WO2020186950A1 - 一种利用蛋白酶k对羊毛织物进行防毡缩整理的方法 - Google Patents

一种利用蛋白酶k对羊毛织物进行防毡缩整理的方法 Download PDF

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WO2020186950A1
WO2020186950A1 PCT/CN2020/075480 CN2020075480W WO2020186950A1 WO 2020186950 A1 WO2020186950 A1 WO 2020186950A1 CN 2020075480 W CN2020075480 W CN 2020075480W WO 2020186950 A1 WO2020186950 A1 WO 2020186950A1
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wool
fabric
proteinase
solution
finishing
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PCT/CN2020/075480
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English (en)
French (fr)
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王强
李文佳
余圆圆
袁久刚
王平
范雪荣
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江南大学
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Publication of WO2020186950A1 publication Critical patent/WO2020186950A1/zh
Priority to US17/475,423 priority Critical patent/US20220002938A1/en

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12Y—ENZYMES
    • C12Y304/00—Hydrolases acting on peptide bonds, i.e. peptidases (3.4)
    • C12Y304/21—Serine endopeptidases (3.4.21)
    • C12Y304/21064—Peptidase K (3.4.21.64)
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
    • D06M11/72—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with metaphosphoric acids or their salts; with polyphosphoric acids or their salts; with perphosphoric acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D06M16/003—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with enzymes or microorganisms
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/10—Animal fibres
    • D06M2101/12—Keratin fibres or silk
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/45—Shrinking resistance, anti-felting properties

Definitions

  • the invention relates to a method for anti-felting finishing of wool fabrics by using proteinase K, and belongs to the technical field of dyeing and finishing of wool fabrics in the wool spinning industry.
  • Wool has a full hand feel, strong moisture absorption capacity, is not easy to stain and has excellent warmth retention. It is a popular high-end textile fabric. However, the special scaly structure on the surface of the wool fiber gives the wool a unique milling property, which is prone to felting when washed with water. In addition, the good elasticity and crimp of wool also promote the generation of felt shrinkage and affect its practicality.
  • the chlorination process is very common in the anti-felting treatment of wool.
  • This method has a good anti-felting effect, and the wetting performance of the fabric is also improved, but it has great damage to the wool and the fabric is easy to yellow after treatment. , And pollute the environment.
  • the enzymatic anti-felting finishing of wool has always been the focus and hotspot of domestic and foreign research due to its environmental protection characteristics, and it is the most promising new technology to replace the traditional chlorinated anti-felting processing.
  • wool is a protein fiber, protease, as a type of enzyme that specifically catalyzes the hydrolysis of peptide bonds in proteins, first entered the field of research.
  • protease anti-felting finishing mainly uses the hydrolysis of enzyme molecules on wool to destroy the scale layer and achieve the purpose of anti-felting.
  • the use of protease is mild, and the waste liquid is easily degraded, which meets environmental protection requirements.
  • the wool fabric treated with protease feels softer, more lustrous, and its pilling resistance is obviously improved.
  • Proteinase K belongs to the class of serine proteases, which is a major type of protease produced by Tritirachium album Limber. Because the microorganisms that can synthesize this kind of protease can grow in an environment with keratin as the sole carbon and nitrogen source, that is, they can digest keratin, so it is named proteinase K.
  • the proteinase K family contains a variety of intracellular peptidases secreted by fungi, yeast and gram-negative bacteria. Compared with other proteases, proteinase K has high activity and high stability.
  • Proteinase K has broad substrate specificity and tends to degrade carboxy-terminal peptide bonds with aliphatic and aromatic amino acids. Its relative molecular weight is about 29.3kDa. Because the enzyme is active in a wide pH range (4 ⁇ 12.5) and high temperature (50 ⁇ 70°C), it has high activity in the buffer for extracting DNA and RNA, and can be used for plasmid or genomic DNA, RNA The separation is the key reagent for DNA extraction.
  • the present invention provides a novel method for protease to perform anti-felting finishing on wool fabrics.
  • proteinase K can effectively degrade keratin, destroy and peel off the scale layer to a greater extent, and obtain ideal wool anti-felting. effect.
  • the CMC is blocked by chitosan oligosaccharides so that the effect of proteinase K on the wool is concentrated on the scale layer. After treatment, the overall strength of the wool is less damaged, which overcomes the shortcomings of ordinary proteases and has a good overall effect of anti-felting.
  • the technical solution of the present invention is: a method for anti-felting finishing of wool fabric by using proteinase K, the method is pretreating the wool fabric or wool fiber with urea peroxide, and then using chitosan to The cell membrane complex CMC is blocked, and the wool is treated with proteinase K and washed with water.
  • the chitosan oligosaccharide is used to block the cell membrane complex CMC, which means that the chitosan oligosaccharide and the cell membrane complex CMC are combined in the form of ionic bonds and hydrogen bonds.
  • Urea peroxide pretreatment fabric the wool fabric or wool fiber is soaked in hot water at 80 ⁇ 100°C for 0.5 ⁇ 1h, then taken out, and then placed in the urea peroxide containing 10 ⁇ 50mL/L, sodium pyrophosphate 1 ⁇ 3g/ L and penetrant JFC 0.5 ⁇ 2g/L, bath ratio 20 ⁇ 50:1, temperature 40 ⁇ 70°C, pH 5 ⁇ 9, treatment time 1 ⁇ 4h; rinse with water after completion, under 50 ⁇ 60°C drying;
  • Proteinase K treated fabric Put the wool fabric or wool fiber pretreated in step (1) in 40-65°C hot water containing 0.5-2g/L chitooligosaccharides and 10-50g/L urea, bath ratio It is 20-50:1, immersed for 0.5-1h, then immersed in proteinase K solution, temperature 80-95°C, pH 6-10, bath ratio 20-50:1, treatment time 2-24h;
  • 0.5-2 mmol/L Ca 2+ is added to the proteinase K solution.
  • the wool fabric or wool fiber after enzyme inactivation is washed with hot water at 90-100° C. and cold water at room temperature for 1 to 2 times in sequence.
  • the inactivation of the enzyme is to add 0.5-5.0 mol/L of trichloroacetic acid to the proteinase K solution to inactivate the proteinase K, and the temperature of the proteinase K solution can also be increased to 80-90 Treat at °C for 10-30min.
  • the amount of proteinase K is 2 ⁇ 32U / g of fabric / fiber, preferably 2 ⁇ 16U / g of fabric / fiber.
  • the treatment time of the proteinase K is preferably 2-6 hours.
  • the wool fabric includes any one of all wool gabardine, serge, and velvet worsted woolen fabrics or all wool gabardine, serge, and velvet woolen woolen varieties.
  • the presence or absence of carbamide peroxide pretreatment has a greater impact on the felting performance of wool fabrics or fibers, and the anti-felting performance of wool fabrics or fibers after pretreatment has been improved to a greater extent.
  • the present invention also provides an anti-felting finishing solution for wool fabrics.
  • the finishing solution is divided into A solution, B solution and C solution.
  • the A solution contains 10-50 mL/L of urea peroxide and 1 to 50 mL/L of sodium pyrophosphate. 3g/L and penetrant JFC 0.5 ⁇ 2g/L
  • solution B is a solution containing 0.5 ⁇ 2g/L chitooligosaccharides and 10 ⁇ 50g/L urea
  • solution C is 0.5 ⁇ 2mmol/L Ca 2+ ⁇ Protease K solution.
  • the present invention provides a method of using the above-mentioned anti-felting finishing solution for wool fabrics.
  • the wool fabric or wool fiber is immersed in hot water at 80-100°C for 0.5-1h, then taken out, and then placed in A solution with a bath ratio of 20-50 :1,
  • the treatment time is 1 ⁇ 4h at 40 ⁇ 70°C; after the end, rinse with water and dry at 50 ⁇ 60°C; then put in B solution, bath ratio is 20 ⁇ 50:1, and immerse at 40 ⁇ 65°C 0.5 ⁇ 1h, then treat it in liquid C at 80 ⁇ 95°C for 2 ⁇ 24h, bath ratio is 20 ⁇ 50:1, inactivate enzyme, wash with water and dry.
  • the present invention uses carbamide peroxide as a pretreatment method of wool fabric or wool fiber for the first time, which can destroy the lipid structure of the surface layer of the wool scale and the disulfide bonds of the scale part, and create better conditions for subsequent enzyme treatment.
  • carbamide peroxide as a pretreatment method of wool fabric or wool fiber for the first time, which can destroy the lipid structure of the surface layer of the wool scale and the disulfide bonds of the scale part, and create better conditions for subsequent enzyme treatment.
  • the urea produced during the decomposition of carbamide peroxide can help the fiber swell, thereby better exerting the oxidation effect of carbamide peroxide on lipids and the surface of scales.
  • the present invention addresses the problem of weak degradation of scaly keratin by ordinary protease and slow processing speed of keratinase.
  • the present invention introduces proteinase K into wool anti-felting finishing for the first time, and proteinase K can hydrolyze keratin at the same time. And ordinary protein, with better innovation.
  • the present invention In order to prevent proteinase K protease from attacking CMC preferentially, and then entering the fiber through the intercellular space, destroying the strength of the fiber, the present invention first uses the ionic bond of chitosan oligosaccharide and wool non-keratinized cell membrane complex CMC (common protein) It is pre-combined with the hydrogen bond form to play a certain role of "closing CMC", and then use proteinase K to effectively degrade keratin to perform anti-felting finishing on wool fabrics, destroying the flake layer of wool (CMC is not easy to be enzymatically degraded due to sealing ), so as to obtain a better anti-felting effect and less strong damage to the wool.
  • CMC common protein
  • the present invention uses carbamide peroxide for pretreatment and then treatment with proteinase K to make wool fabrics or fibers have an anti-felting effect, reduce the degree of fabric washing and felting, and achieve a machine-washable effect, which is better than the traditional chlorination method. It is more in line with the requirements of modern green ecology, health and environmental protection.
  • Proteinase K was purchased from Shanghai Yisheng Biotechnology Co., Ltd., and the product number is 10401ES80.
  • Urea peroxide pretreatment fabric soak the wool fabric in 90°C hot water for 1 hour, then put it in a solution containing 30mL/L carbamide peroxide, 1.5g/L sodium pyrophosphate, and penetrant JFC 1g/L, bath Ratio 35:1, temperature 50°C, pH 8, treatment time 1h. After the end, rinse repeatedly with water and dry at 50°C.
  • Proteinase K treatment fabric The pretreated wool fabric is first immersed in hot water containing 1g/L chitooligosaccharides and 20g/L urea at 90°C for 1h, and then put into 16U/g fabric proteinase K solution ( Enzyme solution temperature is 50°C, pH 8, bath ratio 25:1, and 1mmol/L Ca 2+ ) is immersed for 6h.
  • the enzyme is inactivated at 80°C for 10 minutes. After finishing, wash with hot water at 90°C and cold water at room temperature twice, and dry at 50°C.
  • the felt shrinkage rate of the wool fabric is 5.02%, the weight reduction rate is 9.0%, and the strength loss is 14.1%.
  • Control sample pretreat the fabric according to step (1) in Example 1, and then treat the fabric with the protease of 16 U/g fabric according to step (3).
  • the felt shrinkage rate of the control sample is 8.06%, the weight loss rate is 25.9%, and the strength loss is 42.70%.
  • Pretreatment of fabric with urea peroxide soak the wool fabric in hot water at 90°C for 1 hour, and then place it in a solution containing 30mL/L of urea peroxide, 1.5g/L of sodium pyrophosphate, and 1g/L of penetrant JFC.
  • the bath ratio is 35:1, the temperature is 50°C, the pH is 8, and the treatment time is 1h. After finishing, rinse with deionized water repeatedly, and dry at 50°C.
  • Proteinase K treated fabric The pretreated wool fabric is immersed in 90°C hot water containing 1g/L chitooligosaccharides and 20g/L urea for 1h, and put into 4U/g fabric proteinase K solution (enzyme solution) The temperature was 50°C, pH 8, bath ratio 25:1, and 1mmol/L Ca 2+ ) was immersed for 4h.
  • the enzyme is inactivated at 80°C for 10 minutes. After finishing, wash with hot water at 90°C and cold water at room temperature twice, and dry at 50°C.
  • the felt shrinkage rate of the wool fabric is 5.96%
  • the weight reduction rate is 10.65%
  • the strength loss is 11.28%.
  • Control sample pretreat the fabric according to step (1) in Example 2, and then treat the fabric with 4U/g fabric protease according to step (3).
  • the felt shrinkage rate of the control sample was 7.7%, the weight loss rate was 22.3%, and the strength loss was 39.42%.
  • the wool fabric has a better anti-felting effect after being treated with proteinase K, and the strength loss is significantly reduced compared with ordinary proteinase treatment.
  • Urea peroxide pretreatment fabric soak the wool fabric in 90°C hot water for 1 hour, then put it in a solution containing 10mL/L of urea peroxide, 2g/L of sodium pyrophosphate, and 2g/L of penetrant JFC, bath The ratio is 50:1, the temperature is 70°C, the pH is 6, and the treatment time is 2h. After finishing, rinse with deionized water repeatedly, and dry at 50°C.
  • Proteinase K treated fabric The pretreated wool fabric is immersed in hot water containing 2g/L chitooligosaccharides and 40g/L urea at 90°C for 1h, and put into the proteinase K solution (enzyme solution) of 25U/g fabric .
  • the temperature is 65°C, pH 10, bath ratio 20:1, 2mmol/L Ca 2+ ) is immersed for 4h.
  • the enzyme is inactivated at 80°C for 10 minutes. After finishing, wash with hot water at 90°C and cold water at room temperature twice, and dry at 50°C.
  • the felt shrinkage rate of the wool fabric is 4.92%
  • the weight reduction rate is 12.64
  • the strength loss is 16.47%.
  • Proteinase K treated fabric The wool fabric is immersed in 90°C hot water containing 1g/L chitosan oligosaccharide and 20g/L urea for 1h, and put into 4U/g proteinase K solution (enzyme temperature 50°C, pH 8. Bath ratio 25:1, adding 1mmol/L Ca 2+ ) for 4h immersion treatment.
  • the enzyme is inactivated at 80°C for 10 minutes. After finishing, wash with hot water at 90°C and cold water at room temperature twice, and dry at 50°C.
  • the felt shrinkage rate of the wool fabric is 10.67%, the weight reduction rate is 9.8%, and the strength loss is 10.2%.
  • the anti-felting effect of wool fabrics without carbamide peroxide pretreatment is lower than that of pre-treated wool fabrics, and the felting shrinkage rate is higher.
  • Proteinase K treated fabric the wool fabric is immersed in hot water at 90°C for 1h, and put into 4U/g proteinase K solution (enzyme temperature 50°C, pH 8, bath ratio 25:1, add 1mmol/L Soaking in Ca 2+ ) for 4h.
  • the enzyme is inactivated at 80°C for 10 minutes. After finishing, wash with hot water at 90°C and cold water at room temperature twice, and dry at 50°C.
  • the felt shrinkage rate of the wool fabric is 12.5%
  • the weight reduction rate is 12.1%
  • the strength loss is 18.32%. Comparing Example 4, it can be seen that pretreatment with oligochitosan and urea during proteinase K treatment can help reduce the felt shrinkage and strength damage.
  • Hydrogen peroxide pretreatment fabric soak the wool fabric in 90°C hot water for 1 hour, then put it in a solution containing 30% hydrogen peroxide, 1.5g/L sodium pyrophosphate, penetrant JFC 1g/L, bath ratio 35 :1, temperature 50°C, pH 8, treatment time 1h. After finishing, rinse with deionized water repeatedly, and dry at 50°C.
  • Proteinase K treated fabric The pretreated wool fabric is immersed in 90°C hot water containing 1g/L chitooligosaccharides and 20g/L urea for 1h, and put into 4U/g fabric proteinase K solution (enzyme solution) The temperature is 50°C, pH 8, bath ratio 25:1, and 1mmol/L Ca2+) is immersed for 4h.
  • the felt shrinkage rate of the wool fabric is 9.21%
  • the weight reduction rate is 10.5%
  • the strength loss is 19.18%.
  • the urea produced during the carbamide peroxide treatment helps to swell the fibers, thereby better exerting the oxidation effect of the carbamide peroxide on the lipid and the surface of the scales, which is more beneficial to the subsequent anti-felting deal with.

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Abstract

本发明公开了一种利用蛋白酶K对羊毛织物进行防毡缩整理的方法，属于毛纺行业中毛织物染整加工的应用技术领域。旨在解决普通蛋白酶防毡缩处理对羊毛强力损伤较大，对鳞片层中的角蛋白降解作用较小的问题，达到优化毛织物蛋白酶防毡缩整理的目的。优选工艺为：纯毛织物先用过氧化脲预处理，并利用壳寡糖封闭CMC，再用蛋白酶K处理羊毛织物。通过本方法处理的羊毛织物，防毡缩性能得到明显的改善，织物强力损伤下降。本发明首次将蛋白酶K引入羊毛防毡缩整理中，通过蛋白酶K对羊毛鳞片角蛋白的有效降解，达到了较好的羊毛防毡缩效果，可替代传统氯化防毡缩处理。

Description

一种利用蛋白酶K对羊毛织物进行防毡缩整理的方法 技术领域
本发明涉及一种利用蛋白酶K对羊毛织物进行防毡缩整理的方法，属于毛纺行业中毛织物染整加工的应用技术领域。
背景技术
羊毛手感丰满，吸湿能力强，不易沾染污垢而且具有优良的保暖性，是一种备受喜爱的高档纺织面料。但是，羊毛纤维表面特殊的鳞片结构使得羊毛具有独特的缩绒性，水洗时容易产生毡缩现象。此外，羊毛良好的弹性和卷曲性，也促进了毡缩现象的产生，影响了其实用性。
目前，氯化工艺在羊毛防毡缩处理中十分常见，这种方法的防毡缩效果很好，织物的润湿性能也得到改善，但对羊毛有很大的损伤，织物处理后易泛黄，且污染环境。羊毛的酶法防毡缩整理因其绿色环保的特点，一直是国内外研究的重点和热点，是最有望替代传统氯化防毡缩加工的新技术。其中，由于羊毛为蛋白质纤维，蛋白酶作为专一性催化水解蛋白质中肽键的一类酶最早进入研究视野。
蛋白酶防毡缩整理主要是利用酶分子对羊毛的水解作用，破坏鳞片层，达到防毡缩目的。蛋白酶的使用条件温和，废液易降解，非常符合环保要求。经蛋白酶处理后的羊毛织物手感柔软，更有光泽，抗起球性明显改善。但是，酶法防毡缩整理也存在很多问题：由于羊毛鳞片含有大量的二硫键交联的角质化蛋白质(角蛋白)，因此蛋白酶会优先攻击非角质化的高度可溶胀的细胞膜复合物(CMC)，进而通过细胞间间隙进入纤维内部，对纤维内部进行降解，导致纤维强力急剧下降，极大影响其穿着使用性。采用对鳞片角蛋白具有直接降解作用的酶是羊毛防毡缩加工取得较好综合效果(低毡缩率、低强损)的关键所在。目前已有利用角蛋白酶处理羊毛织物防毡缩的研究，但是角蛋白酶处理的过程非常慢，通常需要30～50h的时间，大大增加了工业生产的时间成本。
因此，亟需一种新的方法使得既能够加快生物酶对角蛋白的处理速度，又能够解决生物酶本身对羊毛内部的强力损失大的问题。
蛋白酶K属丝氨酸蛋白酶类，它是林伯氏白色念球菌(Tritirachium album Limber)等产生的一类主要蛋白酶。因能合成该种蛋白酶的微生物能在以角蛋白(Keratin)为唯一碳氮源的环境中生长，即能够消化角蛋白，因此被命名为蛋白酶K。蛋白酶K家族包含了各种由真菌、酵母及革兰氏阴性细菌分泌的细胞内肽酶。与其它的蛋白酶相比较，蛋白酶K具有高活力和 高稳定性，其酶活不会被尿素、SDS和EDTA等变性剂抑制，且在高温、高盐或较高的pH等条件下，蛋白酶K仍能保持较高活性。蛋白酶K具有广泛的底物特异性，倾向于降解带有脂肪族和芳香族氨基酸的羧基端肽键，其相对分子量约为29.3kDa。因该酶在较广的pH范围(4～12.5)内及高温(50～70℃)均有活性，在提取DNA和RNA的缓冲液中具有很高的活性，可用于质粒或基因组DNA、RNA的分离，是DNA提取的关键试剂。
发明内容
【技术问题】
为了解决现有蛋白酶对羊毛进行处理的过程中，对表层鳞片角蛋白降解作用弱但对羊毛内部损失大等问题。
【技术方案】
本发明提供了一种新型的蛋白酶对羊毛织物进行防毡缩整理的方法，一方面利用蛋白酶K可以有效降解角蛋白的特性，较大程度的破坏和剥离鳞片层，获得理想的羊毛防毡缩效果。另一方面通过壳寡糖封闭CMC使得蛋白酶K对羊毛作用集中在鳞片层，处理后对羊毛整体强力损伤较小，克服了普通蛋白酶的不足，防毡缩综合效果好。
具体的，本发明的技术方案为：一种利用蛋白酶K对羊毛织物进行防毡缩整理的方法，所述方法为用过氧化脲对羊毛织物或羊毛纤维进行预处理，之后利用壳寡糖对细胞膜复合物CMC进行封闭，再用蛋白酶K处理羊毛，水洗即可，所述利用壳寡糖对细胞膜复合物CMC进行封闭即为壳寡糖和细胞膜复合物CMC以离子键和氢键形式结合。
在本发明的一种实施方式中，所述方法的具体步骤为：
(1)过氧化脲预处理织物：将羊毛织物或羊毛纤维用80～100℃热水浸渍0.5～1h后取出，再置于含过氧化脲10～50mL/L、焦磷酸钠1～3g/L和渗透剂JFC 0.5～2g/L的溶液中，浴比20～50:1，温度40～70℃，pH 5～9，处理时间1～4h；结束后用水冲洗，50～60℃条件下烘干；
(2)蛋白酶K处理织物：将步骤(1)预处理后的羊毛织物或羊毛纤维在含壳寡糖0.5～2g/L、尿素10～50g/L的40～65℃热水中，浴比为20～50:1，浸渍0.5～1h，然后在蛋白酶K溶液中浸渍处理，温度80～95℃，pH 6～10，浴比20～50:1，处理时间2～24h；
(3)灭酶：将蛋白酶K灭活，最后将羊毛织物或羊毛纤维水洗，烘干即可。
在本发明的一种实施方式中，在蛋白酶K溶液中添加0.5～2mmol/L Ca 2+。
在本发明的一种实施方式中，所述步骤(3)中灭酶后羊毛织物或羊毛纤维依次分别以90～100℃的热水和常温冷水水洗1～2次。
在本发明的一种实施方式中，所述灭酶为在蛋白酶K溶液中加入0.5～5.0mol/L的三氯乙 酸使蛋白酶K失活，也可以将蛋白酶K溶液温度升高至80～90℃处理10～30min。
在本发明的一种实施方式中，所述蛋白酶K的加入量为2～32U/g 织物/纤维，优选为2～16U/g 织物/纤维。
在本发明的一种实施方式中，所述蛋白酶K的处理时间优选为2～6h。
在本发明的一种实施方式中，所述羊毛织物包括全毛华达呢、哔叽、凡立丁精纺呢绒织物或全毛华达呢、哔叽、凡立丁粗纺呢绒品种中的任一种。
在本发明的一种实施方式中，有无过氧化脲预处理对羊毛织物或纤维的毡缩性能影响较大，经预处理后的羊毛织物或纤维防毡缩性能得到了更大程度的改善。
本发明还提供了一种羊毛织物防毡缩整理液，所述整理液分为A液、B液和C液，其中，A液为含过氧化脲10～50mL/L、焦磷酸钠1～3g/L和渗透剂JFC 0.5～2g/L的溶液，B液为含壳寡糖0.5～2g/L、尿素10～50g/L的溶液，C液为添加了0.5～2mmol/L Ca 2+的蛋白酶K溶液。
最后，本发明提供了上述羊毛织物防毡缩整理液的使用方法，将羊毛织物或羊毛纤维用80～100℃热水浸渍0.5～1h后取出，再置于A液中，浴比20～50:1，40～70℃下处理时间1～4h；结束后用水冲洗，50～60℃条件下烘干；再置于B液中，浴比为20～50:1，40～65℃下浸渍0.5～1h，之后再80～95℃的C液中处理时间2～24h，浴比为20～50:1，灭酶、水洗、烘干即可。
本发明的优点和效果：
(1)本发明首次将过氧化脲作为羊毛织物或羊毛纤维的预处理手段，可破坏羊毛鳞片表层类脂结构和鳞片部分二硫键，为后续酶处理创造更好条件。同时，与过氧化氢预处理相比，过氧化脲处理过程中分解产生的尿素有助于纤维溶胀，从而更好发挥过氧化脲对类脂和鳞片表面的氧化作用。
(2)本发明针对普通蛋白酶对鳞片角蛋白降解作用较弱的问题，且角蛋白酶处理速度较慢的问题，本发明首次将蛋白酶K引入羊毛防毡缩整理中，蛋白酶K能够同时水解角蛋白和普通蛋白，具有较好创新性。
(3)为了防止蛋白酶K蛋白酶会优先攻击CMC，进而通过细胞间间隙进入纤维内部，破坏纤维强力，本发明先利用壳寡糖与羊毛非角质化的细胞膜复合物CMC(普通蛋白)以离子键和氢键形式预结合，起到一定“封闭CMC”作用，再利用蛋白酶K能有效降解角蛋白的特性对羊毛织物进行防毡缩整理，破坏羊毛鳞片层(CMC因封闭而不易受到酶解作用)，从而获得较好防毡缩效果，同时对羊毛强力损伤较小。
(4)本发明利用过氧化脲进行预处理，再用蛋白酶K进行处理，使羊毛织物或纤维具有防毡缩效果，降低织物水洗毡缩程度，达到可机洗效果，比传统的氯化法更符合现代绿色 生态、健康环保的要求。
具体实施方式
减量率：减量率(％)＝(羊毛处理前的干重-羊毛处理后的干重)/羊毛处理前的干重×100％。
毡缩率：面积收缩率(％)＝(洗涤前面积-洗涤后面积)/洗涤前面积×100％。
强力损失：强力损失(％)＝(未处理羊毛断裂强力-羊毛处理后的断裂强力)/未处理羊毛断裂强力×100％。
蛋白酶K购自上海翊圣生物科技有限公司，产品编号为10401ES80。
实施例1
织物品种：纯毛华达呢织物
(3)过氧化脲预处理织物：将羊毛织物用90℃热水浸渍1h，再置于含过氧化脲30mL/L、焦磷酸钠1.5g/L、渗透剂JFC 1g/L溶液中，浴比35:1，温度50℃，pH 8，处理时间1h。结束后用水反复冲洗，50℃条件下烘干。
(4)蛋白酶K处理织物：将预处理后的羊毛织物首先在含壳寡糖1g/L、尿素20g/L的90℃热水中浸渍1h，然后放入16U/g 织物的蛋白酶K溶液(酶液温度50℃，pH 8，浴比25:1，添加1mmol/L Ca 2+)中浸渍处理6h。
(3)80℃酶灭活10min。结束后依次分别以90℃的热水和常温冷水水洗2次，50℃条件下烘干。
经上述工艺处理后，羊毛织物的毡缩率5.02％，减量率9.0％，强力损失14.1％。
对照样：按照实施例1中步骤(1)预处理织物，再用16U/g 织物的蛋白酶按照步骤(3)的方式处理织物。对照样的毡缩率8.06％，减量率25.9％，强力损失42.70％。
实施例2
织物品种：凡立丁织物
(1)过氧化脲预处理织物：将羊毛织物用90℃热水浸渍1小时，再置于含过氧化脲30mL/L、焦磷酸钠1.5g/L、渗透剂JFC 1g/L溶液中，浴比35:1，温度50℃，pH 8，处理时间1h。结束后用去离子水反复冲洗，50℃条件下烘干。
(2)蛋白酶K处理织物：将预处理后的羊毛织物在含壳寡糖1g/L、尿素20g/L的90℃热水中浸渍1h，放入4U/g 织物的蛋白酶K溶液(酶液温度50℃，pH 8，浴比25:1，添加1mmol/L Ca 2+)中浸渍处理4h。
(3)80℃酶灭活10min。结束后依次分别以90℃的热水和常温冷水水洗2次，50℃条件下烘干。
经上述工艺处理后，羊毛织物的毡缩率5.96％，减量率10.65％，强力损失11.28％。
对照样：按照实施例2中步骤(1)预处理织物，再用4U/g 织物的蛋白酶按照步骤(3)的方式处理织物。对照样的毡缩率7.7％，减量率22.3％，强力损失39.42％。
可见，羊毛织物经蛋白酶K处理后取得了较好防毡缩效果，同时强力损失较普通蛋白酶处理显著降低。
实施例3
织物品种：凡立丁织物
(1)过氧化脲预处理织物：将羊毛织物用90℃热水浸渍1小时，再置于含过氧化脲10mL/L、焦磷酸钠2g/L、渗透剂JFC 2g/L溶液中，浴比50:1，温度70℃，pH 6，处理时间2h。结束后用去离子水反复冲洗，50℃条件下烘干。
(2)蛋白酶K处理织物：将预处理后的羊毛织物在含壳寡糖2g/L、尿素40g/L的90℃热水中浸渍1h，放入25U/g 织物的蛋白酶K溶液(酶液温度65℃，pH 10，浴比20:1，添加2mmol/L Ca 2+)中浸渍处理4h。
(3)80℃酶灭活10min。结束后依次分别以90℃的热水和常温冷水水洗2次，50℃条件下烘干。
经上述工艺处理后，羊毛织物的毡缩率4.92％，减量率12.64，强力损失16.47％。
对比例1
织物品种：凡立丁织物
(1)蛋白酶K处理织物：羊毛织物在含壳寡糖1g/L、尿素20g/L的90℃热水中浸渍1h，放入4U/g织物的蛋白酶K溶液(酶液温度50℃，pH 8，浴比25:1，添加1mmol/L Ca 2+)中浸渍处理4h。
(2)80℃酶灭活10min。结束后依次分别以90℃的热水和常温冷水水洗2次，50℃条件下烘干。
经上述工艺处理后，羊毛织物的毡缩率10.67％，减量率9.8％，强力损失10.2％。羊毛织物不经过过氧化脲预处理的防毡缩效果低于经预处理的羊毛织物的效果，毡缩率偏高。
对比例2
织物品种：凡立丁织物
(1)蛋白酶K处理织物：羊毛织物在90℃的热水中浸渍1h，放入4U/g织物的蛋白酶K溶液(酶液温度50℃，pH 8，浴比25:1，添加1mmol/L Ca 2+)中浸渍处理4h。
(2)80℃酶灭活10min。结束后依次分别以90℃的热水和常温冷水水洗2次，50℃条件下 烘干。
经上述工艺处理后，羊毛织物的毡缩率12.5％，减量率12.1％，强力损失18.32％。对比实施例4可知，蛋白酶K处理时预先用壳寡糖和尿素处理有助于降低毡缩率和强损。
对比例3
织物品种：凡立丁织物
(1)过氧化氢预处理织物：将羊毛织物用90℃热水浸渍1小时，再置于含30％双氧水、焦磷酸钠1.5g/L、渗透剂JFC 1g/L溶液中，浴比35:1，温度50℃，pH 8，处理时间1h。结束后用去离子水反复冲洗，50℃条件下烘干。
(2)蛋白酶K处理织物：将预处理后的羊毛织物在含壳寡糖1g/L、尿素20g/L的90℃热水中浸渍1h，放入4U/g 织物的蛋白酶K溶液(酶液温度50℃，pH 8，浴比25:1，添加1mmol/L Ca2+)中浸渍处理4h。
(3)80℃酶灭活10min。结束后用去离子水反复冲洗，50℃条件下烘干。
经上述工艺处理后，羊毛织物的毡缩率9.21％，减量率10.5％，强力损失19.18％。
与过氧化氢预处理相比，过氧化脲处理过程中分解产生的尿素有助于纤维溶胀，从而更好发挥过氧化脲对类脂和鳞片表面的氧化作用，从而更有利后续的防毡缩处理。
虽然本发明已以较佳实施例公开如上，但其并非用以限定本发明，任何熟悉此技术的人，在不脱离本发明的精神和范围内，都可做各种的改动与修饰，因此本发明的保护范围应该以权利要求书所界定的为准。

Claims (16)

  1. 一种利用蛋白酶K对羊毛织物进行防毡缩整理的方法，其特征在于，所述方法为：用过氧化脲对羊毛织物或羊毛纤维进行预处理，之后利用壳寡糖对细胞膜复合物CMC进行封闭，再用蛋白酶K处理羊毛，水洗即可，其中，所述利用壳寡糖对细胞膜复合物CMC进行封闭即为壳寡糖和细胞膜复合物CMC以离子键和氢键形式结合。
  2. 根据权利要求1所述的一种利用蛋白酶K对羊毛织物进行防毡缩整理的方法，其特征在于，所述方法的具体步骤为：
    (1)过氧化脲预处理织物：将羊毛织物或羊毛纤维用80～100℃热水浸渍0.5～1h后取出，再置于含过氧化脲10～50mL/L、焦磷酸钠1～3g/L和渗透剂JFC 0.5～2g/L的溶液中，浴比为20～50:1，温度为40～70℃，pH5～9，处理时间为1～4h；结束后用水冲洗，50～60℃条件下烘干；
    (2)蛋白酶K处理织物：将步骤(1)预处理后的羊毛织物或羊毛纤维在含壳寡糖0.5～2g/L、尿素10～50g/L的80～95℃热水中，浴比为20～50:1，浸渍0.5～1h，然后在蛋白酶K溶液中浸渍处理，温度为40～65℃，pH6～10，浴比为20～50:1，处理时间为2～24h；
    (3)灭酶：将蛋白酶K灭活，最后将羊毛织物或羊毛纤维进行水洗，烘干即可。
  3. 根据权利要求2所述的一种利用蛋白酶K对羊毛织物进行防毡缩整理的方法，其特征在于，在蛋白酶K溶液中添加0.5～2mmol/L Ca 2+。
  4. 根据权利要求2或3所述的一种利用蛋白酶K对羊毛织物进行防毡缩整理的方法，其特征在于，所述步骤(3)中所述水洗为将灭酶后的羊毛织物或羊毛纤维依次分别用90～100℃热水和常温冷水水洗1～2次。
  5. 根据权利要求2或3任一所述的一种利用蛋白酶K对羊毛织物进行防毡缩整理的方法，其特征在于，所述蛋白酶K的加入量为2～32U/g 织物/纤维。
  6. 根据权利要求4所述的一种利用蛋白酶K对羊毛织物进行防毡缩整理的方法，其特征在于，所述蛋白酶K的加入量为2～32U/g 织物/纤维。
  7. 根据权利要求1～3或6任一所述的一种利用蛋白酶K对羊毛织物进行防毡缩整理的方法，其特征在于，所述羊毛织物包括全毛华达呢、哔叽、凡立丁精纺呢绒织物或全毛华达呢、哔叽、凡立丁粗纺呢绒中的任一种。
  8. 根据权利要求4所述的一种利用蛋白酶K对羊毛织物进行防毡缩整理的方法，其特征在于，所述羊毛织物包括全毛华达呢、哔叽、凡立丁精纺呢绒织物或全毛华达呢、哔叽、凡立丁粗纺呢绒中的任一种。
  9. 根据权利要求5所述的一种利用蛋白酶K对羊毛织物进行防毡缩整理的方法，其特征在于，所述羊毛织物包括全毛华达呢、哔叽、凡立丁精纺呢绒织物或全毛华达呢、哔叽、 凡立丁粗纺呢绒中的任一种。
  10. 根据权利要求2所述的一种利用蛋白酶K对羊毛织物进行防毡缩整理的方法，其特征在于，所述方法的具体步骤为：
    织物品种：纯毛华达呢织物；
    (1)过氧化脲预处理织物：将羊毛织物用90℃热水浸渍1h，再置于含过氧化脲30mL/L、焦磷酸钠1.5g/L、渗透剂JFC 1g/L溶液中，浴比35:1，温度50℃，pH8，处理时间1h，结束后用水反复冲洗，50℃条件下烘干；
    (2)蛋白酶K处理织物：将预处理后的羊毛织物首先在含壳寡糖1g/L、尿素20g/L的90℃热水中浸渍1h，然后放入16U/g 织物的蛋白酶K溶液，酶液温度50℃，pH8，浴比25:1，添加1mmol/L Ca 2+，中浸渍处理6h；
    (3)80℃酶灭活10min，结束后依次分别以90℃的热水和常温冷水水洗2次，50℃条件下烘干。
  11. 根据权利要求2所述的一种利用蛋白酶K对羊毛织物进行防毡缩整理的方法，其特征在于，所述方法的具体步骤为：
    织物品种：凡立丁织物；
    (1)过氧化脲预处理织物：将羊毛织物用90℃热水浸渍1小时，再置于含过氧化脲30mL/L、焦磷酸钠1.5g/L、渗透剂JFC 1g/L溶液中，浴比35:1，温度50℃，pH8，处理时间1h，结束后用去离子水反复冲洗，50℃条件下烘干；
    (2)蛋白酶K处理织物：将预处理后的羊毛织物在含壳寡糖1g/L、尿素20g/L的90℃热水中浸渍1h，放入4U/g 织物的蛋白酶K溶液，酶液温度50℃，pH8，浴比25:1，添加1mmol/L Ca 2+，中浸渍处理4h；
    (3)80℃酶灭活10min，结束后依次分别以90℃的热水和常温冷水水洗2次，50℃条件下烘干。
  12. 根据权利要求2所述的一种利用蛋白酶K对羊毛织物进行防毡缩整理的方法，其特征在于，所述方法的具体步骤为：
    织物品种：凡立丁织物
    (1)过氧化脲预处理织物：将羊毛织物用90℃热水浸渍1小时，再置于含过氧化脲10mL/L、焦磷酸钠2g/L、渗透剂JFC 2g/L溶液中，浴比50:1，温度70℃，pH6，处理时间2h，结束后用去离子水反复冲洗，50℃条件下烘干；
    (2)蛋白酶K处理织物：将预处理后的羊毛织物在含壳寡糖2g/L、尿素40g/L的90℃热水中浸渍1h，放入25U/g 织物的蛋白酶K溶液，酶液温度65℃，pH10，浴比20:1，添加2mmol/L  Ca 2+，中浸渍处理4h；
    (3)80℃酶灭活10min，结束后依次分别以90℃的热水和常温冷水水洗2次，50℃条件下烘干。
  13. 权利要求1～12任一所述一种利用蛋白酶K对羊毛织物进行防毡缩整理的方法整理得到的羊毛织物或羊毛纤维。
  14. 包含权利要求13所述的羊毛织物或羊毛纤维的衣物。
  15. 一种羊毛织物防毡缩整理液，其特征在于，所述整理液分为A液、B液和C液，其中，A液为含过氧化脲10～50mL/L、焦磷酸钠1～3g/L和渗透剂JFC 0.5～2g/L的溶液，B液为含壳寡糖0.5～2g/L、尿素10～50g/L的溶液，C液为添加了0.5～2mmol/L Ca 2+的蛋白酶K溶液。
  16. 一种权利要求15所述的羊毛织物防毡缩整理液的使用方法，其特征在于，将羊毛织物或羊毛纤维用80～100℃热水浸渍0.5～1h后取出，再置于A液中，浴比20～50:1，40～70℃下处理时间1～4h；结束后用水冲洗，50～60℃条件下烘干；再置于B液中，浴比为20～50:1，80～95℃下浸渍0.5～1h，之后再40～65℃的C液中处理时间2～24h，浴比为20～50:1，灭酶、水洗、烘干即可。
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