than this unless there is a special reason.
The pH is maintained at 3.5-6.5, preferably 4.5-5.5, during the process of the invention. At this time, an acetic acid buffer, a citrate buffer, or a phosphate buffer is appropriately used as the pH buffer.

【００４０】本発明方法はセルラーゼ加工時の加工液の
攪拌による液流線速度を最高部で５ｍ／秒以下、好まし
くは２ｍ／秒以下、より好ましくは１ｍ／秒以下に規制
することを特徴とする。セルラーゼはセルロース構造の
加水分解反応の触媒であり、消耗されるものではないた
め、処理温度の均一性と保温が図れる場合セルラーゼ加
工は必ずしも攪拌を必要とするものではない。液流線速
度が５ｍ／秒を越えた場合、セルラーゼは加工時間の経
過とともに急速に失活する。その理由は詳しくは分から
ないが、加工液の攪拌によつて発生する該酵素に対する
剪断力で酵素構造が破壊されるからだと思われる。酵素
は蛋白質であり、蛋白質が剪断力で変性することは有り
うる。ただ、セルラーゼが５ｍ／秒程度の液流線速度で
失活することは新しい知見で有り、これは驚くべき事実
である。蛋白質の剪断力による変性については「流動に
よる高分子の結晶化」（高分子刊行会）に詳しい。The method of the present invention is characterized in that the liquid stream linear velocity due to stirring of the working fluid during cellulase processing is restricted to 5 m / sec or less at the maximum, preferably 2 m / sec or less, and more preferably 1 m / sec or less. To do. Since cellulase is a catalyst for the hydrolysis reaction of the cellulose structure and is not consumed, cellulase processing does not necessarily require stirring when the treatment temperature can be kept uniform and the temperature can be maintained. When the liquid stream velocity exceeds 5 m / sec, the cellulase rapidly deactivates with the lapse of processing time. Although the reason for this is not known in detail, it is considered that the enzyme structure is destroyed by the shearing force for the enzyme generated by stirring the processing liquid. The enzyme is a protein, and it is possible that the protein is denatured by shearing force. However, it is a new finding that cellulase is inactivated at a liquid stream linear velocity of about 5 m / sec, which is a surprising fact. For more information on protein denaturation by shearing force, see "Crystallization of Polymers by Flow" (Polymer Publishing Society).

【００４１】本発明方法において、液流線速度を最高部
で５ｍ／秒以下に規制することは、セルラーゼ加工の液
循環径路全般に留意しなければならない。例えば、本発
明で最も好ましい原綿のセルラーゼ加工において、設備
としてオーバーマイヤー型染色機を用いた場合、液流線
速度が最高の部分は加工液の循環ポンプの攪拌羽根の部
分になるが、単純に考えて攪拌羽根の直径が２０ｃｍ、
回転数が１０００ｒｐｍの場合、液流線速度は０．２ｍ
×３．１４×１０００ｒｐｍ÷６０秒＝１０．５ｍ／秒
になる。従って、この場合、回転数が５００ｒｐｍ以
下、好ましくは２００ｒｐｍ以下、より好ましくは１０
０ｒｐｍ以下の攪拌でセルラーゼ加工を実施しなければ
ならないことになる。１００ｒｐｍ程度の攪拌になると
ほとんど静置反応になるが、液組成と温度の均一性が図
られるなら前記の理由で問題にはならない。In the method of the present invention, it should be noted that the liquid flow linear velocity is restricted to 5 m / sec or less at the highest part in all liquid circulation paths for cellulase processing. For example, in the cellulase processing of raw cotton most preferred in the present invention, when an Overmeier type dyeing machine is used as equipment, the portion where the liquid streamline velocity is the highest is the stirring blade portion of the circulating pump for the processing liquid, but simply Considering that the diameter of the stirring blade is 20 cm,
When the rotation speed is 1000 rpm, the liquid stream velocity is 0.2 m
× 3.14 × 1000 rpm ÷ 60 seconds = 10.5 m / second. Therefore, in this case, the rotation speed is 500 rpm or less, preferably 200 rpm or less, more preferably 10 rpm or less.
The cellulase processing must be carried out with stirring at 0 rpm or less. When the stirring is carried out at about 100 rpm, the reaction is almost stationary, but if the composition of the liquid and the temperature are uniform, there is no problem for the above reason.

【００４２】本発明方法のセルラーゼ加工においては、
酵素の触媒毒であるアニオン界面活性剤又はカチオン界
面活性剤のテンセル繊維への付着量を０．０５重量％以
下、好ましくは０．０２５重量％以下、セルラーゼ加工
液の液流線速度を最高部で５ｍ／秒以下に規制している
為、所定の範囲に平均単繊維強度を調整するのに必要な
セルラーゼ濃度を劇的に少なくすることが可能で、総酵
素力価＝酵素力価（単位／ｇ）×酵素濃度（％ｏｗｓ）
×処理時間（分）として１２５００単位以下、好ましく
は６２５０単位以下に規制することが可能となる。これ
によって処理後の、単繊維強度変動率は１０％以下、好
ましくは８％以下になり、その結果、グリシジル化合物
による架橋結合の分布が均一になり、高度の抗ピリング
性と良好なピーチスキン加工性の両立を可能ならしめた
ことが本発明の特徴である。In the cellulase processing of the method of the present invention,
The amount of the anionic or cationic surfactant, which is a catalytic poison of the enzyme, attached to the TENCEL fiber is 0.05% by weight or less, preferably 0.025% by weight or less. Since it is regulated to 5 m / sec or less, it is possible to dramatically reduce the cellulase concentration necessary for adjusting the average single fiber strength within a predetermined range. Total enzyme titer = enzyme titer (unit / G) x enzyme concentration (% ows)
× It becomes possible to regulate the processing time (minutes) to 12,500 units or less, preferably 6250 units or less. As a result, the fluctuation rate of the single fiber strength after the treatment becomes 10% or less, preferably 8% or less, and as a result, the distribution of the cross-linking bond by the glycidyl compound becomes uniform, and the high pilling property and good peach skin processing It is a feature of the present invention that the compatibility of both sexes is possible.

【００４３】本発明方法のセルラーゼ加工においては、
通常、酵素力価１５００〜１８００単位／ｇのセルラー
ゼ、例えば酵素ＯＰ−８８００（ＧＥＮＥＮＣＯＲ
社）、セルクラスト（ノボノルディスク（株））、処理
時間として１〜２時間の場合、酵素濃度は０．５ｇ／ l
程度が適当である。この場合の総酵素力価＝１５００〜
１８００（単位／ｇ）×０．０５（％ｏｗｓ）×６０〜
１２０（分）＝４５００〜１０８００単位である。従っ
て、同一セルラーゼで酵素濃度を２倍にすれば処理時間
は１／２で良い。実用処方としては、むしろ作業の段取
り上最適のセルラーゼ加工時間を設定し、使用酵素の力
価に応じて総酵素力価の規制をクリアーする酵素濃度を
決定することになるが、通常セルラーゼ加工時間は２〜
３時間が適当である。In the cellulase processing of the method of the present invention,
Usually, a cellulase having an enzyme titer of 1500 to 1800 units / g, such as the enzyme OP-8800 (GENENCOR).
Company), Cell Crust (Novo Nordisk Co., Ltd.), when the treatment time is 1 to 2 hours, the enzyme concentration is 0.5 g / l.
The degree is appropriate. Total enzyme titer in this case = 1500-
1800 (unit / g) x 0.05 (% ows) x 60 ~
120 (minutes) = 4500 to 10800 units. Therefore, if the enzyme concentration is doubled with the same cellulase, the treatment time may be halved. As a practical prescription, rather than setting the optimal cellulase processing time for work setup and determining the enzyme concentration that clears the regulation of total enzyme titer according to the titer of the enzyme used, the normal cellulase processing time Is 2
3 hours is appropriate.

【００４４】但し、テンセル繊維に付着しているアニオ
ン又はカチオン界面活性剤が０．０５重量％を超える場
合、触媒毒に打ち勝って抗ピリング性に改質するために
は高濃度の酵素濃度が必要で、酵素ＯＰ−８８００（Ｇ
ＥＮＥＮＣＯＲ社）やセルクラスト（ノボノルディスク
（株））での２〜３時間のバイオ加工に必要な酵素濃度
は５ｇ〜１０ｇ／ lであるが、この場合の総酵素力価は
少なくとも９万単位となる。この程度総酵素力価が大き
くなると、たとえ高度の抗ピリング性と良好なピーチス
キン加工性に改質出来ても単繊維強度変動率が場合によ
っては４０％以上になり、繊維構造物において強力の変
動が大きくなり実用繊維としては使用に耐えない。However, when the amount of the anionic or cationic surfactant attached to the tencel fiber exceeds 0.05% by weight, a high concentration of enzyme is required to overcome the catalyst poison and modify the anti-pilling property. Then, the enzyme OP-8800 (G
The enzyme concentration required for bioprocessing for 2-3 hours with ENENCOR) or CELLCLAST (Novo Nordisk KK) is 5 g to 10 g / l, but the total enzyme titer in this case is at least 90,000 units. Becomes If the total enzyme titer is increased to this extent, the single fiber strength variation rate will be 40% or more in some cases even if it can be modified to have a high degree of anti-pilling property and good peach skin processability. The variation is so large that it cannot be used as a practical fiber.

【００４５】総酵素力価を１２５００単位以下に抑えて
セルラーゼ加工が可能なのは驚くべきことで、例えば、
前記した公報特許で処理条件が明記されているものとし
て、特開平５−１１７９７０号公報の実施例１９の表Ｖ
には溶剤紡糸セルロース系繊維のセルラーゼ加工の処方
が例示されているが、そのなかでセルクラスト（ノボル
ディスク（株）社製、技術資料より力価１５００単位／
ｇ）の１．０％ｏｗｓ溶液で６０分処理しているが、こ
の場合の総酵素力価＝１５００（単位／ｇ）×１（％ｏ
ｗｓ）×６０（分）＝９万単位である。又、特開昭５８
−３６２１７号公報にはセルロース繊維の風合改良をセ
ルラーゼ処理により行っているが、その実施例１の場
合、３０００〜６０００（単位／ｇ）のセルラーゼを溶
液濃度１．０％ｏｗｓで４時間処理しているが、この場
合の総酵素力価＝３０００〜６０００×１×２４０＝７
２万〜１４４万単位である。It is surprising that cellulase processing can be performed with the total enzyme titer kept below 12,500 units.
Table V of Example 19 of Japanese Patent Application Laid-Open No. 5-117970, in which the processing conditions are specified in the above-mentioned Japanese patents.
The formula for cellulase processing of solvent-spun cellulosic fibers is illustrated in the table, and among them, cell crust (manufactured by Novordisk Co., Ltd., a technical value of 1500 units /
g) was treated with a 1.0% ows solution for 60 minutes, and the total enzyme titer in this case was 1500 (unit / g) × 1 (% o
ws) × 60 (minutes) = 90,000 units. Also, JP-A-58
In JP-A-36217, cellulosic treatment is carried out by cellulase treatment, but in the case of Example 1, 3000 to 6000 (unit / g) cellulase is treated at a solution concentration of 1.0% ows for 4 hours. However, the total enzyme titer in this case = 3000 to 6000 x 1 x 240 = 7
It is 20,000 to 1,440,000 units.

【００４６】本発明方法において、セルラーゼ加工の
後、場合によっては前にグリシジル化合物による架橋改
質を行う。架橋改質の方法としては、浸漬加熱法、パッ
ド−スチーム法、パッド−ドライ−スチーム法、コール
ドバッチ法の何れでも可能であるが、均一性の面では浸
漬法が好ましい。何れの方法においても、グリシジル化
合物及び架橋反応の触媒の水溶液にテンセルを浸漬し、
浸漬法の場合はそのまま、パッド法及びコールドバッチ
法の場合はピックアップ量を７０％〜１３０％に搾液し
加温又は加熱下で反応させる。In the method of the present invention, a cross-linking modification with a glycidyl compound is carried out after cellulase processing and in some cases before cellulase processing. As a method of cross-linking modification, any of the immersion heating method, the pad-steam method, the pad-dry-steam method, and the cold batch method can be used, but the immersion method is preferable in terms of uniformity. In any of the methods, the tencel is immersed in an aqueous solution of a glycidyl compound and a catalyst for a crosslinking reaction,
In the case of the dipping method, as it is, in the case of the pad method and the cold batch method, the pickup amount is squeezed to 70% to 130% and the reaction is carried out under heating or heating.

【００４７】本発明方法の架橋反応に必要なグリシジル
化合物の施与量はグリシジル化合物のエポキシ当量等に
よっても異なるが、浸漬法ではテンセル繊維に対して２
〜３０重量％、パッド−スチーム法、パッド−ドライ−
スチーム法では２〜４０重量％、コールドバッチ法では
２〜５０重量％である。The application amount of the glycidyl compound necessary for the crosslinking reaction of the method of the present invention varies depending on the epoxy equivalent of the glycidyl compound, etc.
~ 30% by weight, pad-steam method, pad-dry-
It is 2 to 40% by weight in the steam method and 2 to 50% by weight in the cold batch method.

【００４８】本発明方法の架橋改質反応の触媒として
は、中性塩、弱アルカリ性塩、アルカリ性塩、酸性塩、
アルカリ金属の水酸化物、アンモニア、及びアミン類を
用いることができ、中性塩、弱アルカリ性塩、アミン類
が最も効果的である。中性塩としては、硫酸、塩酸、硝
酸、チオシアン酸、チオ硫酸のナトリウム塩及びカリウ
ム塩、弱アルカリ性塩としては酒石酸、クエン酸、プロ
ピオン酸のナトリウム及びカリウム塩、アミンとしては
エチレンジアミン、ジエチレントリアミン、トリエチレ
ンテトラミン等が好ましい。この内、硫酸ナトリウム又
は硫酸カリウムが効果及び経済性の点で特に好ましい。
本発明の触媒の量は、処理液中の濃度として１〜１５重
量％、好ましくは２〜１０重量％である。グリシジルア
クリレート化合物による架橋改質は上記触媒とアクリル
基をグラフト反応させるべくレドックス触媒とか過酸化
水素等の通常のグラフト触媒を用いる。As the catalyst for the crosslinking reforming reaction of the method of the present invention, a neutral salt, a weak alkaline salt, an alkaline salt, an acidic salt,
Alkali metal hydroxides, ammonia, and amines can be used, with neutral salts, weakly alkaline salts, and amines being most effective. As the neutral salt, sulfuric acid, hydrochloric acid, nitric acid, thiocyanic acid, sodium salt and potassium salt of thiosulfate, as a weak alkaline salt, tartaric acid, citric acid, sodium salt and potassium salt of propionic acid, as the amine ethylenediamine, diethylenetriamine, tritium. Ethylene tetramine and the like are preferred. Among these, sodium sulfate or potassium sulfate is particularly preferable in terms of effect and economy.
The amount of the catalyst of the present invention is 1 to 15% by weight, preferably 2 to 10% by weight, as a concentration in the treatment liquid. In the cross-linking modification with a glycidyl acrylate compound, a redox catalyst or a usual graft catalyst such as hydrogen peroxide is used in order to graft react the above catalyst with an acrylic group.

【００４９】本発明のグリシジル化合物による架橋改質
の処理法としては、浸漬加熱法、パッド−スチーム法、
パッド−ドライ−スチーム法、コールドバッチ法の何れ
も用いることができる。浸漬加熱法の場合、グリシジル
化合物とテンセルを速やかにしかも収率良く反応させる
ためには、処理温度を７０℃以上とする必要がある。浴
比は原綿処理の場合、１０〜３０程度が好ましい。パッ
ド−スチーム法は、例えばテンセルに対して５０〜２０
０重量％、好ましくは８０〜１２０重量％の処理液を付
与後、１２０℃、好ましくは１１０℃以下の飽和蒸気で
１０分〜数１０分間スチーミングする。パッド−ドライ
−スチーム法の場合も、パッド−スチーム法に準ずる
が、スチーミングの前に８０〜１２０℃で乾燥する。The treatment method for cross-linking modification with the glycidyl compound of the present invention includes an immersion heating method, a pad-steam method,
Both the pad-dry-steam method and the cold batch method can be used. In the case of the immersion heating method, it is necessary to set the treatment temperature to 70 ° C. or higher in order to react the glycidyl compound and tencel rapidly and in a good yield. In the case of raw cotton treatment, the bath ratio is preferably about 10 to 30. The pad-steam method is, for example, 50 to 20 for Tencel.
After applying 0% by weight, preferably 80 to 120% by weight of the treatment liquid, steaming is performed for 10 minutes to several tens of minutes with saturated steam at 120 ° C., preferably 110 ° C. or less. In the case of the pad-dry-steam method, the pad-steam method is followed, but drying is performed at 80 to 120 ° C. before steaming.

【００５０】コールドバッチ法では、例えばシート状の
テンセル原綿に５０〜２００重量％、好ましくは８０〜
１２０重量％の処理液を付与した後、ラップ状に巻取
り、乾燥することなくフィルム等で覆って水分の蒸散を
防止した上で室温で２０時間程度置く。この間、反応が
均一に進むように該ラップを回転させることが望まし
い。In the cold batch method, for example, a sheet-shaped tencel raw cotton is 50 to 200% by weight, preferably 80 to 200% by weight.
After the treatment liquid of 120% by weight is applied, the treatment liquid is wound into a wrap and covered with a film or the like without being dried to prevent evaporation of water, and then left at room temperature for about 20 hours. During this time, it is desirable to rotate the wrap so that the reaction proceeds uniformly.

【００５１】グリシジル化合物による架橋改質処理した
テンセル繊維は、常法に従って湯洗、油剤処理等の通常
の工程を経て乾燥する。The tencel fiber which has been subjected to the cross-linking modification treatment with a glycidyl compound is dried by a usual method such as washing with hot water and treatment with an oil agent.

【００５２】なお、本発明の単繊維強度変動率は次の式
で計算する。The variation rate of the single fiber strength of the present invention is calculated by the following formula.

【数１】 (Equation 1)

【００５３】以下実施例にて本発明を具体的に説明す
る。The present invention will be specifically described below with reference to examples.

【００５４】実施例１ テンセル原綿（単繊維：１．５ｄ／３８ｍｍ長、英国コ
ートルズ社製）６０Ｋｇを液容量１８００ｌのオーバー
マイヤーを用いて、セルラーゼ加工及びグリシジル化合
物による架橋改質を行った。まず、セルラーゼ加工に先
立って、７５℃の熱水１８００ｌを循環させて原綿の紡
糸油剤を洗い落とした。この際、３０分間熱水洗した後
一旦自然排水し、再び新鮮な熱水で同様に水洗した。こ
の操作を更に１回繰り返し最後に遠心脱水機で脱水し
た。熱水洗後の原綿の一部を乾燥し、付着している紡糸
油剤を熱テトラクロルエチレンで抽出し、これをエプト
ン法で測定してアニオン界面活性剤の付着量を測定した
結果０．０２５重量％であった。得られた原綿を続いて
セルラーゼ加工した。セルラーゼ加工の条件はセルラー
ゼとして酵素ＯＰ−８８００（ＧＥＮＥＮＣＯＲ社製、
力価１８００単位／ｇ）：０．０５％ｏｗｓ（０．５ｇ
／ｌ）、処理液量：１８００ l、処理温度：５５℃、ｐ
Ｈ：４．５（酢酸／酢酸ソーダ緩衝液）、処理時間：６
０分で行った。この場合の総酵素力価＝１８００（単位
／ｇ）×０．０５（％ｏｗｓ）×６０（分）＝５４００
単位である。この間、攪拌による加工液の剪断力でセル
ラーゼが失活するのを防ぐべく、液流線速度を５ｍ／秒
以下に規制するため、循環ポンプによる液循環は処理開
始後１〜２分で止め、加工液の酵素濃度が均一化した後
は、オーバーマイヤーの染色機の内かごを０．１ｍ／秒
程度で上下に振とうするに留めた。続いて、セルラーゼ
加工済のテンセル原綿を８０℃の熱水で１５分間失活処
理した後、グリシジル化合物で架橋改質した。該架橋改
質の条件は、グリシジル化合物としてエチレングリコー
ルジグリシジルエーテル（デナコール ＥＸ−８１０
ナガセ化成工業）を２０ｇ／ｌ、触媒として無水硫酸ナ
トリウムを１００ｇ／ｌの水溶液１８００ｌにセルラー
ゼ加工済の原綿約６０Ｋｇを室温で浸漬し、良く攪拌し
た後昇温し、９０℃で６０分間反応させた。水洗後、遠
心脱水機で脱水し、パンソフター−Ｓ（商品名 第一工
業製薬製）の水溶液に浸漬し該油剤を１．２％重量付着
させた後乾燥した。得られたテンセル原綿の単繊維強度
は３．５ｇ／ｄ、単繊維強度変動率は８％であった（セ
ルラーゼ加工前の平均単繊維強度４．８ｇ／ｄ、単繊維
強度変動率８％）。又、重量増加率で測定した架橋度は
１１．０％であった。得られた改質原綿を綿番手７２／
１の紡績糸に紡績した。該紡績糸のＩＰＩ値／１０００
ｍのネップ数は２２個で、改質前のテンセル原綿による
糸質とほとんど変わらぬ良好なものであった。続いて、
これを仕上織設計で織幅１１４ｃｍ、径：１２２本／イ
ンチ、緯：１０５本／インチの平織物に製織した。該織
物をビニールスルホン酸系の反応染料で染色後，前記し
た家庭用洗濯機法でピリング試験を実施し、得られた試
験布片をＪＩＳ Ｌ−１０７６法のピリング判定写真を
準用して判定した結果５級で、全くピリングは発現して
おらず良好であった。次に該織物のピーチスキン加工を
実施した。その方法は、上記平織物をポリエステルネッ
トに袋詰めし、ロータリーワッシャーにて温水中で揉み
加工を実施した。この際、粒径１μｍのセラミツクの粒
子を１０重量％含む直径３．８ｃｍのゴムボール（５０
ｇ／個）を平織物と同重量袋詰めした。揉み加工の処理
条件はロータリーワッシャーの回転数が３０回転／分、
浴比１：１００、温度６０℃、時間１８０分、であっ
た。その後、タンブラー乾燥機で乾燥した。得られたピ
ーチスキン加工織物の外観及び感触を専門検査員１０名
により検査したところ、ピーチスキン調の外観の均一
性、滑らかなピーチスキン調感触それにテンセル特有の
反発感に優れた織物風合であった。さらに、反応染色、
ピリング試験は対照資料としてセルラーゼ加工、架橋改
質を施してない通常のテンセル織物を同浴で処理した
が、本発明で改質したテンセル繊維の染色性、染色堅牢
度は対照資料と比較して顕著に良好であった。Example 1 60 kg of Tencel raw cotton (single fiber: 1.5 d / 38 mm length, manufactured by Courtles of England) was subjected to cellulase processing and cross-linking modification with a glycidyl compound using Overmeyer having a liquid volume of 1800 l. First, prior to cellulase processing, 1800 liters of hot water at 75 ° C. was circulated to wash off the spinning oil of raw cotton. At this time, it was washed with hot water for 30 minutes, then naturally drained, and again washed with fresh hot water in the same manner. This operation was repeated once more, and finally the product was dehydrated with a centrifugal dehydrator. After drying a part of the raw cotton after washing with hot water, the adhering spinning oil was extracted with hot tetrachloroethylene, and the result was measured by the Epton method to measure the amount of anionic surfactant attached. %Met. The raw cotton obtained was subsequently subjected to cellulase processing. The conditions for cellulase processing were enzyme OP-8800 (manufactured by GENENCOR,
Titer 1800 units / g): 0.05% ows (0.5g
/ L), processing liquid amount: 1800 l, processing temperature: 55 ° C., p
H: 4.5 (acetic acid / sodium acetate buffer), processing time: 6
It went in 0 minutes. Total enzyme titer in this case = 1800 (unit / g) x 0.05 (% ows) x 60 (min) = 5400
Is a unit. During this period, in order to prevent the cellulase from being deactivated by the shearing force of the working fluid due to stirring, the liquid flow linear velocity is regulated to 5 m / sec or less. Therefore, the liquid circulation by the circulation pump is stopped within 1 to 2 minutes after the treatment is started. After the enzyme concentration of the processing solution was made uniform, the inner basket of the Overmeier dyeing machine was shaken up and down at about 0.1 m / sec. Subsequently, the cellulase-processed Tencel raw cotton was inactivated by hot water at 80 ° C. for 15 minutes, and then crosslinked and modified with a glycidyl compound. The conditions for the cross-linking modification are ethylene glycol diglycidyl ether (Denacol EX-810 as a glycidyl compound.
(Nagase Kasei Co., Ltd.) and about 60 kg of cellulase-processed raw cotton are soaked in 1800 l of an aqueous solution of 100 g / l of anhydrous sodium sulfate as a catalyst at room temperature, well stirred and then heated to 90 ° C. for 60 minutes to react. It was After washing with water, the mixture was dehydrated with a centrifugal dehydrator, immersed in an aqueous solution of Pansofter-S (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), dried by attaching 1.2% by weight of the oil agent. The obtained Tencel raw cotton had a single fiber strength of 3.5 g / d and a single fiber strength variation rate of 8% (average single fiber strength before cellulase processing 4.8 g / d, single fiber strength variation rate of 8%). . The degree of cross-linking measured by the rate of weight increase was 11.0%. The modified raw cotton obtained is cotton count 72 /
The spun yarn of No. 1 was spun. IPI value of the spun yarn / 1000
The number of neps of m was 22, which was almost the same as the thread quality of the original Tencel raw cotton. continue,
This was woven into a plain woven fabric having a weaving width of 114 cm, a diameter of 122 threads / inch, and a weft of 105 threads / inch by a finish weaving design. The woven fabric was dyed with a vinyl sulfonic acid-based reactive dye, and then a pilling test was carried out by the above-mentioned household washing machine method, and the obtained test cloth piece was judged by applying a pilling judgment photograph of JIS L-1076 method. As a result, grade 5 was good, with no pilling. Next, the peach skin processing of the said textile was implemented. As the method, the plain weave was packed in a polyester net and kneaded in warm water with a rotary washer. At this time, a rubber ball (50 cm) containing 10% by weight of ceramic particles having a particle diameter of 1 μm and having a diameter of 3.8 cm.
The same weight as the plain weave was bagged. The processing conditions for the kneading process are that the rotation speed of the rotary washer is 30 rotations / minute,
The bath ratio was 1: 100, the temperature was 60 ° C., and the time was 180 minutes. Then, it dried with the tumbler dryer. The appearance and feel of the obtained peach-skin processed fabric were inspected by 10 expert inspectors, and it was found that the peach-skin-like appearance was uniform, the peach-skin-like feel was smooth, and the feeling of repulsion peculiar to Tencel was excellent. there were. Furthermore, reaction dyeing,
In the pilling test, as a reference material, a normal tencel fabric which was not subjected to cellulase processing and cross-linking modification was treated in the same bath. Remarkably good.

【００５５】比較例１ セルラーゼ加工を実施しない以外は実施例１に準じてテ
ンセル原綿の熱水洗、架橋改質を行い、同じく紡績、製
織、染色、ピリング試験及びピーチスキン加工性試験を
行った。この場合の架橋改質後の平均単繊維強度は４．
５ｇ／ｄ、単繊維強度変動率は１２％、綿番手７２／１
紡績糸のＩＰＩ値／１０００ｍのネップ数は２５個、抗
ピリング性は５級であつた。しかしながら実施例１のピ
ーチスキン加工条件に準じ、但しロータリーワッシャー
での揉み加工を２４０分間実施したが、ピーチスキン調
の立毛は全く起こらず、固い風合、フラットな表面感は
揉み加工の前とほとんど変化なかった。セルラーゼ加工
を施してないテンセル繊維は架橋改質した場合ピーチス
キン加工が困難なことが分かる。Comparative Example 1 Tencel raw cotton was washed with hot water and subjected to cross-linking modification in the same manner as in Example 1 except that cellulase processing was not carried out, and the same spinning, weaving, dyeing, pilling test and peach skin workability test were carried out. In this case, the average single fiber strength after cross-linking modification is 4.
5 g / d, single fiber strength fluctuation rate 12%, cotton count 72/1
The IPN value / 1000 m of the spun yarn was 25, and the pilling resistance was grade 5. However, according to the peach skin processing conditions of Example 1, but rubbing with a rotary washer was carried out for 240 minutes, but peach-skin-like naps did not occur at all, and the firm texture and flat surface feeling were the same as before rubbing. Almost no change. It can be seen that the peach skin processing is difficult when the tencel fiber not subjected to the cellulase processing is crosslinked and modified.

【００５６】比較例２ 実施例１においてセルラーゼ加工前の熱水洗を３回実施
したのを１回だけに留め、しかも自然脱水だけで遠心脱
水は実施しなかった。水洗後のテンセル繊維に付着して
いるアニオン界面活性剤の量は０．１０重量％であっ
た。セルラーゼ加工、架橋改質は実施例１に準じて処理
した。但し、セルラーゼ加工時間は１２０分間行った。
従って、この場合の総酵素力価は１０８００単位であ
る。得られたテンセル原綿の平均単繊維強度は３．８ｇ
／ｄ、単繊維強度変動率は２８％であった。改質原綿を
実施例１と全く同じ条件で綿番手７２／１の紡績糸に紡
績した。該紡績糸のＩＰＩ値／１０００ｍのネップ数は
２５個であった。以降、実施例１に準じて製織、染色し
た後、ピリング試験、ピーチスキン加工性を試験した。
ピリング試験は４級、ピーチスキン加工性は２４０分間
揉み加工の処理をしたが立毛状態が不均一であり不良で
あった。アニオン界面活性剤の洗浄ムラがピーチスキン
加工性の均一性に影響することが分かる。Comparative Example 2 In Example 1, the hot water washing before cellulase processing was carried out three times, but only once, and the natural dehydration was carried out and the centrifugal dehydration was not carried out. The amount of the anionic surfactant attached to the Tencel fiber after washing with water was 0.10% by weight. Cellulase processing and cross-linking modification were carried out according to Example 1. However, the cellulase processing time was 120 minutes.
Therefore, the total enzyme titer in this case is 10800 units. The average tenacity of the obtained Tencel raw cotton is 3.8 g.
/ D, the single fiber strength variation rate was 28%. The modified raw cotton was spun into a spun yarn of cotton count 72/1 under exactly the same conditions as in Example 1. The number of neps of IPI value / 1000 m of the spun yarn was 25 pieces. Thereafter, after weaving and dyeing according to Example 1, the pilling test and the peach skin workability were tested.
The pilling test was grade 4, and the peach skin workability was processed by rubbing for 240 minutes, but the napped state was not uniform and was poor. It can be seen that the uneven cleaning of the anionic surfactant affects the uniformity of the peach skin processability.

【００５７】比較例３ 実施例１に準じて、テンセル原綿の熱水洗、セルラーゼ
加工を行った。但し、架橋改質は行わなかつた。水洗後
のテンセル原綿に付着しているアニオン界面活性剤の量
は０．０２２重量％であつた。得られた改質テンセル原
綿の平均単繊維強度は３．６ｇ／ｄ、単繊維強度変動率
は８％であつた。該原綿を実施例１と全く同じ条件で綿
番手７２／１の紡績糸に紡績した。該紡績糸のＩＰＩ値
／１０００ｍのネップ数は２６個であった。以降、実施
例１に準じて製織、染色した後ピリング試験、ピーチス
キン加工性を試験した。抗ピリング性は４級で架橋改質
が施されていない分、抗ピリング性は低下した。又、染
色性、染色堅牢度も実施例１に比較して劣るものであっ
た。ピーチスキン加工性はほぼ良好であったが、抗ピリ
ング性が４級である分、実施例１に比較して劣ったもの
であった。Comparative Example 3 In accordance with Example 1, Tencel raw cotton was washed with hot water and processed with cellulase. However, no crosslinking modification was performed. The amount of the anionic surfactant attached to the TENCEL raw cotton after washing with water was 0.022% by weight. The obtained modified TENCEL raw cotton had an average single fiber strength of 3.6 g / d and a single fiber strength variation rate of 8%. The raw cotton was spun into a spun yarn of cotton count 72/1 under exactly the same conditions as in Example 1. The number of neps of IPI value / 1000 m of the spun yarn was 26 pieces. Thereafter, weaving and dyeing were performed according to Example 1, and then pilling test and peach skin workability were tested. The anti-pilling property was quaternary and the anti-pilling property was deteriorated because the cross-linking modification was not applied. Further, the dyeability and the dyeing fastness were also inferior to those of Example 1. Although the peach skin processability was almost good, it was inferior to Example 1 because the pilling resistance was grade 4.

【００５８】比較例４ 実施例１に準じて、熱水洗、セルラーゼ加工、架橋改質
を行った。但し、セルラーゼ加工は実施例１の倍時間の
１８０分間処理した。従って、この場合の総酵素力価は
１６２００単位である。水洗後のテンセル原綿に付着し
ているアニオン界面活性剤の量は０．０２０重量％であ
った。セルラーゼ加工及び架橋改質後のテンセル原綿の
平均単繊維強度は２．８０ｇ／ｄ、単繊維強度変動率は
１０％であった。得られた改質原綿を実施例１と全く同
じ条件で綿番手７２／１の紡績糸に紡績したが、該紡績
糸のＩＰＩ値／１０００ｍのネップ数は１２０個で、改
質原綿の平均単繊維強度が３．０ｇ／ｄを切ったことが
紡績性の不良に直結した。以降、実施例１に準じて、製
織、染色、ピリング試験、ピーチスキン加工性試験を実
施した。ピリング試験は５級、ピーチスキン加工性も良
好であったが、実施例１と比較すると糸質が劣る分、ピ
ーチスキン調外観の滑らかさは劣るものであった。Comparative Example 4 In accordance with Example 1, hot water washing, cellulase processing, and cross-linking modification were carried out. However, cellulase processing was performed for 180 minutes, which is double the time of Example 1. Therefore, the total enzyme titer in this case is 16200 units. The amount of the anionic surfactant attached to the TENCEL raw cotton after washing with water was 0.020% by weight. The average single fiber strength of the tencel raw cotton after cellulase processing and cross-linking modification was 2.80 g / d, and the single fiber strength variation rate was 10%. The obtained modified raw cotton was spun into a spun yarn of cotton count 72/1 under exactly the same conditions as in Example 1. The spun yarn had an IPI value / 1000 m nep number of 120, which was an average single yarn of the modified raw cotton. A fiber strength of less than 3.0 g / d was directly linked to poor spinnability. Thereafter, in accordance with Example 1, weaving, dyeing, pilling test, and peach skin workability test were performed. The pilling test was grade 5, and the peach skin processability was also good, but as compared with Example 1, the yarn quality was inferior and the peach skin appearance was not as smooth.

【００５９】実施例２ 実施例１においてセルラーゼ加工前の熱水洗を３回実施
したのを２回に減らし、２回目の終わりに遠心脱水し
た。その他は実施例１に準じてセルラーゼ加工を実施し
た。水洗後のテンセル原綿に付着しているアニオン界面
活性剤の量は０．０４５重量％であつた。セルラーゼ加
工済のテンセル原綿を続いてグリシジル化合物で架橋改
質した。該架橋改質の条件は、グリシジル化合物として
ジエチレングリコールジグリシジルエーテル（デナコー
ル ＥＸ−８５１ ナガセ化成工業）を１０ｇ／ｌ、触
媒として塩化ナトリウムを５０ｇ／ｌを使用した以外は
実施例１に準じて実施した。得られたテンセル原綿の平
均単繊維強度は３．８ｇ／ｄ、単繊維強度変動率は１０
％であった。熱水洗を簡略化した分、セルラーゼ加工が
抑制され、強度変動率も若干大きくなった。架橋度は
３．０％であつた。得られた改質原綿を実施例１と全く
同じ条件で綿番手７２／１の紡績糸に紡績した。該紡績
糸のＩＰＩ値／１０００ｍのネップ数は４８個であっ
た。以降、実施例１に準じて製織、染色した後、ピリン
グ試験、ピーチスキン加工性試験を行った。抗ピリング
性は４級で良好であった。ピーチスキン加工性は、ロー
タリーワッシャーでの揉み加工に２４０分要した以外、
ピーチスキン調の外観、感触それに風合とも実施例１と
ほぼ同様で良好であった。Example 2 In Example 1, washing with hot water before cellulase processing was repeated 3 times, but the number of washings was reduced to 2 times, and centrifugal dehydration was performed at the end of the second time. Otherwise, cellulase processing was carried out according to Example 1. The amount of the anionic surfactant attached to the TENCEL raw cotton after washing with water was 0.045% by weight. The cellulase-processed TENCEL raw cotton was subsequently cross-linked modified with a glycidyl compound. The conditions for the cross-linking modification were carried out according to Example 1 except that 10 g / l of diethylene glycol diglycidyl ether (Denacol EX-851 Nagase Kasei Co., Ltd.) was used as the glycidyl compound and 50 g / l of sodium chloride was used as the catalyst. . The average single fiber strength of the obtained TENCEL raw cotton was 3.8 g / d, and the single fiber strength fluctuation rate was 10.
%Met. As a result of simplifying the hot water washing, cellulase processing was suppressed and the strength variation rate was slightly increased. The degree of crosslinking was 3.0%. The modified raw cotton obtained was spun into a spun yarn of cotton count 72/1 under exactly the same conditions as in Example 1. The number of neps of IPI value / 1000 m of the spun yarn was 48 pieces. Thereafter, after weaving and dyeing according to Example 1, a pilling test and a peach skin workability test were performed. The pilling resistance was good in the fourth grade. Peach skin workability is as follows, except that it took 240 minutes to rub with a rotary washer.
The peach-skin-like appearance, feel and texture were almost the same as in Example 1 and were good.

【００６０】実施例３ セルラーゼ加工を１２０分間実施した以外は実施例２に
準じてテンセル原綿の改質を行った。水洗後のテンセル
繊維に付着しているアニオン界面活性剤の量は０．０４
８重量％であった。又、この場合の総酵素力価は１０８
００単位である。得られた改質テンセル原綿の平均単繊
維強度は３．２ｇ／ｄ、単繊維強度変動率は１０％であ
った。架橋度は３．２％であつた。該原綿を実施例１と
全く同じ条件で綿番手７２／１の紡績糸に紡績した。該
紡績糸のＩＰＩ値／１０００ｍのネップ数は５２個であ
った。以降、実施例１に準じて、製織、染色した後、ピ
リング試験及びピーチスキン加工性を試験した。抗ピリ
ング性は４級、ピーチスキン加工性もロータリーワツシ
ャーでの揉み加工時間が１８０分で実施例１と同程度で
あり、ピーチスキン調の外観、感触それに風合とも実施
例１とほぼ同様で良好であった。Example 3 Tencel raw cotton was modified according to Example 2 except that cellulase processing was carried out for 120 minutes. The amount of anionic surfactant adhering to the Tencel fiber after washing with water is 0.04
It was 8% by weight. The total enzyme titer in this case is 108
It is 00 units. The obtained modified TENCEL raw cotton had an average single fiber strength of 3.2 g / d and a single fiber strength variation rate of 10%. The degree of crosslinking was 3.2%. The raw cotton was spun into a spun yarn of cotton count 72/1 under exactly the same conditions as in Example 1. The number of neps of IPI value / 1000 m of the spun yarn was 52. Thereafter, according to Example 1, after weaving and dyeing, pilling test and peach skin workability were tested. The anti-pilling property is the fourth grade, and the peach skin workability is about the same as in Example 1 with the rubbing time in the rotary Watssha being 180 minutes, and the peach skin appearance, feel and feel are almost the same as in Example 1. Was good.

【００６１】実施例４ 実施例１に準じて、熱水洗、セルラーゼ加工、架橋改質
を行った。但し、セルラーゼとしてエンチロンＣＭ−４
０Ｌ（洛東化成工業 測定力価１５００単位／ｇ）を使
用して１．２５ｇ／ｌの酵素濃度で６０分間反応させ
た。総酵素力価は１１２５０単位／ｇになる。水洗後の
テンセル原綿に付着しているアニオン界面活性剤の量は
０．０１８重量％であった。セルラーゼ加工済のテンセ
ル原綿を続いてグリシジル化合物で架橋改質した。該架
橋改質の条件は、グリシジル化合物としてプロピレング
リコールジグリシジルエーテルを２０ｇ／ｌ、触媒とし
て炭酸ナトリウムを７０ｇ／ｌ含む加工液を使用した以
外は実施例１に準じて実施した。セルラーゼ加工及び架
橋改質後のテンセル原綿の平均単繊維強度は３．２ｇ／
ｄ、単繊維強度変動率は９％であつた。得られた改質原
綿を実施例１と全く同じ条件で綿番手７２／１の紡績糸
に紡績した。該紡績糸のＩＰＩ値／１０００ｍのネップ
数は４７個であった。以降、実施例１に準じて製織、染
色した後、ピリング試験、ピーチスキン加工性試験を実
施した。抗ピリング性は４級、ピーチスキン加工性は揉
み加工時間１８０分で実施例１と同程度であり、ピーチ
スキン調の外観、感触それに風合とも実施例１とほぼ同
様で良好であった。Example 4 Hot water washing, cellulase processing, and cross-linking modification were carried out in the same manner as in Example 1. However, as cellulase, Entilon CM-4
The reaction was carried out for 60 minutes at an enzyme concentration of 1.25 g / l using 0 L (Rakuto Kasei Kogyo titer 1500 unit / g). The total enzyme titer will be 11250 units / g. The amount of the anionic surfactant attached to the TENCEL raw cotton after washing with water was 0.018% by weight. The cellulase-processed TENCEL raw cotton was subsequently cross-linked modified with a glycidyl compound. The conditions for the cross-linking modification were the same as in Example 1 except that a working fluid containing 20 g / l of propylene glycol diglycidyl ether as a glycidyl compound and 70 g / l of sodium carbonate as a catalyst was used. The average single fiber strength of TENCEL raw cotton after cellulase processing and cross-linking modification is 3.2 g /
d, the single fiber strength variation rate was 9%. The modified raw cotton obtained was spun into a spun yarn of cotton count 72/1 under exactly the same conditions as in Example 1. The number of neps of IPI value / 1000 m of the spun yarn was 47 pieces. Then, after weaving and dyeing according to Example 1, a pilling test and a peach skin workability test were carried out. The anti-pilling property was grade 4, and the peach skin workability was about the same as in Example 1 with a rubbing time of 180 minutes, and the peach skin appearance, feel and feel were almost the same as in Example 1 and were good.

【００６２】実施例５ 実施例１に準じて熱水洗、セルラーゼ加工を行った。但
し、セルラーゼとしてセルクラスト１．５Ｌ（ノボノル
ディスク 力価１５００単位／ｇ）を使用して１．０ｇ
／ｌの酵素濃度で６０分間反応させた。総酵素力価は９
０００単位になる。水洗後のテンセル原綿に付着してい
るアニオン界面活性剤の量は０．０２１重量％であっ
た。セルラーゼ加工後の原綿を乾燥後、混打綿しラップ
状に巻取った。該ラツプをポリエチレングリコール（ｎ
＝１３）ジグリシジルエーテルを８０ｇ／ｌ、触媒とし
てトリエチレンテトラミンを１０ｇ／ｌを含む水溶液に
浸漬し、マングルで８５％に絞った後、加熱水蒸気を用
いて１２０℃で１０分間蒸熱した。その後、水洗し実施
例１に準じて油剤処理をし乾燥した。得られた改質テン
セル原綿の平均単繊維強度は３．３ｇ／ｄ、単繊維強度
変動率は８％であった。架橋度は４．５重量％であつ
た。続いて実施例１と全く同じ条件で綿番手７２／１の
紡績糸に紡績した。該紡績糸のＩＰＩ値／１０００ｍの
ネップ数は４０個であつた。以降、実施例１に準じて製
織、染色した後、ピリング試験、ピーチスキン加工性試
験を実施した。抗ピリング性は４級、ピーチスキン加工
性も揉み加工時間１８０分で実施例１と同程度であり、
ピーチスキン調の外観、感触それに風合とも実施例１と
ほぼ同様で良好であった。Example 5 Hot water washing and cellulase processing were carried out in the same manner as in Example 1. However, 1.0g using cell crust 1.5L (Novo Nordisk titer 1500 unit / g) as cellulase
The reaction was performed for 60 minutes at an enzyme concentration of 1 / l. Total enzyme titer is 9
000 units. The amount of the anionic surfactant attached to the TENCEL raw cotton after washing with water was 0.021% by weight. The raw cotton after cellulase processing was dried, then mixed-plied and wound into a wrap. The wrap is polyethylene glycol (n
= 13) It was immersed in an aqueous solution containing 80 g / l of diglycidyl ether and 10 g / l of triethylenetetramine as a catalyst, squeezed to 85% with mangle, and then steamed with heated steam at 120 ° C. for 10 minutes. Then, it was washed with water, treated with an oil agent according to Example 1, and dried. The obtained modified TENCEL raw cotton had an average single fiber strength of 3.3 g / d and a single fiber strength variation rate of 8%. The degree of crosslinking was 4.5% by weight. Subsequently, a spun yarn of cotton count 72/1 was spun under exactly the same conditions as in Example 1. The number of neps of IPI value / 1000 m of the spun yarn was 40 pieces. Then, after weaving and dyeing according to Example 1, a pilling test and a peach skin workability test were carried out. The anti-pilling property is grade 4, the peach skin workability is about the same as in Example 1 with the rubbing working time of 180 minutes,
The peach-skin-like appearance, feel and texture were almost the same as in Example 1 and were good.

【００６３】[0063]

【発明の効果】以上のように、テンセル繊維の抗ピリン
グ加工において、該繊維の紡糸油剤として付着している
アニオン界面活性剤を主とするイオン性界面活性剤がセ
ルラーゼの触媒毒であり、該触媒毒作用を軽減するため
セルラーゼ加工の前処理として熱水洗を徹底的に行い、
該活性剤の付着量を０．０５重量％以下、好ましくは
０．０２５重量％以下に規制し、さらにセルラーゼが剪
断力で失活するため該セルラーゼ加工の加工液の液流線
速度を最高部で５ｍ／秒に規制した場合、単位力価（単
位／ｇ）×酵素濃度（％ｏｗｓ）×酵素加工時間（分）
で表される総酵素力価が１２５００単位、好ましくは６
２５０単位以下の非常に穏やかなセルラーゼ加工を可能
にし、これに架橋改質、特にグリシジル化合物による架
橋改質を組み合わせることにより、高度の抗ピリング性
と良好なピーチスキン加工性が両立した改質テンセル繊
維及びその製造方法を開発した。その効果として次ぎの
項目等があげられる。INDUSTRIAL APPLICABILITY As described above, in the anti-pilling process of tencel fiber, the ionic surfactant mainly composed of the anionic surfactant attached as a spinning oil agent for the fiber is a catalyst poison of cellulase, and In order to reduce the catalyst poisoning effect, thorough washing with hot water is carried out as a pretreatment for cellulase processing.
The adhering amount of the activator is regulated to 0.05% by weight or less, preferably 0.025% by weight or less, and the cellulase is deactivated by shearing force. When regulated to 5 m / sec with, unit titer (unit / g) x enzyme concentration (% ows) x enzyme processing time (min)
Total enzyme titer represented by 12,500 units, preferably 6
A modified tencel that enables extremely gentle cellulase processing of 250 units or less and combines it with cross-linking modification, especially cross-linking modification with a glycidyl compound to achieve both high anti-pilling property and good peach skin processability. A fiber and its manufacturing method have been developed. The following items can be cited as the effects.

【００６４】本発明は徹底的な熱水洗とセルラーゼ加工
液の液流線速度の規制により総酵素力価が従来の２分の
１、乃至は４分の１と非常に穏やかなセルラーゼ加工が
可能になり、単繊維強度変動率が１０％以下、好ましく
は８％以下の小さい範囲に抑制できるようになり、その
分、繊維強度調整の度合を大きく取れるようになつた。
これと架橋改質を組み合わせることにより、従来のセル
ラーゼ加工を施さないで架橋改質のみの場合にピーチス
キン加工性が阻害されたのに対して、本発明の場合、高
度の抗ピリング性と良好なピーチスキン加工性が両立す
る改質テンセル繊維の製造が可能になった。先の本発明
者等による発明が平均単繊維強度が３．０ｇ／ｄ以上の
場合に抗ピリング性が完全に満足し得なかったのに対し
て、本発明は、これに架橋改質を組み合わせることによ
りこれを改善し５級を満足するようになつた。先の本発
明者等による発明が、セルラーゼ加工で平均単繊維強度
が３．０ｇ／ｄ未満に調整した場合に、通常のテンセル
繊維の紡績条件、特にカード条件で糸質がかなり損傷を
受ける問題点があったが、上記の結果、平均単繊維強度
３．０ｇ／ｄ以上でも高度の抗ピリング性になり、大規
模生産、短時間処理、しかもピーチスキン加工性を阻害
しない、テンセル原綿での抗ピリング加工が可能になつ
た。従来、テンセル繊維のセルラーゼ加工の前処理とし
て、必ず必要であった揉み叩き加工が不要になり、単繊
維表面がフィブリル化又はミクロフィブリル化構造を呈
していなくて、しかも高度な抗ピリング性のテンセル原
綿の製造が可能になつた。これにより経済的に有利で良
好な品質の抗ピリング性テンセル紡績糸の製造が可能に
なった。グリシジル化合物による架橋改質により、反応
染料による染色性、染色堅牢度が改善された。The present invention enables extremely gentle cellulase processing with a total enzyme titer of half or one-fourth of that of the conventional one by thoroughly rinsing with hot water and regulating the flow velocity of the cellulase processing solution. As a result, the fluctuation rate of the single fiber strength can be suppressed to a small range of 10% or less, preferably 8% or less, and the degree of fiber strength adjustment can be increased correspondingly.
By combining this with cross-linking modification, the peach skin processability was hindered only by cross-linking modification without conventional cellulase processing, whereas in the case of the present invention, high anti-pilling property and good It has become possible to produce modified tencel fibers that are compatible with various peach skin processability. Whereas the previous inventions by the present inventors could not completely satisfy the anti-pilling property when the average single fiber strength was 3.0 g / d or more, the present invention combines this with crosslinking modification. As a result, this was improved and the grade 5 was satisfied. In the invention by the present inventors, when the average single fiber strength is adjusted to less than 3.0 g / d by cellulase processing, the yarn quality is considerably damaged under ordinary spinning conditions of Tencel fiber, particularly card conditions. However, as a result of the above, even with an average single fiber strength of 3.0 g / d or higher, a high degree of anti-pilling property is achieved, and large-scale production, short-time processing, and peach skin processability are not impaired. Anti-pilling processing has become possible. In the past, the pre-treatment for cellulase processing of TENCEL fiber eliminates the necessity of rubbing and tapping, and the single fiber surface does not exhibit a fibrillated or microfibrillated structure, and yet has high anti-pilling properties. Raw cotton can now be manufactured. This made it possible to produce an economically advantageous and good quality anti-pilling tencel spun yarn. The cross-linking modification with the glycidyl compound improved the dyeability and the dye fastness with the reactive dye.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 北村 優 長野県小県郡丸子町大字東内774番地１ (72)発明者 宮田 昌平 神戸市東灘区深江南町１丁目３番５号 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Yu Kitamura, 774, Higashiuchi, Maruko-cho, Oka-gun, Nagano Prefecture 1 (72) Shohei Miyata 1-3-5 Fukaeminami-cho, Higashinada-ku, Kobe

Claims (3)

【特許請求の範囲】[Claims] 【請求項１】 溶剤紡糸セルロース系繊維において、単
繊維の表面が揉み叩き加工によるフィブリル化又はミク
ロフィブリル化構造を呈しておらず、しかも該繊維から
なる織編物の家庭用洗濯機法での抗ピリング試験にＪＩ
Ｓ Ｌ−１０７６法のピリング判定標準写真を準用して
の判定で４級以上の抗ピリング性に架橋改質されていな
がら、ピーチスキン加工性が改質前と同等或いは改質前
より良好であり、さらに反応染料での染色性及び染色堅
牢度が改質前より改善されていることを特徴とする溶剤
紡糸セルロース系繊維及び該繊維からなる繊維構造物。1. In a solvent-spun cellulosic fiber, the surface of a single fiber does not exhibit a fibrillated or microfibrillated structure by rubbing and beating, and the woven or knitted fabric made of the fiber is resistant to a domestic washing machine method. JI for pilling test
Pilling judgment of SL-1076 method It was judged by applying the standard photograph mutatis mutandis that while it was cross-linked and modified to have an anti-pilling property of grade 4 or higher, the peach skin processability was equal to or better than that before modification. And a solvent-spun cellulosic fiber and a fiber structure comprising the fiber, which are further improved in dyeing property and dyeing fastness with a reactive dye as compared with before modification. 【請求項２】 溶剤紡糸セルロース系繊維において、単
繊維の表面が揉み叩き加工によるフィブリル化又はミク
ロフィブリル化構造を呈しておらず、しかも、平均単繊
維強度が３．０ｇ／ｄ以上、４．３ｇ／ｄ以下、単繊維
強度変動率が１０％以下に改質されていて、さらに、ジ
グリシジルエーテル又はポリグリシジルエーテル或いは
グリシジルアクレレート化合物により架橋改質されてい
ることを特徴とする、該繊維からなる織編物の家庭用洗
濯機法での抗ピリング試験にＪＩＳ Ｌ−１０７６法の
ピリング判定標準写真を準用しての判定で４級以上の抗
ピリング性でありながら、該繊維からなる織編物のピー
チスキン加工性が架橋改質前と同等或いは架橋改質前よ
り良好であり、さらに反応染料での染色性及び染色堅牢
度が改質前より改善されていることを特徴とする溶剤紡
糸セルロース系繊維及び該繊維からなる繊維構造物。2. The solvent-spun cellulosic fiber does not exhibit a fibrillated or microfibrillated structure by rubbing and beating the surface of the single fiber, and has an average single fiber strength of 3.0 g / d or more. The fiber is modified to have a single fiber strength variation rate of 3 g / d or less and 10% or less, and is further crosslinked and modified with a diglycidyl ether or polyglycidyl ether or a glycidyl acrylate compound. A woven or knitted fabric made of the above-mentioned fiber having an anti-pilling property of 4 or more as determined by applying a standard photograph of pilling judgment of JIS L-1076 method to an anti-pilling test in a domestic washing machine method. Has the same or better peach-skin processability than before cross-linking modification, and has improved dyeability and dyeing fastness with reactive dyes before modification. It solvent-spun cellulosic fibers and fiber structures made of the fiber characterized that. 【請求項３】 溶剤紡糸セルロース系繊維の原綿、スラ
イバー、紡績糸或いは織編物の改質において、紡糸油剤
として残留付着しているアニオン界面活性剤又はカチオ
ン界面活性剤の付着量を０．０５重量％以下となるよう
に熱水で洗い落とした該繊維についてセルラーゼ加工を
実施し、その際、該セルラーゼ加工の総酵素力価（酵素
力価（単位／ｇ）×酵素濃度（％ｏｗｓ）×酵素加工時
間（分））を１２５００単位以下、且つ、該セルラーゼ
加工液の液流線速度を最高部で５ｍ／秒以下に規制して
該加工を実施し、さらに、ジグリシジルエーテル又はポ
リグリシジルエーテル或いはグリシジルアクリレート化
合物により架橋改質することを特徴とする請求項１の溶
剤紡糸セルロース系繊維及び該繊維からなる繊維構造物
の製造方法。3. In the modification of raw cotton, sliver, spun yarn or woven or knitted fabric of solvent-spun cellulosic fibers, the amount of anionic surfactant or cationic surfactant remaining as a spinning oil agent is 0.05% by weight. Cellulase processing was performed on the fiber washed off with hot water so as to be not more than 10%, and at that time, the total enzyme titer of the cellulase processing (enzyme titer (unit / g) x enzyme concentration (% ows) x enzyme treatment) The time (minutes) is 12,500 units or less, and the liquid stream linear velocity of the cellulase processing liquid is restricted to 5 m / sec or less at the highest part to carry out the processing, and further, diglycidyl ether or polyglycidyl ether or glycidyl. A solvent-spun cellulosic fiber according to claim 1, which is cross-linked and modified with an acrylate compound, and a method for producing a fiber structure comprising the fiber.
JP8220661A 1995-08-09 1996-08-01 Solvent-spun cellulose fiber excellent in pill resistance and peach-skin processability, its fiber structure and its production Pending JPH09137387A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP8220661A JPH09137387A (en) 1995-08-09 1996-08-01 Solvent-spun cellulose fiber excellent in pill resistance and peach-skin processability, its fiber structure and its production

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP22586495 1995-08-09
JP7-225864 1995-08-09
JP8220661A JPH09137387A (en) 1995-08-09 1996-08-01 Solvent-spun cellulose fiber excellent in pill resistance and peach-skin processability, its fiber structure and its production

Publications (1)

Publication Number Publication Date
JPH09137387A true JPH09137387A (en) 1997-05-27

Family

ID=26523842

Family Applications (1)

Application Number Title Priority Date Filing Date
JP8220661A Pending JPH09137387A (en) 1995-08-09 1996-08-01 Solvent-spun cellulose fiber excellent in pill resistance and peach-skin processability, its fiber structure and its production

Country Status (1)

Country Link
JP (1) JPH09137387A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012131897A1 (en) * 2011-03-25 2012-10-04 グンゼ株式会社 Anti-pilling fiber product
WO2018135139A1 (en) * 2017-01-23 2018-07-26 パナソニックＩｐマネジメント株式会社 Polymer and method for producing polymer film
CN113818167A (en) * 2021-08-27 2021-12-21 常熟市宏芳针织服饰有限公司 Washing process for increasing flexibility of synthetic fiber cloth

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012131897A1 (en) * 2011-03-25 2012-10-04 グンゼ株式会社 Anti-pilling fiber product
JP2012202005A (en) * 2011-03-25 2012-10-22 Gunze Ltd Fiber product with anti-pilling property
WO2018135139A1 (en) * 2017-01-23 2018-07-26 パナソニックＩｐマネジメント株式会社 Polymer and method for producing polymer film
JPWO2018135139A1 (en) * 2017-01-23 2019-11-07 パナソニックＩｐマネジメント株式会社 Method for producing polymer and polymer film
US10851181B2 (en) 2017-01-23 2020-12-01 Panasonic Intellectual Property Management Co., Ltd. Polymer and method for producing polymer membrane
CN113818167A (en) * 2021-08-27 2021-12-21 常熟市宏芳针织服饰有限公司 Washing process for increasing flexibility of synthetic fiber cloth

Similar Documents

Publication Publication Date Title
CN111254724A (en) Dyeing process of woven wool, application of woven wool and wool textile
JPH09137387A (en) Solvent-spun cellulose fiber excellent in pill resistance and peach-skin processability, its fiber structure and its production
JPH09137386A (en) Solvent-spun cellulose fiber excellent in pill resistance and peach-skin processability, its fiber structure and its production
JPH09137384A (en) Solvent-spun cellulose fiber excellent in pill resistance and peach-skin processability, its fiber structure and its production
KR20050106402A (en) Process for producing a dyed and finished lyocell fabric
JPH0931855A (en) Solvent-spun antipilling cellulosic fiber, its fiber structure and its production
JPH08325955A (en) Solvent-spun cellulosic fiber having antipilling property, its fiber structure and its production
JP4015289B2 (en) Method for preventing fibrillation of solvent-spun cellulose fiber
JPH02175975A (en) Shrink and fluff proofing method for pineapple fiber-containing fibrous structure
JPH09158050A (en) Antipilling solvent-spun cellulosic fiber, its fiber structure and its production
Buschle-Diller Substrates and their structure
GB2314568A (en) Fibre finishing treatment
KR20040011534A (en) Dyeing and finishing of lyocell fabrics
JPH10158921A (en) Anti-pilling solvent-spun cellulosic fiber, its fiber structure and production
JPH1046477A (en) Production of structure of fiber, spun by using solvent, having peach skin-like touch
JP3655007B2 (en) Method for preventing fibrillation of solvent-spun cellulose fiber
JP3204915B2 (en) Method for producing modified acetate fiber fabric
JP2003342875A (en) Method for processing cellulosic fiber
JP4254440B2 (en) Textile manufacturing method
JP2007154395A (en) Modified silk fiber and method for producing the same
JPH10110389A (en) Antipilling solution-spun cellulosic fiber and production of its fiber structure
JPH10212671A (en) Cellulosic fiber and crosslinking modification of structural material of the same
JP2002088659A (en) Processing method for fibrillation prevention of solvent- spun cellulose fiber-containing fabric
JP2000054268A (en) Finishing of solvent spun cellulose textile fabric
JP3419671B2 (en) Processing method of artificial cellulose fiber