JPH01132877A - Method for processing silk product - Google Patents

Method for processing silk product

Info

Publication number
JPH01132877A
JPH01132877A JP28959287A JP28959287A JPH01132877A JP H01132877 A JPH01132877 A JP H01132877A JP 28959287 A JP28959287 A JP 28959287A JP 28959287 A JP28959287 A JP 28959287A JP H01132877 A JPH01132877 A JP H01132877A
Authority
JP
Japan
Prior art keywords
silk
processing
resistance
organic solvent
dibasic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP28959287A
Other languages
Japanese (ja)
Other versions
JPH0141754B2 (en
Inventor
Masuhiro Tsukada
益裕 塚田
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.)
NORINSUISANSHO SANSHI SHIKENJO
Original Assignee
NORINSUISANSHO SANSHI SHIKENJO
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 NORINSUISANSHO SANSHI SHIKENJO filed Critical NORINSUISANSHO SANSHI SHIKENJO
Priority to JP28959287A priority Critical patent/JPH01132877A/en
Publication of JPH01132877A publication Critical patent/JPH01132877A/en
Publication of JPH0141754B2 publication Critical patent/JPH0141754B2/ja
Granted legal-status Critical Current

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Abstract

PURPOSE: To improve wrinkle resistance, yellowing resistance and dyeability without impairing characteristic physical properties of silk by immersing and treating a silk yarn, a silk woven fabric. etc., with a processing solution composed of an organic solvent containing a dibasic acid anhydride. CONSTITUTION: A silk yarn, a silk woven fabric, etc., are immersed and treated with a processing solution at 50-85 deg.C containing 0.1-1.5 mols of a dibasic acid anhydride of the formula (n is 2-4) such as succinic anhydride, glutaric anhydride, etc., in a basic organic solvent such as dimethylformamide, etc., as an organic solvent. By this method, a processed silk product has more improved wrinkle resistance, yellowing resistance and dyeability than an unprocessed silk without changing mechanical characteristics such as strength, initial tensile resistance degree, elongation, etc.

Description

【発明の詳細な説明】 (産業上の利用分野) 本発明は、絹糸、絹織物等の絹製品の加工方法に関する
DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for processing silk products such as silk threads and silk fabrics.

(従来の技術) 絹繊維は光沢、染色性、力学的性質及び吸放湿性など衣
料繊維として優れた特性を有する反面、防しわ性、耐洗
濯性、耐摩耗性、耐候性ならびにWaW性等の諸性質に
おいては現代衣料素材として適性に欠ける問題を有する
。そのため、絹繊維の機能的実用性を改善あるいは向上
させるための加工剤としては、スチレン、メタクリル酸
メチルあるいは2−ハイドロキシエチルメタクリレート
、メタクリルアミドに代表される親水性ビニール系モノ
マー等のグラフト重合加工剤が一般に知られている。
(Prior art) Silk fiber has excellent properties as a clothing fiber, such as luster, dyeability, mechanical properties, and moisture absorption/desorption properties. It has various properties that make it unsuitable as a material for modern clothing. Therefore, as processing agents for improving or improving the functional utility of silk fibers, graft polymerization processing agents such as hydrophilic vinyl monomers represented by styrene, methyl methacrylate, 2-hydroxyethyl methacrylate, and methacrylamide are used. is generally known.

(発°明が解決しようとする問題点) 前記従来の加工剤のうち、前者のスチレン、メタクリル
酸メチルの加工剤は、絹製品に用いたときグラフト加工
反応が進むと絹のヤング率が増大し、未加工時のしなや
かでやわらかな絹本来の柔軟的な性質は損われ、防しわ
性を低下させることに加えて、該加工剤は悪臭を有する
ため取扱いにくいという不都合を有する。
(Problems to be Solved by the Invention) Among the conventional processing agents mentioned above, the former styrene and methyl methacrylate processing agents increase the Young's modulus of silk as the grafting reaction progresses when used for silk products. However, the pliable and soft properties of unprocessed silk are impaired, and in addition to reducing the wrinkle resistance, the processing agent has a bad odor and is difficult to handle.

また後者の親水性ビニール系モノマー加工剤は、絹製品
に加工処理を施す際、該加工剤を含む混合液に酸を加え
てpHを調整し、さらに重合開始剤を添加して、一定条
件下での温度制御操作が必要であるため管理がなかなか
困難であり、またグラフト反応の進行に伴い絹糸の断面
積は増大するため、絹糸繊度当りの絹糸強度は未加工時
のl/3近くにまで低下し、かつ絹糸のやわかさや伸び
易さの目安となる初期引張抵抗度が増加して絹糸は固く
、伸び難くなるとともに、その染色性能が低下するなど
の問題を有する。
The latter hydrophilic vinyl monomer processing agent is used when processing silk products by adding an acid to the mixed solution containing the processing agent to adjust the pH, and then adding a polymerization initiator under certain conditions. It is quite difficult to control the temperature because it requires temperature control, and the cross-sectional area of the silk increases as the grafting reaction progresses, so the silk strength per silk fineness is close to 1/3 of the unprocessed state. As a result, the initial tensile resistance, which is a measure of softness and stretchability of the silk thread, increases, making the silk stiff and difficult to stretch, and the dyeing performance of the silk thread decreases.

本発明は、前記問題点を解消し、未加工絹製品と同等の
優れた機械的性質が得られると共に、防しわ率、黄変防
止性および染色性を向上させることが出来る絹製品の加
工方法を提供することを目的とする。
The present invention solves the above-mentioned problems, and provides a method for processing silk products that can provide excellent mechanical properties equivalent to those of unprocessed silk products, as well as improve wrinkle resistance, yellowing resistance, and dyeability. The purpose is to provide

(問題点を解決するための手段) 本発明者は、前記目的を達成する絹製品の加工方法につ
いて鋭意検討した結果、2塩基酸無水物を含む有機溶剤
から成る加工溶液を用いることによって、未加工絹製品
と同等の強度、伸びおよび初期引張抵抗度等の機械的性
質が得られ、また防しわ性、染色性を向上させると共に
、優れた黄変防止効果があることを知見した。
(Means for Solving the Problems) As a result of intensive study on a method for processing silk products that achieves the above object, the present inventor has discovered that by using a processing solution consisting of an organic solvent containing a dibasic acid anhydride, It was found that mechanical properties such as strength, elongation, and initial tensile resistance equivalent to those of processed silk products can be obtained, and that it has improved wrinkle resistance and dyeability, and has an excellent yellowing prevention effect.

本発明は、前記知見に基づいてなされたものであって、 一般式 (ただし式中nは2〜4である) で示される2塩基酸無水物を含有する有機溶剤から成る
加工溶液で浸漬処理することを特徴とする。
The present invention has been made based on the above findings, and includes immersion treatment with a processing solution consisting of an organic solvent containing a dibasic acid anhydride represented by the general formula (where n is 2 to 4). It is characterized by

本発明の加工方法に用いる2塩基酸無水物としては、無
水コハク酸、無水グルタル酸、無水アジピン酸が挙げら
れる。また有機溶剤としては、ジメチルホルムアミド、
ジメチルスルホキシド、ピリジン等の塩基性有機溶剤が
挙げられる。
Examples of dibasic acid anhydrides used in the processing method of the present invention include succinic anhydride, glutaric anhydride, and adipic anhydride. In addition, examples of organic solvents include dimethylformamide,
Examples include basic organic solvents such as dimethyl sulfoxide and pyridine.

有機溶剤中における2塩基酸無水物の濃度を0.1〜1
.5Mとする。
The concentration of dibasic acid anhydride in the organic solvent is 0.1 to 1.
.. It will be 5M.

絹糸または絹製品を浸漬する溶液は前記濃度溶液の浴比
20倍前後が好ましく、また溶液の温度は50〜85℃
、好ましくは75℃前後であり、浸漬時間は30〜48
0分間、好ましくは240分間とする。
The solution in which the silk thread or silk product is immersed is preferably about 20 times the bath ratio of the above concentration solution, and the temperature of the solution is 50 to 85°C.
, preferably around 75°C, and the immersion time is 30 to 48
0 minutes, preferably 240 minutes.

浸漬処理後はイソプロパツールのような低級アルコール
で洗浄し、更に水洗処理を施して絹糸または絹製品から
未反応2塩基酸無水物等を完全除去させる。
After the soaking treatment, the silk thread or silk product is washed with a lower alcohol such as isopropanol, and further washed with water to completely remove unreacted dibasic acid anhydride and the like from the silk thread or silk product.

尚2塩基酸無水物を含有する有機溶剤がら成る加工溶液
を用いることによって、黄変防止性が向上するのは、2
塩基酸無水物が黄変の際の原因の一つともなっている絹
分子中のチロシン分子側鎖の活性OH基と選択的に反応
するためと考えられる。
The yellowing prevention property is improved by using a processing solution consisting of an organic solvent containing a dibasic acid anhydride.
This is thought to be because the basic acid anhydride reacts selectively with the active OH group of the side chain of the tyrosine molecule in the silk molecule, which is one of the causes of yellowing.

(実施例) 以下、本発明の具体的実施例並びにその比較例に基づき
説明する。
(Example) Hereinafter, description will be made based on specific examples of the present invention and comparative examples thereof.

実験例1 精練された31.2dの絹糸(21dの生糸2本より構
成された下撚は750回/ m s上撚は850回/m
の双撚絹糸)を無水コハク酸1部にジメチルホルムアミ
ド9部を加えて溶解した浴比20倍の溶液中に、温度7
5℃で、時間45分間処理し、処理後イソプロパツール
で、さらに温度55℃のアセトンで1時間抽出して未反
応の無水コハク酸を除去し最後に充分水洗、風乾処理を
して、これを実施例1とした。
Experimental Example 1 Refined 31.2 d silk thread (first twist composed of two 21 d raw silks is 750 times/m s, final twist is 850 times/m
twin-twisted silk thread) was dissolved in a solution of 20 times the bath ratio by adding 9 parts of dimethylformamide to 1 part of succinic anhydride at a temperature of 7.
It was treated at 5°C for 45 minutes, and after the treatment, it was extracted with isopropanol and then with acetone at 55°C for 1 hour to remove unreacted succinic anhydride.Finally, it was thoroughly washed with water and air-dried. was designated as Example 1.

更に時間90分、270分の加工処理を施した絹糸を夫
々実施例2、実施例3とした。
Silk threads further processed for 90 minutes and 270 minutes were designated as Example 2 and Example 3, respectively.

また全く加工処理を施さなかった絹糸を比較例1とした
Comparative Example 1 was a silk thread that was not processed at all.

各絹糸の夫々について重量増加率、強度、伸度ならびに
初期引張抵抗度を測定した。
The weight increase rate, strength, elongation, and initial tensile resistance of each silk thread were measured.

尚重量増加率は処理前後における試料の重量差から、ま
た強度“、伸度及び初期引張抵抗度は東洋ボールドウィ
ン製、テンシロン(UTM−■)によって測定した。得
られた重量増加率、強度、伸度、初期引張抵抗度の測定
結果を表−1に示す。
The weight increase rate was measured from the difference in weight of the sample before and after treatment, and the strength, elongation, and initial tensile resistance were measured using Tensilon (UTM-■) manufactured by Toyo Baldwin. Table 1 shows the measurement results of initial tensile resistance.

表−1 表−1から明らかなように実施例1,2.3の強度、初
期引張抵抗度は比較例1とほぼ同等或いは若干増加傾向
を示し、また実施例1,2゜3の伸度は比較例に比して
向上した。従って実施例1,2.3は加工処理が施して
いるのにかかわらず、全く加工処理が施されていない比
較例1に比して強度、初期引張抵抗度、伸度等の機械的
性質は何ら遜色がなかったことが確認された。
Table 1 As is clear from Table 1, the strength and initial tensile resistance of Examples 1 and 2.3 are almost the same as those of Comparative Example 1, or show a slight tendency to increase, and the elongation of Examples 1 and 2. was improved compared to the comparative example. Therefore, although Examples 1 and 2.3 were processed, mechanical properties such as strength, initial tensile resistance, and elongation were lower than that of Comparative Example 1, which was not processed at all. It was confirmed that there was no difference.

実験例2 2塩基酸無水物として無水コハク酸の代りに無水グルタ
ル酸を同量用いた以外は実施例1(処理時間45分)と
同様の方法で加工処理を施し、これを実施例4とした。
Experimental Example 2 Processing was performed in the same manner as in Example 1 (processing time 45 minutes) except that the same amount of glutaric anhydride was used instead of succinic anhydride as the dibasic acid anhydride, and this was carried out in Example 4. did.

更に時間90分、270分の加工処理を施した絹糸を実
施例5、実施例6とした。また全く加工処理を施さなか
った絹糸を前記実験例1と同様に比較例1とした。
Silk threads further processed for 90 minutes and 270 minutes were designated as Examples 5 and 6. In addition, a silk thread that was not subjected to any processing treatment was used as Comparative Example 1 in the same manner as in Experimental Example 1 above.

各絹糸の夫々について前記実施例1の71Pj定方法に
準拠して重量増加率、強度、伸度および初期引張抵抗度
を測定した。得られた各測定結果を表−2に示す。
The weight increase rate, strength, elongation, and initial tensile resistance of each silk thread were measured according to the 71Pj method of Example 1 above. The measurement results obtained are shown in Table 2.

表−2 表−2から明らかなように実施例4,5.6の強度、初
期引張抵抗度は比較例1とほぼ同等傾向を示し、また実
施例4,5.6の伸度は比較例に比して向上した。
Table 2 As is clear from Table 2, the strength and initial tensile resistance of Examples 4 and 5.6 are almost the same as those of Comparative Example 1, and the elongation of Examples 4 and 5.6 is similar to that of Comparative Example 1. improved compared to.

従って実施例4,5.6は加工処理が施しているのにか
かわらず、全く加工処理が施されていない比較例1に比
して強度、初期引張抵抗度、伸度等の機械的性質は何ら
遜色がなかったことが確認された。
Therefore, although Examples 4, 5, and 6 were processed, mechanical properties such as strength, initial tensile resistance, and elongation were lower than that of Comparative Example 1, which was not processed at all. It was confirmed that there was no difference.

また加工剤処理時間毎の重量増加率を調べたところ、処
理時間が100分以内では無水グルタル酸の急激な反応
の進行に伴って重量増加率は著しい傾向を示し、処理時
間が100分を越えると重量増加率は鈍化傾向を示して
いた。また各加工絹糸の水分率についても調べたところ
、加工後も未加工時のそれとほぼ同一であった。
Furthermore, when we investigated the weight increase rate for each processing agent treatment time, we found that within 100 minutes of treatment time, the weight increase rate tended to be significant due to the rapid progress of the reaction of glutaric anhydride, and when the treatment time exceeded 100 minutes, The weight increase rate showed a slowing trend. We also investigated the moisture content of each processed silk thread, and found that it was almost the same after processing as when it was unprocessed.

実験例3 絹糸の代りに精練した絹布(14刃目付 羽二重)を用
い、また2塩基酸無水物として無水コハク酸の代りに無
水グルタル酸を同量用いた以外は実施例1(処理時間4
5分)と同様の方法で加工処理を施し、これを実施例7
とした。
Experimental Example 3 Example 1 (processing time 4
5 minutes) was processed in the same manner as in Example 7.
And so.

更に時間90分、270分の加工処理を施した絹布を実
施例8.9とした。また全く加工処理を施さなかった絹
布を比較例2とした。
A silk fabric further processed for 90 minutes and 270 minutes was designated as Example 8.9. Comparative Example 2 was a silk fabric that was not subjected to any processing.

各絹布の夫々について防しわ率を測定すると共に、射光
試験を行なった。尚防しわ率はJISF 1509 方
法(センサンド法)によって測定し、また射光試験はキ
セノンロングライフ フェードメータWEL−25AX
−IC−PC(、スガ試験機)ニテ紫外線100時間照
射後の黄色度をカラーコンピュータ5M−3(スガ試験
機)の直読によって1IIJ定した。
The wrinkle resistance rate of each silk fabric was measured, and a light emission test was also conducted. The wrinkle prevention rate was measured using the JISF 1509 method (sensand method), and the light test was performed using a xenon long life fade meter WEL-25AX.
-IC-PC (Suga Test Instruments) The yellowness after 100 hours of irradiation with ultraviolet light was determined by direct reading on a color computer 5M-3 (Suga Test Instruments).

得られた防しわ率のi’1llI定結果および射光試験
の試験結果を表−3に示す。
Table 3 shows the i'1llI determination results of the wrinkle prevention rate and the test results of the light test.

表−3 表−3から明らかなように実施例7,8.9の防しわ率
は比較例2に比して著しく向上した。
Table 3 As is clear from Table 3, the wrinkle prevention rates of Examples 7 and 8.9 were significantly improved compared to Comparative Example 2.

また実施例7,8.9は比較例2に比して紫外線照射1
00時間の苛酷な条件下で優れた黄変防止効果が得られ
た。
In addition, Examples 7, 8, and 9 were different from Comparative Example 2 when UV irradiation was performed at 1
Excellent anti-yellowing effect was obtained under severe conditions for 0.00 hours.

従って、実施例7,8.9は加工処理を施すことによっ
て絹製品のドレープ性、絹特有の柔軟性等の風合い特性
を損うことなく弾力的性質を向上でき、かつ優れた黄変
防止効果を有することが確認された。
Therefore, Examples 7, 8, and 9 can improve elastic properties without impairing the drape properties of silk products, the softness and other texture characteristics unique to silk, and have excellent anti-yellowing effects. It was confirmed that the

実験例4 前記実施例7および比較例2の各絹布を絹布重量の0.
02%のカチオン染料(メチレンブルー)を含んだ水溶
液に浸漬し、温度25℃で24時間反応させた後、夫々
の表面染着濃度を測定した。尚表面染む濃度(K/S値
)は自記分光光度計(品性製作所MPS−50L型)で
反射率を測定し、クベルカ・ムンクの式より算出した。
Experimental Example 4 Each of the silk fabrics of Example 7 and Comparative Example 2 was mixed with 0.0% of the weight of the silk fabric.
After immersion in an aqueous solution containing 0.2% cationic dye (methylene blue) and reacting at a temperature of 25°C for 24 hours, the surface dyeing concentration of each was measured. The density of surface staining (K/S value) was calculated by measuring the reflectance with a self-recording spectrophotometer (Model MPS-50L, manufactured by Kinsei Seisakusho) and using the Kubelka-Munk equation.

得られたalll定値は実施例7は14J41であり、
また比較例2は8.178であった。
The obtained all constant values are 14J41 in Example 7,
Moreover, Comparative Example 2 was 8.178.

従って実施例7は加工処理が施しているにもかかわらず
優れた染色性を有することが確認された。
Therefore, it was confirmed that Example 7 had excellent dyeability despite being subjected to processing.

(発明の効果) このように本発明によるときは、絹糸または絹織物の絹
製品を2塩基酸無水物を含有する有機溶剤から成る加工
溶液で浸漬処理するようにしたので、処理加工された絹
製品を未加工絹製品と同等の優れた機械的性質が得られ
、しかも処理加工された絹製品に対して良好な防しわ率
、黄変防止性および染色性の向上が得られる絹製品の加
工方法を提供することが出来る効果がある。
(Effects of the Invention) According to the present invention, a silk product made of silk thread or silk fabric is soaked in a processing solution consisting of an organic solvent containing a dibasic acid anhydride. Processing of silk products that provides products with excellent mechanical properties equivalent to those of unprocessed silk products, and with improved wrinkle resistance, anti-yellowing properties, and dyeability compared to treated silk products. It has the effect of providing a method.

特 許 出 願 人  農林水産省蚕糸試験場長堀  
江  保  宏
Patent applicant Nagahori Sericulture Experiment Station, Ministry of Agriculture, Forestry and Fisheries
Hiroshi Eyasu

Claims (1)

【特許請求の範囲】 一般式 ▲数式、化学式、表等があります▼ (ただし式中nは2〜4である) で示される2塩基酸無水物を含有する有機溶剤から成る
加工溶液で浸漬処理することを特徴とする絹製品の加工
方法。
[Claims] Immersion treatment with a processing solution consisting of an organic solvent containing a dibasic acid anhydride represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (where n is 2 to 4) A method for processing silk products characterized by:
JP28959287A 1987-11-18 1987-11-18 Method for processing silk product Granted JPH01132877A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP28959287A JPH01132877A (en) 1987-11-18 1987-11-18 Method for processing silk product

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP28959287A JPH01132877A (en) 1987-11-18 1987-11-18 Method for processing silk product

Publications (2)

Publication Number Publication Date
JPH01132877A true JPH01132877A (en) 1989-05-25
JPH0141754B2 JPH0141754B2 (en) 1989-09-07

Family

ID=17745231

Family Applications (1)

Application Number Title Priority Date Filing Date
JP28959287A Granted JPH01132877A (en) 1987-11-18 1987-11-18 Method for processing silk product

Country Status (1)

Country Link
JP (1) JPH01132877A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03152272A (en) * 1989-11-07 1991-06-28 Norin Suisansyo Sanshi Konchiyuu Nogyo Gijutsu Kenkyusho Modified protein fiber, protein fiber product and production thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017070873A1 (en) * 2015-10-28 2017-05-04 南通纺织丝绸产业技术研究院 High performance natural silk fiber and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03152272A (en) * 1989-11-07 1991-06-28 Norin Suisansyo Sanshi Konchiyuu Nogyo Gijutsu Kenkyusho Modified protein fiber, protein fiber product and production thereof
JPH0536534B2 (en) * 1989-11-07 1993-05-31 Norinsuisansho Sanshi Konchu Nogyo Gijutsu Kenkyushocho

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