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CN1028781C - Enzymatic treatment of wool - Google Patents

Enzymatic treatment of wool Download PDF

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Publication number
CN1028781C
CN1028781C CN88108412A CN88108412A CN1028781C CN 1028781 C CN1028781 C CN 1028781C CN 88108412 A CN88108412 A CN 88108412A CN 88108412 A CN88108412 A CN 88108412A CN 1028781 C CN1028781 C CN 1028781C
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CN
China
Prior art keywords
wool
fiber
enzyme
protease
chlorination
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN88108412A
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Chinese (zh)
Other versions
CN1034032A (en
Inventor
路易吉·钱皮
奥托·福斯特
汉斯-鲁道夫·黑费利
弗兰茨·克瑙西达
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Schoeller Hardtrum AG
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Schoeller Hardtrum AG
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Publication date
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Publication of CN1034032A publication Critical patent/CN1034032A/en
Application granted granted Critical
Publication of CN1028781C publication Critical patent/CN1028781C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D06M16/003Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with enzymes or microorganisms

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • Microbiology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)

Abstract

The invention relates to a method for processing wool or animal fibres with low or no felting and a soft feel and special shrink-resistance and strength properties, in which method the wool is treated with a proteolytic enzyme and then at a temperature between room temperature and 140 ℃.

Description

Enzymatic treatment of wool
The invention relates to and make wool and animal fiber have low felting or do not play the production technology of felt and the product that obtains therefrom.
For many years, the wool that how can not to obtain felt has become a problem, is head it off, has released many methods, comprises the enzyme processing.This method is as at " weaving is put into practice " 18(1963.3) disclosed by E.P.Friester among the 236-240, his reference be that W.R.Middlebrook and H.Phillips are at " dyeing man " magazine 57(1941) 137-144 page or leaf and ANDavidson and RPreston be at weaving monthly magazine 47(1956) in the 685-707 page or leaf (same be described in belgian patent 536819).Although do not resemble detailed explanation the european patent application 134267, the purpose of handling with enzyme is in order to remove the scale layer of wool, promptly to remove the extexine of fiber fully, thus fiber just lost wool intrinsic natural crimp feature.
The objective of the invention is to process wool and animal fiber, not only keep their natural crimp and intact scale layer, still hang down felting simultaneously or do not play felt.Just can finish this purpose by the enzyme processing, as a comparison, existing treatment technology is shallow and not deep enough.Can in common home laundry machine, wash with the product that this method obtained, and not have adverse consequences.Differentiation is an IWS test method 31 from effective ways of this product that natural wool comes, and is announced by international wool association.Therefore, untreated fiber has just begun felt after three times at the most in described 7A washing, and can stand at least five times and do not play felt with the wool after the enzyme processing according to of the present invention.
Another measure wool fibre whether do not rise felt be according to IWS test method 185 fixed known Cubax test, wherein, the shrinkage of wool was measured by handling with three-dimensional form in a standardized washing facility in one hour.In this test, after the Cubex test continued one hour at least, wool had the shrinkage area less than 10%.This area is interpreted as in the shrinking percentage of length direction and the wrinkle percentage sum on width.Correspondingly in family's washing machine, wash 15-20 time, and do not have contraction or its surface and shape not to have significant change with high speed.
Further, the intensity decreases of the wool that the strength ratio of processing back Woolen yarn is untreated is less than 15%RKM, and percentage elongation descends less than 20%.
Thereby, the invention relates to the processing method of wool or proteinaceous animal fiber, and make it the performance (following character is arranged) that has low felting and do not play felt except that the outward appearance of soft hand feeling, natural wool:
A) Cubax test continued one hour at least or according to five times after-contraction areas of IWS TM317A circulation less than 10%;
B) compare with the untreated wool or the yarn of animal fiber, intensity decreases is less than 15%RKM;
C) percentage elongation descends less than 20%.
The invention is characterized in wool introduced in the bath that protease is arranged to contact, under temperature is the condition of room temperature (20 ℃)~140 ℃, handle subsequently.
Protease is interpreted as any protein cleavage enzyme.Suitable protease is the enzyme that reclaims from bacterium, abstinyl enzyme (esperase) pronase e for example, protease P, subtilysin, thermolysin and the enzyme that from animal-plant material, obtains, for example trypsase, pepsin, pancreatin or bromelain.The mixture of various enzymes also can use, and these enzymes can obtain on market, but the method according to this invention, the preferential protease of selecting is animal and plant enzyme, particularly bromelain.
Add special activating agent, cysteine for example, two sulphur moss sugar alcohols, two sulphur threose or mercaptoethanols can increase the activity of the enzyme that uses.Other additive, the salt of for example known energy stabilized enzyme also can use, as calcium chloride and zinc chloride.Use these salt with the amount that adapts with enzyme.
In long or short a bath, also can use Protease Treatment wool or animal fiber.Handle the mode of preferably selecting dipping, for example, in short the bath by pad, injection, coating or printing wait and carry out.Protease energy and water-bearing media or organic solvent are used together, can also use with the form of slurry or foam.In continuous processing procedure, bath raio is 1: 0.7~1: 10, is preferably 1: 1 to 1: 5, is in a long bath if handle, and then is 1: 10~1: 40.
The temperature preferred values that protease is used is room temperature~60 ℃, and when using conventional buffer, treatment fluid or pH value of slurry are 4~9, are preferably 5-7.
The common use amount of protease is 0.1~2%, and correspondingly the activity of enzyme is 400~1500cDu/mg, with over dry wool re-computation.
After directly handling with enzyme, wool or animal fiber stay to be shelved and/or through heat-treated, and at fabric portions or all under the dry situation, dwelling period can be from being as short as a few hours very much.According to temperature, heat treatment may be carried out several minutes until a few hours, until the wool drying.Saturated vapor, superheated steam, hot blast or high frequency waves (HF) all can be used as heat treatment.When with the saturated vapor decatize, wool or animal fiber stay and shelve 10-30 minute is exactly very favorable.When HF was dry, wool or animal fiber were handled 10 minutes to 1 hour at 100 to 102 ℃ usually.Dwelling period or heat treated condition are to select like this: to obtain the wool of required character, preferably when processing finished, selected enzyme lost activity simultaneously.After processing, the also available known method of enzyme of activity of still having makes it to lose activity.
Subsequently, wool or animal fiber wash, dry and other operation.
According to method of the present invention, employed bath can be used for wool and other proteinaceous animal fiber.Fibrous material can be present in the various procedure of processings, for example, and with the form of loose hair, wool top, rove, yarn, plain cloth, braided fabric, bondedfibre fabric or felt.According to the present invention, can both handle at wool reset condition or that give processing.
In order to obtain the certain effect and/or the optimum efficiency of Protease Treatment, conventional is to carry out the special processing of giving before enzyme is handled, be suitable for giving of wool or animal fiber and handle oxidation processes, for example, use hydrogen peroxide, in the presence of optional stabilizer, with potassium permanganate, Caro ' s acid, chlorine or chloride compound, for example chlorine, hypochlorous acid or organochlorine carrier or ozone; Processing is given in reduction, for example uses hydrogen sulfide, oxo sulfate or sulfide; Alkali treatment, with acid, solvent or enzyme be lipase for example, catalyzing enzyme, oxidizing ferment, peroxidase give to be handled or physical treatment, the ripple of for example using various ways is HF ripple or cold body discharge (Cold dischazge) for example, and these give and handling is known, and uses in partially modified wool.
After giving processing, wool or animal fiber are by rinsing and drying.
Feature according to the selected technology of the present invention is that wool or animal fiber come chlorination by oxidation, uses Protease Treatment then.
Preferably use to have active chlorine and carry out the oxidation chlorination of wool or animal fiber and handle, for example, the chlorine form in water or to contain the clorox form of hydrochloric acid.Give processing with known method, wool or animal fiber stand gentle chloridized, and the amount of active chlorine is 0.1~2%, calculate with the weight of over dry wool or animal fiber.PH during processing is 2-3, and the time is 1-10 second, and temperature is 10~30 ℃.
After giving processing, in order to obtain required enzyme effect, remove for wool or animal fiber and to give finishing agent, and be favourable when making its pH for neutral range.
After chloridized, fibrous material is proceeded to handle to remove residual chlorine, neutralizes subsequently or simultaneously.By the chlorine that uses reductant to remove in fiber or fiber surface exists, for example sodium hydrogensulfite, sodium sulfite etc., with alkali compounds for example alkali carbonate to neutralize also be favourable.
According to selected process conditions, be with or without and give processing, the phosphorus lamella of wool or animal fiber part or slight change or activation are only arranged.Because the result that enzyme is handled, wool that is obtained or animal fiber have a kind of low felting property and in further processing (spin, bleach, dye) and after making fabric use and wash in can not have problems.With the wool after the method processing of the present invention is soft, and more superior is the feel that natural wool is arranged, and when it just is subjected to chloridized in the wool top stage, handles with above-mentioned enzyme then, and the product of gained is just special soft.Adverse influence will not take place in the wool according to the present invention after the processing or the stainability and the dyefastness of animal fiber, comparatively speaking, sizable improvement be arranged.
Following Example will illustrate the present invention, and all percentage all is weight, and all temperature all are degree centigrade.
Example one
Wool tops pads with a kind of liquid bath shampoo [pH is 6.0, contains 0.5% abstinyl enzyme (esperase), and (BacLich, can from NoVo(Denmark) obtains] in the time of 40 ℃, and its amount is a benchmark with weight of over dry wool tops.Pick-up is 50%.
Wool tops behind the dipping was shelved in 102 ℃ superheated steam 15 minutes subsequently.After processing, wool tops is washed and is dry.
The wool of resulting softness has low felting property, and has spinnability, does not almost have waste material.
Example two
Repeat the method for example one, pad and roll do after, wool tops at first during transition all stays, and handles 30 minutes in 100~102 ℃ HF drier then.
Example three
Wool tops at first padded 3 seconds in 10~20 ℃ on the split padding machine, made wool tops contain the chlorine water of 0.4% effective chlorine.And then rinsing was handled 45 seconds with the liquid solution of the sodium hydrogensulfite that contains the sodium carbonate of 4g/l and 1g/l subsequently, and the washing secondary.
After drying, the wool top of chlorination is accepted to handle as example one or example two described enzymes.
Example four
Wool tops contains the solution (PH is 5.5~6.0) of stabilizer of hydrogen peroxide of the no silicate of 15ml hydrogen peroxide (40% percent by volume) 3ml routine to be handled 60 minutes in 30 ℃ with every liter of solution; bath raio is 1: 20; wool is subsequently by rinsing, and and then the method for use-case one is carried out enzyme and handled.
Example six
Wool tops contains the liquid (pH=7.5 to 8.5) of the sodium hypophosphite of 15ml hydrogen peroxide (40% percent by volume) 4g/l to be handled 5 hours in 45 ℃ with every liter of solution.Bath raio is 1: 20, and wool tops is subsequently by rinsing, and and then the method for use-case one is carried out the enzyme processing.
Example seven
Wool tops was handled 60 minutes in 20 ℃ with the liquid that contains 6% permonosulphuric acid (Caro ' s acid).Bath raio is 1: 20, adds 2% sulfuric acid subsequently in bath, and wool tops was handled 30 minutes with this body lotion further in 26 ℃, adds 12% sodium sulfite subsequently in bath, and wool tops was further handled 20 minutes in 30 ℃.
After washing, handle with enzyme as the method for example one.
Example eight
Wool tops pH be 7 body lotion (every liter of body lotion contains the hydrogen peroxide (40% percent by volume) of 25ml and the potassium peroxydisulfate of 25g/l] pad in 30 ℃, pick-up is 60%, shelved 10 hours in room temperature, wool tops is washed, subsequently with handling as example one or the two described enzymes that carry out.
Example nine
Wool tops was handled 6 hours in 40 ℃ with containing 0.5% conventional peroxidase and 0.25mol/l hydrogen peroxide body lotion, and bath raio is 1: 25, with post rinse, uses as the abstinyl enzyme (esperase) of example one or example two again and handles.
Example ten
Wool tops was handled 6 hours in 40 ℃ with the body lotion that contains 0.5% normal fat enzyme, and bath raio is 1: 20, with post rinse, uses then as example one or example two described abstinyl enzymes (esperase) and handles.
Example 11
Wool tops pads with the body lotion of the hydrogen peroxide (40% percent by volume) that contains 0.2% conventional catalase and 40ml/l, and pick-up is 50%, and the wool behind the dipping was shelved 6 hours in room temperature subsequently, then flushing.
Giving wool after the processing uses then as example one or example two described abstinyl enzymes (esperase) and handles.
A kind of protease, for example pancreatin can replace abstinyl enzyme (esperase) to use in example one to 11.And soft hand feeling and anti-shrink wool have been obtained to have therefrom.
Example 12 and 13
Repeat example one and example two, the bromelain with 0.5% replaces 0.5% abstinyl enzyme (esperase).
Obtain to have soft feel and anti-shrink wool therefrom.
Use an amount of bromelain to replace abstinyl enzyme (esperase) to repeat example three to 11, can obtain soft feel and anti-shrink wool therefrom.

Claims (6)

1, make wool or contain the processing method that the protein animal fiber has low felting or do not play felt, said low felting or do not rise felt be by following a), b) and c) limit:
A) according to IWS test method 185 determined Cubex test continued 1 hour at least or according to IWS test method 31 between after the 7A circulation 5 times, the shrinkage factor of press length direction and width contraction sum is less than 10%;
B) compare with untreated wool or fiber, yarn strength descends less than 15%;
C) compare with untreated wool or fiber, percentage elongation descends less than 20%;
Said method comprises that chlorination by active chlorine is with wool or fiber oxidation, then protease is introduced in the wool or fiber of dipping in short the bath, the wool that to handle through enzyme or fiber are under the temperature between 20 ℃ and 140 ℃ again, thereby with high frequency waves directly handle give above-mentioned a), b) and c) characteristic, the processing conditions of this method is to preserve the natural intact wool or the scale layer of fiber.
2, according to the process of claim 1 wherein that the time of handling with high frequency waves is 10 minutes to 1 hour.
3, according to the process of claim 1 wherein that the consumption of protease is to press 0.1 to 2% of wool or the calculating of fiber dry weight, the enzyme activity corresponding to 400 to 1500CDU/mg.
4, according to the process of claim 1 wherein that chlorination is a chlorine or carry out with clorox and hydrochloric acid in the water.
5, according to the method for claim 4, wherein chlorination is by carrying out with the chlorination of 0.1 to 2% the active chlorine of calculating by wool or fiber dry weight.
6, according to each the method among the claim 1-5, protease wherein is bromelain.
CN88108412A 1987-10-28 1988-10-27 Enzymatic treatment of wool Expired - Fee Related CN1028781C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH04214/87 1987-10-28
CH421487 1987-10-28

Publications (2)

Publication Number Publication Date
CN1034032A CN1034032A (en) 1989-07-19
CN1028781C true CN1028781C (en) 1995-06-07

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EP (1) EP0344250B1 (en)
JP (1) JPH02502032A (en)
KR (1) KR890701833A (en)
CN (1) CN1028781C (en)
AT (1) ATE89349T1 (en)
AU (1) AU626818B2 (en)
BR (1) BR8807268A (en)
DE (1) DE3881033T2 (en)
ES (1) ES2009361A6 (en)
WO (1) WO1989003909A1 (en)

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US5529928A (en) * 1987-10-28 1996-06-25 Schoeller Hardtrum Ag Enzymatic treatment of wool
US5232851A (en) * 1990-10-16 1993-08-03 Springs Industries, Inc. Methods for treating non-dyed and non-finished cotton woven fabric with cellulase to improve appearance and feel characteristics
TR199501643A2 (en) * 1994-12-21 1996-07-21 Nova Nordisk As Method for the treatment of wool with enzymes.
US5980579A (en) * 1996-12-17 1999-11-09 Genencor International, Inc. Process for improved shrink resistance in wool
US6723550B1 (en) 1997-07-15 2004-04-20 Genencor International, Inc. Proteases from gram-positive organisms
FR2769647B1 (en) * 1997-10-09 2000-05-12 Peignage Amedee PROCESS FOR THE MECHANICAL / BIOCHEMICAL TREATMENT OF TEXTILE FIBERS OF ANIMAL ORIGIN, AND THE NEW FIBERS AND NEW ARTICLES THUS OBTAINED
FR2769646B1 (en) * 1997-10-09 1999-12-03 Peignage Amedee PROCESS FOR THE MECHANICAL / BIOCHEMICAL TREATMENT OF TEXTILE FIBERS OF ANIMAL ORIGIN, AND THE NEW FIBERS AND NEW ARTICLES THUS OBTAINED
ES2368718T3 (en) 1997-10-23 2011-11-21 Danisco Us Inc. SUBTILISINE VARIATIONS WITH MULTIPLE SUBSTITUTIONS.
GB9727470D0 (en) 1997-12-30 1998-02-25 Genencor Int Bv Proteases from gram positive organisms
US6465186B1 (en) 1997-12-30 2002-10-15 Genecor International, Inc. Proteases from gram positive organisms
US6528255B1 (en) 1997-12-30 2003-03-04 Genencor International, Inc. Proteases from gram positive organisms
US6599731B1 (en) 1997-12-30 2003-07-29 Genencor International, Inc. Proteases from gram positive organisms
DE19807456B4 (en) * 1998-02-21 2008-01-17 Textilchemie Dr. Petry Gmbh Felt-free wool and process for its production
US6051033A (en) * 1998-05-20 2000-04-18 Novo Nordisk Brochem North America Inc. Method for enzymatic treatment of wool
US6140109A (en) * 1998-05-20 2000-10-31 Novo Nordisk Biochem North America, Inc. Method for enzymatic treatment of wool
WO2004070106A1 (en) * 2003-02-06 2004-08-19 Daiwa Kasei K.K. Method of shrink-proofing animal hair fiber
CN1316117C (en) * 2005-05-18 2007-05-16 陕西省科学院酶工程研究所 Finishing method for preventing felting and shrinking of wood fabric
CN102965955A (en) * 2012-10-19 2013-03-13 江南大学 A kind of cutinase, keratinase and protease one-bath wool anti-felting process
CN102965960B (en) * 2012-11-21 2014-12-17 山东来利来毛纺有限公司 Shrink-proof technique of chemical fiber
CN103643485A (en) * 2013-11-30 2014-03-19 江苏金泰针织有限责任公司 Anti-felting finishing process for knitted woolen sweater
EP3092335B1 (en) * 2014-01-06 2019-05-15 Reliance Industries Limited A process for recovering polyester
CN105986484B (en) * 2015-02-13 2018-05-29 天津滨海东方科技有限公司 Continuous processing technology without chlorine wool tops and wool product anti-shrinking
CN104727154B (en) * 2015-03-12 2017-01-18 浙江米皇羊绒股份有限公司 Machine-washable cashmere sweater
CN105908309A (en) * 2016-06-30 2016-08-31 江苏华信亚麻纺织有限公司 Wet spinning technique for spun silk and flax blending
CN107964687A (en) * 2017-11-28 2018-04-27 黄桂凤 A kind of degreasing method of animal wool
CN113430815B (en) * 2021-07-28 2022-03-04 武汉纺织大学 A kind of continuous processing method and device for improving millet resistance of wool fabric
CN114230855A (en) * 2021-12-18 2022-03-25 河北省微生物研究所有限公司 Method for recycling wool fibers by using complex enzyme preparation

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BE536819A (en) *
JPS58144105A (en) * 1982-02-12 1983-08-27 Kurabo Ind Ltd Production of descaled animal fiber

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WO1989003909A1 (en) 1989-05-05
ES2009361A6 (en) 1989-09-16
BR8807268A (en) 1989-10-31
DE3881033T2 (en) 1993-12-02
JPH02502032A (en) 1990-07-05
ATE89349T1 (en) 1993-05-15
AU626818B2 (en) 1992-08-13
KR890701833A (en) 1989-12-21
CN1034032A (en) 1989-07-19
AU2710188A (en) 1989-05-23
DE3881033D1 (en) 1993-06-17
EP0344250A1 (en) 1989-12-06
EP0344250B1 (en) 1993-05-12

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