CN114369957B - Protease-based wool fabric intermittent functional finishing method and equipment - Google Patents
Protease-based wool fabric intermittent functional finishing method and equipment Download PDFInfo
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- 239000004744 fabric Substances 0.000 title claims abstract description 161
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- 239000004365 Protease Substances 0.000 title claims abstract description 50
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000003814 drug Substances 0.000 claims abstract description 43
- 238000005406 washing Methods 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 102000004190 Enzymes Human genes 0.000 claims abstract description 20
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000012530 fluid Substances 0.000 claims abstract description 11
- 238000012544 monitoring process Methods 0.000 claims abstract description 11
- 230000002779 inactivation Effects 0.000 claims abstract description 7
- 238000009736 wetting Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 35
- 239000000835 fiber Substances 0.000 claims description 33
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 230000000149 penetrating effect Effects 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- 238000007865 diluting Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
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- 239000011229 interlayer Substances 0.000 claims description 8
- 238000012806 monitoring device Methods 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
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- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 5
- 239000003085 diluting agent Substances 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- YICAEXQYKBMDNH-UHFFFAOYSA-N 3-[bis(3-hydroxypropyl)phosphanyl]propan-1-ol Chemical compound OCCCP(CCCO)CCCO YICAEXQYKBMDNH-UHFFFAOYSA-N 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- PZBFGYYEXUXCOF-UHFFFAOYSA-N TCEP Chemical compound OC(=O)CCP(CCC(O)=O)CCC(O)=O PZBFGYYEXUXCOF-UHFFFAOYSA-N 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- VHJLVAABSRFDPM-QWWZWVQMSA-N dithiothreitol Chemical compound SC[C@@H](O)[C@H](O)CS VHJLVAABSRFDPM-QWWZWVQMSA-N 0.000 claims description 3
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- 238000009940 knitting Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- 230000037303 wrinkles Effects 0.000 claims description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 3
- 108091005508 Acid proteases Proteins 0.000 claims description 2
- 108090000145 Bacillolysin Proteins 0.000 claims description 2
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- 125000000129 anionic group Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
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- 208000003251 Pruritus Diseases 0.000 abstract description 17
- 230000007803 itching Effects 0.000 abstract description 16
- 239000000675 fabric finishing Substances 0.000 abstract description 6
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- 238000012545 processing Methods 0.000 abstract description 3
- 235000019419 proteases Nutrition 0.000 description 40
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- 206010003549 asthenia Diseases 0.000 description 4
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- 102000004169 proteins and genes Human genes 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 108010067770 Endopeptidase K Proteins 0.000 description 2
- 102000018697 Membrane Proteins Human genes 0.000 description 2
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- 238000010586 diagram Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- 238000011160 research Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 102000006395 Globulins Human genes 0.000 description 1
- 108010044091 Globulins Proteins 0.000 description 1
- 101710180012 Protease 7 Proteins 0.000 description 1
- 102000019307 Sclerostin Human genes 0.000 description 1
- 108050006698 Sclerostin Proteins 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000021120 animal protein Nutrition 0.000 description 1
- 238000010006 anti-felting Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229940078916 carbamide peroxide Drugs 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- RQFQJYYMBWVMQG-IXDPLRRUSA-N chitotriose Chemical compound O[C@@H]1[C@@H](N)[C@H](O)O[C@H](CO)[C@H]1O[C@H]1[C@H](N)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)N)[C@@H](CO)O1 RQFQJYYMBWVMQG-IXDPLRRUSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 210000004209 hair Anatomy 0.000 description 1
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- 238000009776 industrial production Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
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- 230000035699 permeability Effects 0.000 description 1
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- 108010056599 proteinase C Proteins 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical compound [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
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- 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
- D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
- D06B23/00—Component parts, details, or accessories of apparatus or machines, specially adapted for the treating of textile materials, not restricted to a particular kind of apparatus, provided for in groups D06B1/00 - D06B21/00
- D06B23/04—Carriers or supports for textile materials to be treated
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
- D06B23/00—Component parts, details, or accessories of apparatus or machines, specially adapted for the treating of textile materials, not restricted to a particular kind of apparatus, provided for in groups D06B1/00 - D06B21/00
- D06B23/20—Arrangements of apparatus for treating processing-liquids, -gases or -vapours, e.g. purification, filtration or distillation
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
- D06B23/00—Component parts, details, or accessories of apparatus or machines, specially adapted for the treating of textile materials, not restricted to a particular kind of apparatus, provided for in groups D06B1/00 - D06B21/00
- D06B23/20—Arrangements of apparatus for treating processing-liquids, -gases or -vapours, e.g. purification, filtration or distillation
- D06B23/22—Arrangements of apparatus for treating processing-liquids, -gases or -vapours, e.g. purification, filtration or distillation for heating
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- 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
- D06M11/51—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 sulfur, selenium, tellurium, polonium or compounds thereof
- D06M11/54—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 sulfur, selenium, tellurium, polonium or compounds thereof with sulfur dioxide; with sulfurous acid or its salts
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- 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
- D06M13/244—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 sulfur or phosphorus
- D06M13/248—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 sulfur or phosphorus with compounds containing sulfur
- D06M13/252—Mercaptans, thiophenols, sulfides or polysulfides, e.g. mercapto acetic acid; Sulfonium compounds
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- 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
- D06M13/244—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 sulfur or phosphorus
- D06M13/282—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 sulfur or phosphorus with compounds containing phosphorus
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- 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
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/35—Abrasion, pilling or fibrillation resistance
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/45—Shrinking resistance, anti-felting properties
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- 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
- D06M2200/50—Modified hand or grip properties; Softening compositions
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
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- General Chemical & Material Sciences (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The intermittent functional wool fabric finishing method based on protease comprises the steps of wool fabric wetting, normal temperature feeding, heating reaction, water washing, enzyme inactivation and water washing again; the finishing equipment comprises a tank body, a heating and heat preserving system, a medicament circulating system and a treatment fluid monitoring system. The wool fabric shrink-proof, fuzzing and pilling resistant and hand feeling good performances can be endowed by the finishing method and the equipment, the fuzzing and pilling resistant performance of the treated fabric can be improved by 1-2 levels, the washing shrinkage index can meet the requirement of machine washability, the itching feeling can be obviously reduced, and the problem that the existing industrial wool fabric shrink-proof, fuzzing and pilling resistant and itching feeling finishing needs multiple steps of processing is solved.
Description
Technical Field
The invention relates to the technical field of wool fabric finishing, in particular to a protease-based wool fabric intermittent functional finishing method and equipment.
Background
The wool fiber is animal protein fiber, and the wool fiber product has the excellent characteristics of soft luster, plump hand feeling, high elasticity, good drapability and the like, belongs to high-grade textiles, and is deeply favored by consumers at home and abroad. However, due to the special scale layer structure of the wool fibers, the wool fabric is easy to shrink, fuzzing and pilling and easy to produce itching feeling after washing, so that the shrink-proof, fuzzing and pilling-resistant and other characteristics of the wool fabric can be improved by partially stripping the scale layer or performing covering modification on the scale layer. At present, the chlorination process is generally adopted in industry to carry out oxidative stripping finishing on wool scales so as to improve the shrink-proof performance of wool fabrics, and the chlorination process can only improve the shrink-proof performance, but has less improvement on fuzzing and pilling resistance, itching feeling and the like; for anti-pilling finishing, a covering auxiliary agent is generally used for covering wool scales, a layer of continuous film is spread on the wool surfaces by using the covering agent, and the wool scale structure is covered, so that the fiber surfaces are flattened, the directional friction effect on the wool surfaces is reduced, the mutual meshing among the fiber scales is prevented, the anti-pilling performance and the like of the wool fabric are improved, and the itching feeling is reduced. However, the adsorbable organic halide (AOX) produced during the production process of the chlorination process causes serious environmental pollution, and the fabric feel is roughened or hard by adopting a covering method for finishing, so that the wearability of the product is affected, and the covering method is often not resistant to water washing. For itching, softening agents and the like are generally added to reduce itching of fabrics and improve comfort, but the improvement mode is short and not durable. The shrink-proof finishing, fuzzing and pilling resistant finishing and itching feeling finishing are needed to be performed in multiple steps by adopting different methods, and the industrial process has not yet been available for solving the problems at the same time.
As is well known, the protease finishing technology is always a research hot spot of the green dyeing and finishing processing technology in the textile industry with the characteristics of mild conditions and easily degradable waste liquid. Wool is protein fiber, and the wool shrink-proof and fuzzing and pilling resistant performances are necessarily improved by adopting protease to partially degrade the scale tissue. However, wool fiber flake layers are complex protein mixtures and belong to hard keratin, researches show that the hydrolysis rate of protease on wool keratin is far lower than that on common globulin, the protease is difficult to hydrolyze the flake surface layers of wool, and no specific protease variety capable of efficiently degrading the wool keratin is found at present. The main reason is that the wool flake layer contains a large amount of disulfide bonds, and the existence of the disulfide bonds prevents the contact and reaction of macromolecular protease and peptide bonds on wool protein molecular chain segments, so that the wool fiber has extremely strong enzymolysis resistance, and the effect of the protease on the wool fiber is extremely low or even no effect.
Therefore, the traditional protease finishing technology is often combined with oxidation/reduction pretreatment to hydrolyze the wool flake layer to a certain extent, even so, the treatment time is still tens of hours, the efficiency is extremely low, industrialization cannot be realized, in addition, in the long-time enzyme treatment process, protease diffuses into the fiber along the flake root, and the cell membrane composite structure with lower disulfide bond content in the fiber is preferentially hydrolyzed, so that the mechanical property of the treated fiber is deteriorated. The method for carrying out anti-felting finishing on the wool fabric by using proteinase K according to the patent publication No. CN109972390A comprises the steps of firstly carrying out soaking treatment for 0.5-1 hour by using hot water, then carrying out pretreatment for 1-4 hours by using carbamide peroxide, then carrying out pretreatment for 0.5-1 hour by using chitosan oligosaccharide to seal CMC, and then carrying out treatment for 2-24 hours by using proteinase K, wherein the treated fabric achieves a better treatment effect. However, the treatment process is complex, the treatment time is long, the strength loss of the fabric is large, and the industrial application is not realized.
Also disclosed are a continuous processing technology for chlorine-free wool tops and shrink-proof treatment of wool products, such as patent application number CN201510078177.8, and a chlorine-free shrink-proof treatment technology and equipment for wool raw materials and products, such as patent application number CN201610086083.X, wherein a continuous wool biological enzyme method shrink-proof treatment technology is disclosed, the method has high reaction efficiency and high treatment speed, the treatment time is only 1-2 minutes, but when the method is used for treating fabrics, the fabrics are very easy to treat unevenly because of compact fiber structures, dyeing of white-blank fabrics is very easy to dye flowers after the treatment, the color fabrics are very easy to generate stripes and spots after the treatment, in addition, the fabric is relatively compact in structure, the phenomenon of treatment imperviousness, namely the inconsistent treatment degree of surface fibers and inner fibers, the good treatment degree of surface fibers and the poor treatment degree of inner fibers, so that the overall treatment effect of the fabrics is poor, and the requirements of shrink prevention, fuzzing and pilling resistance and the like are difficult to be achieved. The requirements of industrial production on uniformity and stability cannot be met, and therefore, the continuous rapid enzyme treatment cannot be applied to industrial finishing of the wool fabric. The continuous treatment is also a belt tension treatment and is not suitable for wool knitting products.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a protease-based wool fabric intermittent functional finishing method and equipment, which can endow wool fabrics with shrink-proof, fuzzing and pilling-resistant and good hand feeling properties, the fuzzing and pilling resistance of the treated fabrics can be improved by 1-2 levels, the washing shrinkage index can meet the machine washability requirement, and the itching feeling can be obviously reduced.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a protease-based wool fabric intermittent functional finishing method comprises the following steps:
s1, wool fabric wetting: introducing the wool fabric to be treated into equipment according to the ratio of 1:8-1: adding normal-temperature clean water into the bath ratio of 20, adding penetrating agent 0.1-3% owf, controlling the pH value to be 6.5-7.5, and operating the fabric in a circulating mode for 5 minutes to fully wet the fabric;
s2, charging at normal temperature: mixing 0.1-5.0% owf of protease, 0.1-3.0% owf of disulfide bond reducer and 0.1-2% owf of penetrant, fully diluting, fully and uniformly mixing the diluted solution to form medicament mixed diluted solution, slowly and uniformly adding the medicament mixed diluted solution within 10-30 minutes under the conditions that the temperature is lower than 30 ℃, the pH value is controlled to be 6-8 and the fabric is circularly operated, and circularly operating the fabric for 10-30 minutes under the low temperature condition after the medicament addition is completed, so that the medicament is fully and uniformly dispersed;
s3, heating reaction: under the condition of the cyclic operation of the fabric, the temperature of the treatment fluid is raised to 25-50 ℃ at the heating rate of 0.1-1 ℃ per minute, and the temperature is kept for 20-120 minutes, so that the medicament reacts with wool, the surface scales of the wool fiber are modified, the scale tissue is partially softened and stripped, and then the treatment fluid is emptied;
s4, washing: adding clear water, washing for 5-15 minutes at normal temperature under the condition of circularly running the fabric, and then evacuating;
s5, enzyme inactivation: adding 1-3% owf of acetic acid, diluting, adding and rapidly heating to 75 ℃, pickling for 5-20 minutes under the condition of circularly running the fabric, inactivating residual protease on the fabric, and then evacuating the treatment liquid;
s6, washing: adding clear water, washing for 5-15 minutes at normal temperature under the condition of circulating operation of the fabric, then emptying, and finishing the treatment after cloth discharging.
Aiming at the problem of poor treatment uniformity of a protease method, the finishing method provided by the invention has the advantages of long-time slow feeding through the bottom temperature, low medicament concentration and low-speed uniform temperature rise. Because protease does not react at low temperature, the reagent is uniformly adsorbed on the fabric by slow feeding at bottom temperature for a long time, the uneven treatment caused by high-temperature feeding is avoided, the protease gradually reacts with wool flakes by low-speed uniform temperature rise, the uneven treatment caused by efficient instant reaction of the enzyme and wool is avoided, the target temperature is controlled at a lower value of 25-50 ℃, the reaction efficiency of the enzyme is reduced, and the enzyme is uniformly reacted.
Preferably, the pH controlling agent is acetic acid or sodium bicarbonate diluent.
Preferably, the treatment liquid in the device is circulated into and out of the device, and the circulation amount is adjusted to be 5 m/min 3 ～50m 3 . The function is to make the medicine in each part of the equipment uniform, and the circulation quantity of the medicine can be calculated and adjusted according to the thickness of the fabric.
Preferably, in the step S5, the enzyme may be inactivated by adding 0.5-3% owf of hydrogen peroxide, diluting and then adding the diluted solution, washing the fabric with water at normal temperature for 5-15 minutes under the condition of circulating operation of the fabric, inactivating the protease remained on the fabric, and then evacuating the treatment solution.
Preferably, the protease may be an acid protease, a neutral protease or an alkaline protease, and may be one enzyme or a combination of a plurality of enzymes.
Preferably, the disulfide bond reducing agent is one or more of dithiothreitol, mercaptoethanol, sodium bisulphite, tris (2-carboxyethyl) phosphine, tris (3-hydroxypropyl) phosphine.
Preferably, the penetrant may be a nonionic, anionic or a complex penetrant, for example: permeate JFC-1 and permeate FFA.
Preferably, the wool fabric is a pure wool fabric or a wool-containing blended fabric, and the weave form of the fabric can be knitting or weaving.
The intermittent functional wool fabric finishing equipment includes one circular arc tank with water draining pipe in the bottom, one guide roller set with driving rollers, and one heating and heat insulating system. The tank body is provided with an interlayer, and the heating and heat preservation system comprises a hot water tank, a water inlet pipe and a water outlet pipe which are communicated with the interlayer and provided with a circulating pump. The guide roller group with the driving roller provides the running power of the fabric, the fabric rises from one side of the tank body and descends from the other side, the fabric circularly moves in the tank body in an annular open width in the treatment process, and the circular arc-shaped tank body is beneficial to the uniform stacking of the fabric at the bottom of the tank body. The interlayer intermittent heating mode is adopted, the problem that enzyme inactivation is caused by high-temperature direct heating is solved, hot water in the hot water tank is output and input through the water inlet pipe and the water outlet pipe, and the temperature can be regulated and controlled according to requirements.
Preferably, the upper part of the tank body is provided with a cloth folding device, and the fabric is folded to be stacked uniformly in an open width at the bottom of the tank body. The cloth folding device is positioned at one side of the fabric which descends into the treatment fluid and can realize folding in a reciprocating swinging mode.
Preferably, an expanding roller is arranged between the guide rollers, the fabric is expanded and wrinkles are removed, and the expanding roller is a driving roller.
Preferably, the device is also provided with a medicament circulating system, wherein the medicament circulating system comprises a plurality of liquid outlet branch pipes and liquid inlet branch pipes which are respectively positioned at two sides of the tank body, and the liquid outlet branch pipes and the liquid inlet branch pipes are respectively connected with a circulating main pipe with a circulating pump. The medicine is pumped from one side of the tank body through the circulating pump and then pumped from the other side of the tank body, so that medicines at all parts in the tank body are uniform, and a plurality of inlets and outlets are arranged on the tank body for the purpose of medicine circulation uniformity.
Preferably, the tank body is provided with a monitoring device A for temperature monitoring, pH monitoring, water level monitoring and medicament concentration monitoring of the treatment fluid, and the hot water tank is provided with a monitoring device B for temperature monitoring and water level monitoring. Wherein, the temperature is automatically regulated and controlled by a heating and heat preserving system.
The invention has the beneficial effects that: (1) The method and the equipment provided by the invention can be used for treating the wool fabric, so that the comprehensive performance of the treated wool fabric is greatly improved, the properties of shrink resistance, fuzzing and pilling resistance, good hand feeling, moisture absorption and permeability enhancement and the like are given to the wool fabric at one time, the fuzzing and pilling resistance of the treated fabric can be improved by 1-2 levels, the washing shrinkage index can meet the requirement of machine washability, and the itching feeling can be obviously reduced;
(2) The method and the equipment adopt the chemical agents with low concentration, low bottom temperature for long time and low temperature rise, and are matched with the relaxation type open width finishing equipment, so that the production procedures are reduced, the production efficiency and the product quality are improved, the production cost is reduced, the problems that the existing industrial wool fabric shrink-proof, fuzzing-resistant and itching-feeling finishing needs multiple processes and steps to be treated are solved, the existing protease wool fabric finishing procedure is complex, the treatment uniformity is poor and the like, and the industrial application of the protease wool fabric finishing is hindered, and the industrial application of the protease wool fabric is realized;
(3) Thoroughly solves the problem of AOX release with high pollution and high toxicity in the shrink-proof process of the wool fabric in the prior industry, protects the ecological environment, has small pollution in the treatment process, low cost, uniform and stable treatment and has great economic and social values.
Drawings
FIG. 1 is a schematic diagram of the reaction of a disulfide bond reducing agent in the present invention;
FIG. 2 is a schematic view of the arrangement of the finishing apparatus of the present invention;
FIG. 3 is a schematic diagram of the circulation system of the traditional Chinese medicine preparation.
The main reference symbols in the drawings indicate: 1. a tank body; 1.1, an interlayer; 2. a drain pipe; 3. a guide roller; 4. a hot water tank; 5. a circulation pump; 6. a water inlet pipe; 7. a water outlet pipe; 8. a cloth folding device; 9. a spreader bar; 10. a liquid outlet branch pipe; 11. a liquid inlet branch pipe; 12. a circulation header pipe; 13. a monitoring device A; 14. a monitoring device B; 100. a fabric.
Detailed Description
The invention is further illustrated by the following detailed description.
Aiming at the problem of poor treatment uniformity of the protease method, the invention solves the problem of poor treatment uniformity of the wool fabric by the rapid protease method and the neck clamping problem which cannot be industrialized by slowly feeding at bottom temperature for a long time, low medicament concentration, low-speed and uniform temperature rising and matching with loose open width finishing equipment. Because the protease does not react at low temperature, the medicament is uniformly adsorbed on the fabric by slowly feeding the protease at the bottom temperature for a long time, so that uneven treatment caused by high-temperature feeding is avoided; the protease gradually reacts with wool scales through low-speed uniform temperature rise, so that uneven treatment caused by efficient instantaneous reaction of the protease and wool is avoided. The target temperature is controlled to be 25-50 ℃ lower, the reaction efficiency of the enzyme is reduced, and the enzyme is enabled to react uniformly. The circulation of the liquid medicine is increased, and macromolecular protease permeates and shifts on the surface of the fabric fiber, so that the phenomenon that the protease macromolecules act on the adsorption points for a long time to cause weak nodes of the fiber and influence the treatment uniformity and strength is avoided.
The process principle of the treatment fluid is as follows: the wool fabric finishing treatment fluid comprises protease, disulfide bond reducing agent and penetrating agent, wherein the penetrating agent can promote fabric wetting, and the disulfide bond reducing agent can quickly break disulfide bonds in the scale layer, so that the scale layer sclerostin is converted into common protein, and the protease shows high efficiency of enzyme reaction on hair fiber hydrolysis as shown in figure 1.
Principle of improving shrink resistance of treated fabric: the wool fiber scales are partially hydrolyzed and stripped, so that the directional friction effect on the wool surface is reduced, and the shrink-proof performance is improved.
Principle of improving anti-pilling performance: disulfide bonds are opened to generate sulfhydryl (-SH) in the fabric treatment process, and the nearby sulfhydryl can be oxidized to regenerate disulfide bonds (-S-S-) in the fabric after treatment and drying processes, so that the spiral crimp of the fibers in the yarns is shaped, the fibers are kept in a stable spiral shape, and the fibers are not easy to release out of the surface of the fabric, thereby improving the fuzzing and pilling resistance.
The principle of improving itching feeling: (a) The treated scales are partially stripped, the scales are thinned, and sharp corners of the scales are weakened; (b) The disulfide bond of the surface protein chain segment is opened, the hard keratin is transformed into soft, the tissue structure of the surface protein of the fabric is soft, and the itching feeling is reduced; (c) As the wool fiber scale layer is stripped, the activity space of the fiber root is increased, so that the fiber is easy to bend and the itching feeling is reduced.
Specifically, in the first embodiment of the finishing method of the present invention: a protease-based wool fabric intermittent functional finishing method adopts pure wool knitted fabric as raw materials, and comprises the following steps:
s1, wool fabric wetting: the wool fabric to be treated is introduced into the apparatus according to a ratio of 1: adding normal-temperature clean water into the bath ratio of 20, adding 1% owf of penetrating agent, controlling the pH value to be 6.5-7.5, and running the fabric in a circulating mode for 5 minutes to fully wet the fabric.
S2, charging at normal temperature: the preparation method comprises the steps of mixing 3.0% owf of protease A, 0.5% owf of tris (3-hydroxypropyl) phosphine and 0.3% owf of penetrating agent, fully diluting, fully mixing the diluted solution uniformly to form medicament mixed diluted solution, slowly and uniformly adding the medicament mixed diluted solution within 20 minutes under the conditions that the temperature is lower than 30 ℃ and the pH value is controlled to be 6-8 and the fabric circularly operates at 10 meters per minute, and circularly operating the fabric for 20 minutes under the low-temperature condition after the medicament addition is completed, so that the medicament is fully and uniformly dispersed. Wherein the pH regulator is acetic acid and sodium bicarbonate diluent.
S3, heating reaction: under the condition of circularly running the fabric, the temperature of the treatment liquid is raised to 40 ℃ at the heating rate of 1 ℃ per minute, the temperature is kept for 40 minutes, the chemical reacts with wool, the surface scales of the wool fibers are modified, the scale tissues are partially softened and stripped, and then the treatment liquid is emptied.
S4, washing: adding clear water, washing for 5 minutes at normal temperature under the condition of circularly running the fabric, and then emptying.
S5, enzyme inactivation: adding 2% owf of hydrogen peroxide, washing for 5 minutes at normal temperature under the condition of circularly running the fabric, inactivating the residual protease on the fabric, and then evacuating the treatment liquid.
S6, washing: adding clear water, washing for 5 minutes at normal temperature under the condition of circularly running the fabric, then emptying, and finishing the treatment after the fabric is discharged.
The treated fabric can meet the requirement of 'machine washability' of TM 31X 5A, the shrinkage is 1.65%, the fuzzing and pilling resistance is improved by 1.5 level, the itching feeling is obviously reduced, and the strength loss of the fabric is 5.6%.
Embodiment two of the finishing method of the invention: a protease-based wool fabric intermittent functional finishing method adopts pure wool woven fabric as raw materials, and comprises the following steps:
s1, wool fabric wetting: the wool fabric to be treated is introduced into the apparatus according to a ratio of 1: adding normal-temperature clean water into the bath ratio of 20, adding 1% owf of penetrating agent FFA, controlling the pH value to be 6.5-7.5, and running the fabric in a circulating mode for 5 minutes to fully wet the fabric.
S2, charging at normal temperature: the preparation method comprises the steps of mixing 3.0% of owf of protease B, 0.5% of dithiothreitol, 0.2% of owf of tris (3-hydroxypropyl) phosphine and 0.3% of owf of penetrating agent FFA, fully diluting, fully and uniformly mixing the diluted solution to form medicament mixed diluted solution, slowly and uniformly adding the medicament mixed diluted solution within 10 minutes under the conditions that the temperature is lower than 30 ℃ and the pH value is controlled to be 6-8 and the fabric circularly operates at 20 meters per minute, and circularly operating the fabric for 10 minutes under the low temperature condition after the medicament addition is completed, so that the medicament is fully and uniformly dispersed. Wherein the pH regulator is acetic acid and sodium bicarbonate diluent.
S3, heating reaction: under the condition of the circulation operation of the fabric, the temperature of the treatment liquid is raised to 35 ℃ at the temperature rising rate of 0.1 ℃ per minute, the treatment liquid is kept for 100 minutes, the chemical reacts with wool, scales on the surface of the wool fiber are modified, the scales are partially softened and stripped, and then the treatment liquid is emptied.
S4, washing: adding clear water, washing for 5 minutes at normal temperature under the condition of circularly running the fabric, and then emptying.
S5, enzyme inactivation: adding 2% owf of acetic acid, diluting, adding and quickly heating to 75 ℃, pickling for 5-20 minutes under the condition of circularly running the fabric, inactivating residual protease on the fabric, and then evacuating the treatment liquid.
S6, washing: adding clear water, washing for 5 minutes at normal temperature under the condition of circularly running the fabric, then emptying, and finishing the treatment after the fabric is discharged.
The treated fabric can meet the requirement of 'machine washability' of TM 31X 5A, the shrinkage is 1.25%, the fuzzing and pilling resistance is improved by 2 levels, the itching feeling is obviously reduced, and the strength loss of the fabric is 4.9%.
Embodiment III of the finishing method of the invention: a protease-based wool fabric intermittent functional finishing method comprises the following steps of:
s1, fabric wetting: the fabric to be treated is introduced into the apparatus according to a ratio of 1: adding normal-temperature clean water into the fabric according to the bath ratio of 10, adding penetrating agent JFC-1% owf, controlling the pH value to be 6.5-7.5, and running the fabric in a circulating mode for 5 minutes to fully wet the fabric.
S2, charging at normal temperature: the preparation method comprises the steps of mixing 4.0% of compound proteinase C, 0.2% of mercaptoethanol, 0.1% of sodium bisulphite, 0.1% of tris (2-carboxyethyl) phosphine and 10.3% of penetrating agent JFC-10.3% of owf, fully diluting, fully and uniformly mixing the diluted solution to form medicament mixed diluted solution, slowly and uniformly adding the medicament mixed diluted solution within 20 minutes under the conditions that the temperature is lower than 30 ℃ and the pH value is controlled to be 6-8 and the fabric circularly operates at 25 meters per minute, and circularly operating the fabric for 15 minutes under the low-temperature condition after the medicament addition is completed, so that the medicament is fully and uniformly dispersed. Wherein the pH regulator is acetic acid and sodium bicarbonate diluent.
S3, heating reaction: the temperature of the treatment liquid is raised to 38 ℃ at a heating rate of 0.5 ℃ per minute under the condition of the cyclic operation of the fabric, the treatment liquid is kept for 80 minutes, the chemical reacts with wool, scales on the surface of the wool fiber are modified, the scales are partially softened and stripped, and then the treatment liquid is emptied.
S4, washing: adding clear water, washing for 5 minutes at normal temperature under the condition of circularly running the fabric, and then emptying.
S5, enzyme inactivation: adding 2% owf of acetic acid, diluting, adding and quickly heating to 75 ℃, pickling for 5-20 minutes under the condition of circularly running the fabric, inactivating residual protease on the fabric, and then evacuating the treatment liquid.
S6, washing: adding clear water, washing for 5 minutes at normal temperature under the condition of circularly running the fabric, then emptying, and finishing the treatment after the fabric is discharged.
The treated fabric can meet the requirement of 'machine washability' of TM 31X 5A, the shrinkage is 0.75%, the fuzzing and pilling resistance is improved by 1.5 level, the itching feeling is obviously reduced, and the strength loss of the fabric is 6.3%.
Embodiment one of the finishing apparatus of the present invention: as shown in figure 2, the wool fabric intermittent functional finishing equipment comprises a tank body 1 and a heating and heat-insulating system, wherein the tank body 1 is arc-shaped, a drain pipe 2 is arranged at the bottom, a certain number of guide rollers 3 are arranged at the upper part, at least the guide rollers 3 at the two most sides are guide roller groups with driving rollers, the fabric 100 circularly runs between the guide rollers 3 and the tank body 1 in an annular open width, and the running linear speed of the fabric is adjustable (5-100 m/min). The tank body 1 is provided with an interlayer 1.1, and the heating and heat preservation system comprises a hot water tank 4, a water inlet pipe 6 and a water outlet pipe 7 which are communicated with the interlayer 1.1 and provided with a circulating pump 5.
Wherein, the upper part of the tank body 1 is provided with a cloth folding device 8, and the fabric 100 is folded to be piled up evenly in an open width at the bottom of the tank body 1. An expanding roller 9 is arranged between the guide rollers 3 to expand the width of the fabric 100 and remove wrinkles.
Embodiment two of the finishing device of the invention: as shown in fig. 3, on the basis of the first embodiment of the finishing apparatus, a medicine circulation system is further provided, the medicine circulation system includes a plurality of liquid outlet branch pipes 10 and liquid inlet branch pipes 11 respectively located at two sides of the tank body 1, and the liquid outlet branch pipes 10 and the liquid inlet branch pipes 11 are respectively connected with a circulation main pipe 12 with the circulation pump 5. The treatment liquid in the tank body 1 enters and exits the equipment in a circulating way, so that the medicines at all parts in the tank body 1 are filledThe agent is uniform, and a plurality of inlets and outlets are arranged on the tank body 1 to connect the liquid outlet branch pipe 10 and the liquid inlet branch pipe 11 for the uniformity of agent circulation. The circulation amount of the medicament can be adjusted according to the thickness of the fabric, and the adjustment range of the circulation amount is 5m per minute 3 ～50m 3 . In addition, the direction of circulation can also be adjusted.
In the embodiment of the two finishing devices, the tank body 1 is provided with a monitoring device A13 for monitoring the temperature, the pH, the water level and the concentration of the treatment liquid, and the hot water tank 4 is provided with a monitoring device B14 for monitoring the temperature and the water level.
The above embodiments are merely examples of the present invention, but the present invention is not limited thereto, and the present invention may be applied to similar products, and any person skilled in the art who is skilled in the field of the present invention shall make changes or modifications within the scope of the present invention.
Claims (9)
1. The intermittent functional finishing method of the wool fabric based on the protease is characterized by comprising the following steps of:
s1, wool fabric wetting: introducing the wool fabric to be treated into equipment according to the ratio of 1:8-1: adding normal-temperature clean water into the bath ratio of 20, adding penetrating agent 0.1-3% owf, controlling the pH value to be 6.5-7.5, and operating the fabric in a circulating mode for 5 minutes to fully wet the fabric;
s2, charging at normal temperature: mixing 0.1-5.0% owf of protease, 0.1-3.0% owf of disulfide bond reducer and 0.1-2% owf of penetrant, fully diluting, fully and uniformly mixing the diluted solution to form medicament mixed diluted solution, slowly and uniformly adding the medicament mixed diluted solution within 10-30 minutes under the conditions that the temperature is lower than 30 ℃, the pH value is controlled to be 6-8 and the fabric is circularly operated, and circularly operating the fabric for 10-30 minutes under the low temperature condition after the medicament addition is completed, so that the medicament is fully and uniformly dispersed;
s3, heating reaction: under the condition of the cyclic operation of the fabric, the temperature of the treatment fluid is raised to 25-50 ℃ at the heating rate of 0.1-1 ℃ per minute, and the temperature is kept for 20-120 minutes, so that the medicament reacts with wool, the surface scales of the wool fiber are modified, the scale tissue is partially softened and stripped, and then the treatment fluid is emptied;
s4, washing: adding clear water, washing for 5-15 minutes at normal temperature under the condition of circularly running the fabric, and then evacuating;
s5, enzyme inactivation: adding 1-3% owf of acetic acid, diluting, adding and rapidly heating to 75 ℃, pickling for 5-20 minutes under the condition of circularly running the fabric, inactivating residual protease on the fabric, and then evacuating the treatment liquid;
s6, washing: adding clear water, washing for 5-15 minutes at normal temperature under the condition of circulating operation of the fabric, then emptying, and finishing the treatment after cloth discharging;
the protease is one or more enzymes selected from acid protease, neutral protease and alkaline protease, the disulfide bond reducing agent is one or more of dithiothreitol, mercaptoethanol, sodium bisulphite, tri (2-carboxyethyl) phosphine and tri (3-hydroxypropyl) phosphine, the penetrating agent is nonionic, anionic or compound penetrating agent, the wool fabric is a pure wool fabric or wool-containing blended fabric, and the tissue form of the fabric is knitting or weaving.
2. The protease-based wool fabric batch functional finishing method of claim 1, wherein: the pH value controlling regulator is acetic acid and sodium bicarbonate diluent.
3. The protease-based wool fabric batch functional finishing method of claim 1, wherein: the treatment liquid in the equipment is fed into and discharged from the equipment in a circulating way, and the regulating range of the circulating quantity is 5 m/min 3 ～50m 3 。
4. The protease-based wool fabric batch functional finishing method of claim 1, wherein: in the step S5, the enzyme is inactivated, 0.5-3% owf of hydrogen peroxide is added, the diluted hydrogen peroxide is added, the water is washed for 5-15 minutes at normal temperature under the condition of circularly running the fabric, the protease remained on the fabric is inactivated, and then the treatment fluid is emptied.
5. A wool fabric batch function finishing apparatus for carrying out the method of any one of claims 1-4, characterized in that: the device comprises a groove body (1) and a heating and heat-preserving system, wherein the groove body (1) is arc-shaped, the bottom is provided with a drain pipe (2), the upper part is provided with a certain number of guide rollers (3), at least the guide rollers (3) at the two sides are guide roller groups with driving rollers, and a fabric (100) circularly runs in the guide rollers (3) and the groove body (1);
the tank body (1) is provided with an interlayer (1.1), and the heating and heat preservation system comprises a hot water tank (4), and a water inlet pipe (6) and a water outlet pipe (7) which are communicated with the interlayer (1.1) and provided with a circulating pump (5).
6. The wool fabric intermittent functional finishing apparatus of claim 5, wherein: the upper part of the tank body (1) is provided with a cloth folding device (8) for folding the fabric (100) to enable the fabric to be stacked uniformly in an open width at the bottom of the tank body (1).
7. The wool fabric intermittent functional finishing apparatus of claim 5, wherein: an expanding roller (9) is arranged between the guide rollers (3) to expand the width of the fabric (100) and remove wrinkles.
8. The wool fabric intermittent functional finishing apparatus of claim 7, wherein: the device is also provided with a medicament circulation system, wherein the medicament circulation system comprises a plurality of liquid outlet branch pipes (10) and liquid inlet branch pipes (11) which are respectively positioned at two sides of the tank body (1), and the liquid outlet branch pipes (10) and the liquid inlet branch pipes (11) are respectively connected with a circulation main pipe (12) with a circulation pump (5).
9. The wool fabric intermittent functional finishing apparatus of claim 8, wherein: the tank body (1) is provided with a monitoring device A (13) for monitoring the temperature, pH, water level and medicament concentration of the treatment fluid, and the hot water tank (4) is provided with a monitoring device B (14) for monitoring the temperature and the water level.
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| CN102965958A (en) * | 2012-10-31 | 2013-03-13 | 江南大学 | Wool product two-bath process anti-felting treatment technology based on composite bio-enzyme |
| CN108560268A (en) * | 2018-04-23 | 2018-09-21 | 嘉兴市锦福缩染有限公司 | The fulling process of woollen sweater |
| CN109853262A (en) * | 2018-12-30 | 2019-06-07 | 天津工业大学 | A kind of ink-jet printed method of the method for enzymatically treating and wool fabric of wool fabric |
| CN113774656A (en) * | 2021-09-17 | 2021-12-10 | 河北多维康助剂有限公司 | Cashmere and wool anti-pilling finishing method and cashmere and wool knitted fabric |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20090060933A1 (en) * | 2004-06-14 | 2009-03-05 | Estell David A | Proteases producing an altered immunogenic response and methods of making and using the same |
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| CN102965958A (en) * | 2012-10-31 | 2013-03-13 | 江南大学 | Wool product two-bath process anti-felting treatment technology based on composite bio-enzyme |
| CN108560268A (en) * | 2018-04-23 | 2018-09-21 | 嘉兴市锦福缩染有限公司 | The fulling process of woollen sweater |
| CN109853262A (en) * | 2018-12-30 | 2019-06-07 | 天津工业大学 | A kind of ink-jet printed method of the method for enzymatically treating and wool fabric of wool fabric |
| CN113774656A (en) * | 2021-09-17 | 2021-12-10 | 河北多维康助剂有限公司 | Cashmere and wool anti-pilling finishing method and cashmere and wool knitted fabric |
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