EP3258009A1 - Procédé et dispositif pour traitement irrétrécissable sans chlore de matière première de laine et d'article de cette dernière - Google Patents

Procédé et dispositif pour traitement irrétrécissable sans chlore de matière première de laine et d'article de cette dernière Download PDF

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Publication number
EP3258009A1
EP3258009A1 EP16748752.9A EP16748752A EP3258009A1 EP 3258009 A1 EP3258009 A1 EP 3258009A1 EP 16748752 A EP16748752 A EP 16748752A EP 3258009 A1 EP3258009 A1 EP 3258009A1
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EP
European Patent Office
Prior art keywords
wool
treatment
shrinkproof
chlorine
free
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.)
Withdrawn
Application number
EP16748752.9A
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German (de)
English (en)
Inventor
Jinbo YAO
Jianyong Liu
Zhongfa Wan
Weimin Zhang
Wanjun YANG
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Tianjin Lvyuan Tianmei Technology Ltd
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Tianjin Lvyuan Tianmei Technology Ltd
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Publication of EP3258009A1 publication Critical patent/EP3258009A1/fr
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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
    • D06M13/285—Phosphines; Phosphine oxides; Phosphine sulfides; Phosphinic or phosphinous acids or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • D06L1/12—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents
    • D06L1/16—Multi-step processes
    • 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
    • D06B9/00—Solvent-treatment of textile materials
    • 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
    • D06M11/07—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 halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—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 halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D06M11/155—Halides of elements of Groups 2 or 12 of the Periodic Table
    • 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
    • D06M13/52—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment combined with mechanical treatment
    • D06M13/522—Fulling
    • 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
    • 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
    • D06B21/00—Successive treatments of textile materials by liquids, gases or vapours
    • 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
    • D06B3/00—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating
    • D06B3/10—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of fabrics
    • D06B3/18—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of fabrics combined with squeezing, e.g. in padding machines
    • 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 present invention relates to wool product processing field, and particularly, to a process and device for chlorine-free shrinkproof treatment of wool raw material and article thereof, and more particularly to a chlorine-free continuous processing process and device for shrinkproof treatment of wool and wool article.
  • Wool is an important raw material of textile industry and has many excellent characteristics, such as good elasticity, strong hygroscopicity, not easy to stain, good warmth retention and soft luster.
  • Wool as a natural protein fiber, has a scale layer attached onto the surface thereof which is mainly composed of keratin and overlapped with each other as fish scales. Due to different friction coefficients along scale direction and against scale direction, under repeated external force, wool fibers will intersperse, entangle, wrap and felt with each other, thereby producing fulling. Although fulling makes wool fabric have effects such as beautiful appearance, rich and soft feel, and good warmth retention, it also makes wool fabric prone to size shrinkage and deformation in a washing process. Therefore, in order to improve shrinkproof properties of wool textile, surface modification treatment of wool fiber scale is necessary from the beginning so that the dimensional stability of wool fabric product is improved and the product can achieve "machine washable" effect.
  • the main modification shrinkproof treatment methods of wool surface scale include: chlorination method, covering method, protease method and so on.
  • the most extensive method is chlorination shrinkproof treatment method.
  • organic halide AOX which is absorbable organic halide generated during the chlorination process will seriously pollute environment.
  • Chinese patent CN201010605809.9 has reported a shrinkproof scale-stripping process in which potassium permanganate and DCCA as a catalyst are added into water, and then chlorine gas is passed into so as to conduct a shrinkproof scale-stripping for wool tops.
  • This method reduces 30% of chlorine usage on the basis of the original chlorine usage.
  • This method has improved traditional chlorination method, but it still uses chlorine gas and causes serious environmental pollution.
  • the covering method makes the wool surface scale voids filled by depositing a layer of resin film on surface of wool so as to make wool surface become smooth, thereby reducing surface friction effect of fibers.
  • this treatment method can improve felting performance of fibers to a certain extent, it seriously affects the touching feel of wool fabric and has a shortage of poor durability.
  • Protease method makes the scales and cell membrane complex etc. of wool partially dissolved by using protease hydrolysis of peptide bonds of macromolecules on wool fiber surface, so as to partially or totally remove the scales.
  • This treatment method has advantages such as mild handling conditions, energy conservation and pollution reduction etc., and is an environmentally friendly wool shrinkproof treatment method.
  • the shrinkproof effect obtained by using protease alone to treat wool is still unable to meet the actual requirements at present, so when protease is used for biological modification treatment of wool, in many cases, the wool firstly needs pretreatment (such as preoxidation by using strong oxidants such as potassium permanganate etc., or pretreatment by using a chloride solvent).
  • pretreatment methods have disadvantages such as the treatment time is too long, the enzyme is easy to inactivate, the treatment condition is difficult to control and so on.
  • the object of the present invention is to provide a wool shrinkproof treatment process which is environmentally friendly, simple and easy to control, of long-lasting anti-felting effect, of high (or fast) treatment efficiency and suitable for mass production.
  • a shrinkproof treatment agent for chlorine-free shrinkproof treatment comprises: (a) an optional solvent; (b) a protease; and (c) an organic phosphine compound represented by formula A; and an optional inorganic salt; P-(X) 3 A wherein each X is independently selected from the group consisting of substituted or unsubstituted C1-C10 hydrocarbyl, wherein the term "substituted” refers to one or more substituents selected from the group consisting of -OH, -COOH (carboxy), C2-C8 ester group, -SH, -CN, C1-C3 alkyl, and C1-C3 alkoxy; and at least one X is a substituted C1-C10 hydrocarbyl having a -OH or COOH substituent; the weight ratio of the protease to the organic phosphine compound is (0.2 to 10) : (0.5 to 20); and the
  • the chlorine-free treatment comprises descaling/shrinkproof treatment for a wool raw material and/or a wool product.
  • the wool raw material comprises wool top.
  • the weight ratio of the protease to the organic phosphine compound is (0.5 to 5): (1 to 10); and more preferably (1 to 5): (1 to 10).
  • the shrinkproof treatment agent further comprises a basic compound.
  • the basic compound is selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates, alkali metal bicarbonates, alkaline earth metal bicarbonate, and combinations thereof.
  • the basic compound is selected from the group consisting of NaOH, KOH, Ca(OH) 2 , Na 2 CO 3 , K 2 CO 3 , and combinations thereof.
  • the "chlorine-free" means that the shrinkproof treatment agent does not contain an organochlorine compound and does not include a hypochlorous compound selected from the group consisting of: a compound containing ClO - ion (root) and a compound which can produce ClO - ion (such as chlorine gas).
  • a hypochlorous compound selected from the group consisting of: a compound containing ClO - ion (root) and a compound which can produce ClO - ion (such as chlorine gas).
  • the content of the hypochlorous compound is ⁇ 0.05% by weight, preferably ⁇ 0.01% by weight, more preferably ⁇ 0.001% by weight, and most preferably about 0.
  • the shrinkproof treatment agent is a liquid (i.e., a treatment solution).
  • the solvent is selected from the group consisting of water or an aqueous solvent.
  • the shrinkproof treatment agent is a solid or semi-solid, and can be reconstituted into a treatment solution by adding a solvent (e.g., water) upon application.
  • a solvent e.g., water
  • the concentration of the organic phosphine compound is from 1 to 10 g/L, preferably from 1.5 to 10 g/L, and more preferably from 5 to 10 g/L.
  • the concentration of the protease is 0.1 to 25 g/L, preferably 0.2 to 10 g/L, and more preferably 0.5 to 5 g/L.
  • the concentration of the inorganic salt is 0.01 to 10 g/L, preferably 0.05 to 5 g/L, and more preferably 0.1 to 2 g/L.
  • two X are identical.
  • three X are identical.
  • three X are different from each other.
  • each X is independently selected from the group consisting of substituted or unsubstituted C1-C6 hydrocarbyl.
  • the C1-C10 hydrocarbyl includes C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl and C3-C8 cycloalkyl.
  • the C1-C10 hydrocarbyl includes C1-C10 alkyl and C3-C8 cycloalkyl.
  • the shrinkproof treatment agent contains one or more components selected from the group consisting of a protease, an organic phosphine compound, an inorganic salt and a surfactant the contents thereof are as follows: component content preferred content more preferred content protease 0.01 to 2.5wt% (or 0.1 to 25g/L) 0.02 to 1.0wt% (or 0.2 to 10g/L) 0.05 to 0.5wt% (or 0.5 to 5g/L) organic phosphine compound 0.01 to 5.0wt% or 0.1 to 50g/L 0.05 to 2.0wt% or 0.5 to 20g/L 0.1 to 1.0wt% or 1 to 10g/L inorganic salt 0.001 to 1.0wt% or 0.01 to 10g/L 0.005 to 0.5wt% 0.05 to 5g/L 0.01 to 0.2wt% 0.1 to 2g/L surfactant 0.001 to 1.0wt% or 0.01 to 10g/L 0.005 to 0.5wt% or 0.01 to 10
  • the amount (wt) of the protease is less than or equal to ( ⁇ ) the amount (wt) of the organic phosphine compound.
  • the shrinkproof treatment agent when the shrinkproof treatment agent is an aqueous solution or a reconstituted aqueous solution, pH thereof is from 6.5 to 12, preferably from 7 to 11.5, and more preferably from 7.5 to 10.5.
  • the protease is an alkaline protease.
  • the organic phosphine compound is a water-soluble aliphatic organic phosphine compound.
  • the water-soluble refers to solubility of the organic phosphine compound in 100 g of water at 25 °C is ⁇ 0.1g, preferably ⁇ 0.5g, and more preferably ⁇ 2g, such as 0.1 to 10g or 0.5 to 5g.
  • the organic phosphine compound has the following structure formula: P-(R 1 -R 2 ) 3 I wherein,
  • R 1 is selected from the group consisting of methylene, ethylene, propylene, butylene, pentylene, hexylene, and combinations thereof.
  • the aliphatic organic phosphine compound is selected from the group consisting of tris(3-hydroxypropyl)phosphine, tris(3-carboxypropyl)phosphine, tris(2-hydroxyethyl)phosphine, tris(4-carboxybutyl)phosphine, and combinations thereof.
  • the inorganic salt is selected from the group consisting of Ca salts, Mg salts, Na salts, Zn salts, Al salts, Ba salts, and combinations thereof.
  • the inorganic salt is selected from the group consisting of hydrochlorate, sulfate, carbonate, bicarbonate, nitrate, nitrite, phosphate, monohydrogen phosphate, dihydrogen phosphate, and combinations thereof.
  • the inorganic salt is selected from the group consisting of Mg(NO 3 ) 2 , sodium phosphate, calcium hydrogen phosphate, CaCl 2 , and combinations thereof.
  • the surfactant is selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and combinations thereof.
  • the shrinkproof treatment agent further comprises a pH buffer.
  • the amount of the pH buffer is from 0.1 to 10 g/L, and preferably from 0.2 to 5 g/L.
  • the pH buffer is selected from the group consisting of disodium hydrogen phosphate - sodium dihydrogen phosphate buffer (PBS), NaHCO 3 -Na 2 CO 3 buffer, and combinations thereof.
  • the shrinkproof treatment agent is liquid at 25 to 80 °C.
  • the shrinkproof treatment agent is liquid at an application temperature of from 30 to 70 °C, preferably from 40 to 60 °C, and more preferably from 45 to 55 °C.
  • the size of wool tops to be treated is 10-30 g/m/piece, and preferably 20 to 25 g/m/piece.
  • n pieces of wool tops are treated in parallel and simultaneously, wherein n is from 10 to 100, from 20 to 70, and preferably from 30 to 60.
  • a shrinkproof treatment device for chlorine-free wool tops or wool products which comprises:
  • n is a positive integer of 3 to 10.
  • a treatment agent containing only the protease but not the organic phosphine compound may be additionally used to treat.
  • total time T of the padding treatment of step (b) is ⁇ 15 minutes, preferably ⁇ 10 minutes, more preferably ⁇ 5 minutes, and most preferably ⁇ 3 minutes.
  • the chlorine-free wool tops or wool products to be treated in step (a) is flattened.
  • the wool tops has a component selected from the group consisting of wool, cashmere, and a combination thereof.
  • the wool tops has a size of 40 to 150 branches, preferably 40 to 120 branches, and more preferably 56 to 100 branches.
  • the temperature for the padding treatment is 5 to 80 °C, preferably 10 to 60 °C, more preferably 25 to 50 °C, and most preferably 40 to 50 °C.
  • total time for the padding treatment is not particularly limited, and is usually 1 to 20 minutes, preferably 1 to 10 minutes, and more preferably 1 to 5 minutes.
  • the temperature for the water washing is not particularly limited and is usually from 5 to 60 °C, preferably from 10 to 50 °C, more preferably from 20 to 40 °C, and most preferably from 20 to 30 °C.
  • time for the water washing is not particularly limited and is usually 30 seconds to 120 minutes, preferably 1 minute to 60 minutes, and more preferably 2 to 30 minutes.
  • the enzyme inactivation treatment uses conventional inactivation conditions as long as the residual protease is inactivated or substantially inactivated.
  • no hypochlorous compound is used in the method.
  • ratio of the volume of the shrinkproof treatment agent to the weight of the wool products to be treated is not particularly limited as long as the wool tops or wool products to be treated can be wetted.
  • times of the padding may be the same or different, and preferably the same.
  • the times of the padding is 3 to 15 times, preferably 4 to 12 times, and more preferably 5 to 10 times.
  • treatment time of the padding in step (b) is 3 to 1000 s, preferably 5 to 800 s, more preferably 8 to 600 s, and most preferably 10 to 300 s.
  • the padded wool products obtained in step (b) has a liquid-containing rate of 50 to 160 wt%, preferably 60 to 150 wt%, and more preferably 80 to 140 wt%.
  • step (b) is repeated, and repetition times is 3 to 15 times, preferably 4 to 12 times, and more preferably 5 to 10 times.
  • step (b) before repeating step (b) for every time, it further comprises a step of replacing the shrinkproof treatment agent.
  • the temperature of water used for the water washing is 10-40 °C, and preferably 20 to 30 °C.
  • pH of water used for the water washing is 6.5-7.5, preferably 7.
  • step (c) the padded wool products obtained in step (b) is water washed with a certain amount of water.
  • step (c) the water washing is conducted 1 to 6 times, preferably 2 to 4 times.
  • the time for the water washing in step (c) is 1 to 60 minutes, preferably 1 to 30 minutes, and more preferably 1 to 10 minutes.
  • step (c) is repeated and repetition times are 1 to 6 times, preferably 2 to 4 times.
  • step (d) the inactivation treatment is carried out by using a method selected from the group consisting of hot water inactivation, hydrogen peroxide (H 2 O 2 ) inactivation, and combination thereof.
  • the temperature of hot water used in the hot water inactivation is 85 to 100 °C, preferably 90 to 98 °C, and more preferably 92 to 96 °C.
  • treatment time of the hot water inactivation is from 5 to 300 s, preferably from 8 to 200 s, more preferably from 10 to 100 s.
  • treatment time of the hydrogen peroxide inactivation treatment is from 5 to 300 s, preferably from 8 to 200 s, and more preferably from 10 to 100 s.
  • step (d) it optionally further comprises following steps:
  • the soft treatment in step 5) is to soak the product obtained in step (d) with a soft treatment agent.
  • a ratio of the product obtained in step (d) to the soft treatment agent is a conventional ratio.
  • the soft treatment in step 5 has a soaking time in the treatment agent of 5 to 200 s, preferably 8 to 100 s, and more preferably 10 to 50 s.
  • the soft treatment in step 5 has a frequency of 1 to 10 times, preferably 2 to 5 times, and more preferably 3 to 4 times.
  • the treatment agent employed in the soft treatment in step 5) has a temperature of from 25 to 65 °C, and preferably from 30 to 50 °C.
  • pH of the treatment agent employed in the soft treatment in step 5 is from 5 to 8, and preferably from 5.5 to 7.5.
  • concentration of the treatment agent used in the soft treatment in step 5 is from 5 to 100 g/L, preferably from 10 to 50 g/L, and more preferably from 15 to 30 g/L.
  • the treatment agent used in the soft treatment in step 5) is selected from the group consisting of wool smoothing agents, wool softening agents, and combinations thereof.
  • treatment temperature for the drying treatment in step 6 is 60 to 100 °C, preferably 70 to 90 °C.
  • drying treatment time at the treatment temperature is from 1 to 30 minutes, and preferably from 3 to 15 minutes.
  • the fourth aspect of the present invention provides a shrinkproof chlorine-free wool product in which there is no residual organic chlorine.
  • the wool product is shrinkproof treated by the shrinkproof treatment process (method) of the present invention.
  • the wool product is shrinkproof treated with the shrinkproof treatment agent for chlorine-free wool tops or wool products according to the first aspect of the present invention.
  • the wool product is chlorine-free treated by using the shrinkproof treatment device according to the second aspect of the present invention.
  • a scale layer removal rate of wool surface layer of the treated chlorine-free wool product is 80 to 100%, preferably from 90 to 100%, more preferably from 95 to 100%, such as from 99 to 100%, when it is compared with that of the wool product to be treated.
  • the absolute value of shrinkage rate of the treated chlorine-free wool product is ⁇ 10%, preferably ⁇ 8%, preferably ⁇ 6%, more preferably ⁇ 5%, and most preferably ⁇ 3% when it is compared with that of the wool product to be treated, wherein measurement method thereof is TWC.TM31 test method of the International Wool Bureau.
  • the strength retention of the treated chlorine-free wool product is ⁇ 80%, preferably ⁇ 82%, more preferably ⁇ 84% when it is compared with that of the wool product to be treated.
  • the elongation retention of the treated chlorine-free wool product is ⁇ 70%, preferably ⁇ 75%, and more preferably ⁇ 80% when it is compared with that of the wool product to be treated.
  • the drip diffusion time of the treated chlorine-free wool product is ⁇ 30 s, preferably ⁇ 15 s, and more preferably ⁇ 10 s.
  • an article is provided, and the article comprises the wool product or is made up of the wool product according to the fourth aspect of the present invention.
  • the article comprises a wool tops, a wool blanket and a garment.
  • the sixth aspect of the present invention provides a use of the shrinkproof treatment agent according to the first aspect of the present invention in the chlorine-free shrinkproof treatment of a wool top or a wool product.
  • a shrinkproof treatment agent for chlorine-free wool tops and wool products comprises: a protease, a water-soluble aliphatic trisubstituted organic phosphine compound, and an inorganic salt, wherein the water-soluble aliphatic trisubstituted organic phosphine compound has a structure of P-(R-S) 3 , wherein R is hydrocarbyl containing 1 to 6 carbon, S is hydroxyl or carboxyl and derivatives thereof; and mass concentration thereof is 1 to 10 g/L; the inorganic salt is calcium chloride, and has a concentration of 0 to 2g/L.
  • the trisubstituted organic phosphine compound is at least one of tris(3-hydroxypropyl)phosphine, tris(3-carboxypropyl)phosphine, tris(2-hydroxyethyl)phosphine and tris(4-carboxybutyl) phosphine.
  • a continuous processing process of shrinkproof treatment of chlorine-free wool tops and wool products which comprises the following steps:
  • the soaking and rolling (or extruding) treatment is repeated for 3 to 10 times; total time for the padding treatment is 1-5 minutes; and process delivery speed is 3 to 8 m/min.
  • the wool tops are wool or cashmere of 56 to 100 branches.
  • the process and the shrinkproof treatment agent of the invention can efficiently and rapidly remove the scale layer on the surface of the wool fiber under chlorine-free condition and modify the scale layer, thereby improving felting property of the wool product and dimensional stability of product.
  • the inventors have completed the present invention.
  • a continuous processing process of shrinkproof treatment of chlorine-free wool tops and wool products comprises shrinkproof treatment, water washing, protease inactivation, soft treatment, dehydration and drying steps.
  • the wool fiber is a protein fiber
  • a highly efficient integrated catalytic system composed of a protease, an activator of a water-soluble aliphatic trisubstituted organic phosphine structure, a metal salt and non-ionic surfactant is selected, which can synergistically and efficiently remove the scale layer on the surface of wool fiber and modify the scale layer, thereby improving felting property of the wool product and dimensional stability of product and conferring the fabric with anti-pilling characteristics and smooth feel.
  • the invention can completely replace the chlorination shrinkproof method in the art, and avoid the environmental pollution caused by the chlorination method.
  • the present invention is a cleaning treatment process which meets the environmental requirements, and has no problem of chlorination pollution.
  • the method has following advantages such as: reagent usage amount is small, the cost is low, the process is simple, the requirement for equipment is low, it can be continuously conducted, and it can realize industrial production.
  • wool raw material includes wool, wool top, or semi-finished products thereof without subjecting to a descaling shrinkproof treatment.
  • the term may also include wool raw material which has been subjected to descaling shrinkproof treatment, but has not completely been descaled.
  • wool top/wool product and “wool top and/or wool product” can be used interchangeably and refer to wool top, or wool product, or a combination thereof.
  • the term may include both the wool top/ wool product to be treated and the treated or being treated wool top/ wool product.
  • chlorine-free product of the present invention and “chlorine-free wool top/ wool article of the present invention” can be used interchangeably and refer to the wool top/ wool product obtained by the chlorine-free descaling shrinkproof treatment process of the present invention. Since the chlorine-free descaling shrinkproof treatment process of the present invention does not use any organochlorine compound and does not use any hypochlorous compound (i.e., a compound containing ClO - ion or a compound capable of producing ClO - ion), the chlorine-free wool products (including wool tops/ wool products) have excellent safety.
  • hypochlorous compound i.e., a compound containing ClO - ion or a compound capable of producing ClO - ion
  • shrinkproof agent (or liquid) of the present invention can be used interchangeably and refer to the shrinkproof treatment agent (or liquid) for the chlorine-free wool top/ wool product in the present invention.
  • a descaling shrinkproof treatment agent for the chlorine-free wool top/ wool product of the present invention is provided in the present invention.
  • the descaling shrinkproof treatment agent of the present invention may be solid or liquid.
  • the chlorine-free shrinkproof agent of the present invention is solid, it can be reconstituted into a corresponding shrinkproof treatment liquid used for a chlorine-free wool top/ wool product by adding water (or an aqueous solvent).
  • every combination may have been mixed together (i.e. in a mixed form), or the components of the agent may also be present in an unmixed form and are mixed into a formulation in situ when one need to use such agent.
  • main components of a shrinkproof treatment liquid for chlorine-free wool top and wool product comprise a protease, a water-soluble aliphatic trisubstituted organic phosphine compound, and an inorganic salt.
  • the structure of the water-soluble aliphatic trisubstituted organic phosphine is P-(R-S) 3 , wherein R is hydrocarbyl containing 1 to 6 carbons, S is hydroxyl or carboxyl and derivatives thereof; and mass concentration thereof is 1 to 10 g/L.
  • the inorganic salt is calcium chloride, and the concentration thereof is 0 to 2 g/L.
  • the preferred trisubstituted organic phosphine includes (but is not limited to): tris(3-hydroxypropyl)phosphine, tris(3-carboxypropyl)phosphine, tris(2-hydroxyethyl)phosphine, tris(4-carboxybutyl)phosphine, or combinations thereof.
  • the protease includes a neutral protease, an alkaline protease, or a combination thereof.
  • the neutral protease refers to a protease whose optimal pH is neutral (e.g. about 6.8 to 7.0), and molecular weight thereof is generally from 35 to 40 kD.
  • Neutral proteases suitable for use in the present invention include neutral proteases that are commercially available or prepared by conventional methods, such as neutral proteases from microorganisms, Neutrase, or combinations thereof.
  • the alkaline protease refers to a protease whose optimal pH is alkaline (e.g. about 9 to 11), and molecular weight thereof is generally from 26 to 34 kD.
  • Alkaline proteases suitable for use in the present invention include alkaline proteases that are commercially available or prepared by conventional methods, such as alkaline proteases from Bacillus licheniformis (a protease belong to serine-type endoprotease and having a molecular weight of about 27300), alkaline proteases from Streptomycetes , 2709 alkaline protease, Novo protease, Carsberg protease and the like.
  • the concentration of protease is generally 0.1 to 25 g/L, preferably 0.2 to 10 g/L, and more preferably 0.5 to 5 g/L.
  • the amount (or concentration) of protease is generally 1 ⁇ 10 4 -1 ⁇ 10 8 U/L, preferably 5 ⁇ 10 4 -5 ⁇ 10 7 U/L, and more preferably 1 ⁇ 10 5 -1 ⁇ 10 7 U/L.
  • the shrinkproof treatment liquid of the present invention further comprises a nonionic surfactant (e.g. JFC) or an anionic surfactant.
  • non-ionic surfactants include (but are not limited to): polyoxyethylene type surfactants such as alkylphenol polyoxyethylene ether (APEO), fatty acid polyoxyethylene esters (AE), fatty acid methyl ester ethoxylates (FMEE), and polyol type surfactants (such as sorbitan esters, including Tween and Span), or combinations thereof.
  • Representative examples include Tween, Span, JFC, or combinations thereof.
  • Representative anionic surfactants include (but are not limited to): sodium dodecylbenzenesulfonate, sodium dodecyl sulfate (SDS), hexadecylsulfonate, or combinations thereof.
  • the concentration of surfactant is 0.001 to 1.0 wt% or 0.01 to 10 g/L, and preferably 0.1 to 2 g/L.
  • the pH of the shrinkproof treatment liquid of the present invention is from 7 to 10.5.
  • a shrinkproof treatment liquid for chlorine-free wool tops and wool products is provided in the present invention, which has main components in mass as follows:
  • the shrinkproof treatment agent (liquid) of the present invention can directly treat the wool top/ wool product to obtain a descaling shrinkproof wool top/ wool product.
  • the shrinkproof treatment liquid of the present invention contains neither an organochlorine compound nor a hypochlorous compound (i.e., a compound containing ClO - ion or a compound capable of producing ClO - ion such as Cl 2 ).
  • the organochlorine compounds include DCCA, chloroform, carbon tetrachloride, TCCA and the like.
  • the main components of the shrinkproof treatment liquid of the chlorine-free wool top and wool product of the present invention are protease, water-soluble aliphatic trisubstituted organic phosphine compound and inorganic salt.
  • the water-soluble aliphatic trisubstituted organic phosphine has a structure of P-(R-S) 3 , wherein R is a hydrocarbyl having 1 to 6 carbon (C), and S is hydroxyl (-OH) or carboxyl (-COOH) and derivatives thereof.
  • R is a hydrocarbyl having 1 to 6 carbon (C)
  • S is hydroxyl (-OH) or carboxyl (-COOH) and derivatives thereof.
  • the usage amount is 1g ⁇ 10g/L.
  • the inorganic salts are calcium chloride etc., and usage amount thereof is 0g/L ⁇ 2g/L.
  • the trisubstituted organic phosphine is at least one of tris(3-hydroxypropyl)phosphine, tris(3-carboxypropyl)phosphine, tris(2-hydroxyethyl)phosphine and tris(4-carboxybutyl)phosphine.
  • the protease is a neutral protease, an alkaline protease and the like, and the concentration of protease is 0.5 g/L to 5 g/L.
  • the pH of the shrinkproof treatment liquid is 7 to 10.5.
  • the main components of the shrinkproof treatment liquid in mass comprises:
  • a shrinkproof treatment method for chlorine-free wool top or wool product is also provided in the present invention, in which the wool top/ wool product is treated with the chlorine-free descaling shrinkproof treatment liquid of the present invention, thereby obtaining a wool top/ wool product with excellent shrinkproof properties.
  • the shrinkproof treatment liquid and method of the present invention can achieve a sufficient descaling to obtain a fully descaled wool product, the method of the present invention can also be used to produce a wool product that is not fully descaled (i.e. partially descaled).
  • a continuous processing process of shrinkproof treatment of chlorine-free wool top and wool product is provided in the invention, and comprises the following steps:
  • the immersion (or soaking) and rolling operation may be repeated for a plurality of times, for example, 3 to 10 times.
  • the total time of the soaking and rolling treatment is not particularly limited, and is usually 0.5 to 20 minutes, preferably 1 to 10 minutes, and more preferably 1 to 5 minutes.
  • the present invention requires only a very short total time for the soaking / rolling operation, since the chlorine-free descaling shrinkproof treatment agent of the present invention can descale very efficiently and with almost no damage.
  • the chlorine-free shrinkproof treatment process of the present invention is continuous, wherein the delivery speed in the continuous process may be from 0.5 to 20 m/min, and preferably from 1 to 10 m/min.
  • the process comprises:
  • a chlorine-free treatment device for use in the method of invention is also provided in the present invention.
  • a typical treatment device is shown in Figure 7 .
  • the device comprises:
  • the multiple padding apparatus, the water washing apparatus, the enzyme inactivation apparatus, the optional soft processing apparatus and the optional dryer are arranged in sequence.
  • one or more auxiliary padding machines are further set between or behind every padding machine of the multiple padding apparatus, and every auxiliary padding machines independently comprises an auxiliary soaking tank and an auxiliary rolling roller, wherein the auxiliary soaking tank is filled with a protease treatment solution containing no organic phosphine compound and/or an organic phosphine compound treatment liquid containing no protease.
  • the auxiliary soaking tank is an enzyme treatment tank.
  • the enzyme treatment bath is located after the second, third, fourth or fifth padding machine.
  • n is 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, preferably 3 to 15, and more preferably 4 to 10.
  • the shape and size of every padding machine may be the same or different.
  • every padding machine is arranged in sequence.
  • the soaking tank is filled with the shrinkproof treatment agent (or liquid) according to the first aspect of the present invention.
  • the soaking tank is a suction roller tank.
  • the soaking tank is independently equipped with or without a heating apparatus or a temperature control apparatus.
  • every heating apparatus or every temperature control apparatus controls the temperature in a range of 25 to 80 °C by, preferably 30 to 70 °C, more preferably 40 to 60 °C, and most preferably 45 to 55 °C.
  • the water washing apparatus comprises m water scrubbers, wherein m is a positive integer of 1 to 10, preferably 1 to 6, and preferably 2 to 4.
  • every water scrubber is filled with a solvent of water.
  • temperature of the solvent water is 10-40 °C, preferably 20 to 30 °C.
  • pH of the solvent water is 6.5-7.5, preferably 7 ⁇ 0.2.
  • the enzyme inactivation apparatus is a high temperature inactivation tank and/or a hydrogen peroxide inactivation tank.
  • the temperature of the solvent water is from 85 to 100 °C, preferably from 90 to 98 °C, and more preferably from 92 to 96 °C.
  • the enzyme inactivation apparatus is filled with a H 2 O 2 solution.
  • the concentration of the H 2 O 2 in the solution is 0.01 to 50 g/L, preferably 0.05 to 30 g/L, and more preferably 0.1 to 10 g/L.
  • the soft treatment apparatus is filled with the soft treatment agent selected from the group consisting of: wool smoothing agents, wool softening agents, or combinations thereof.
  • the soft treatment agent in the soft treatment apparatus, has a concentration of about 1 to 50 g/L, preferably 2 to 40 g/L, and more preferably 5 to 25 g/L.
  • the wool softening agent includes an organic silicon softening agent.
  • the organic silicon softening agent is selected from the group consisting of: silicone oil, hydrogen silicone oil, amino silicone oil, modified silicone oil, or combinations thereof.
  • ecoshine or "ecoshine product” refers to a shrinkproof chlorine-free wool top/ wool product with little or no organochlorine residue obtained with the chlorine-free shrinkage treatment process of the present invention.
  • the chlorine-free treated wool tops or wool products (i.e. ecoshine product) of the present invention have excellent properties including (but not limited to):
  • the present inventors have found that there are some specific structures and substances in the scale layer of the wool surface, such as disulfide bond-containing cystine and lipids and so on, which make it difficult for the protease to efficiently digest and decompose the high-sulfur protein on the surface of the scale and therein.
  • the structure of the scale layer on the surface of the wool can be effectively altered, which makes that proteins such as high-sulfur protein are more prone to be decomposed by protease, and on the other hand, the vitality of the protease can be maintained or enhanced, thereby achieving descaling and shrinkproof treatment of wool with very high efficiency and high speed.
  • the action of the protease is mainly to degrade the scale on the surface of wool fiber by hydrolysis; on the one hand, the water-soluble aliphatic trisubstituted organic phosphine rapidly reduces a large number of disulfide bond existed in the scale and activates the reaction substrate by its unique effect on the disulfide bonds in the wool so as to facilitate the reaction between the protease and wool macromolecule. Furthermore, it has good stabilizing effect on the activity of the protease, and can effectively reduce the decline of protease activity in the integrated catalytic system, while at the same time it is also able to further activate the catalytic action of protease, resulting in a rapid reaction effect.
  • the main role of the inorganic salt catalyst is to further activate the protease; and the main role of the surfactant is to assist treatment solution to wet and infiltrate the surface of wool fiber as soon as possible.
  • multiple padding or repeated padding is also a necessary condition for the present invention to achieve a rapid process.
  • repeated padding rapid contact and interaction between the protease, the activator and wool fiber surface are realized compulsively, and it is helpful to clear the reactants and hydrolyzes so as to facilitate further reaction.
  • the present invention has following main advantages:
  • the treatment liquid of the present invention is prepared by weighing the protease, the water-soluble aliphatic trisubstituted organic phosphine compound, the inorganic salt and the surfactant according to the amount of the main formula and using the general mass concentration (g/L) preparation method.
  • the organic phosphine compound were purchased from TianJin Littoral Orient Technology Co., Ltd..
  • the wool tops were subjected to a chlorine-free shrinkproof treatment using a continuous process having five-multiple padding.
  • the wool tops were evenly arranged side by side on the roller and uniformly transported into the treatment liquid at a speed of 8 m/min, so that the wool tops were completely wet to ensure that the surface of every fiber of the wool tops was evenly and thoroughly treated. Then the wool tops were squeezed by the pressure roller to ensure that the liquid-containing rate of the wool tops was about 135%. Afterwards, the wool tops containing the enzyme fluid entered into the second treatment tank at a speed of 8 m/min. It took 15 seconds from the time when the wool tops entered into the first tank treatment liquid to the time when the wool tops entered into the second tank treatment liquid.
  • the second tank padding treatment solution. They are the same as those for the first tank.
  • the third tank padding treatment solution. They are the same as those for the first tank.
  • the fourth tank padding treatment solution. They are the same as those for the first tank.
  • the sixth tank water washing.
  • the wool tops were rolling washed by rolling, so that the reagents, enzymes and degraded products attached on the surface of the wool fiber were cleaned.
  • the water temperature was room temperature, and pH was 7.0.
  • the seventh tank the second water washing. They are the same as those for the sixth tank.
  • the eighth tank water washing at high temperature. It played a role of enzyme inactivation, so as to prevent subsequent continuous erosion of wool fibers. Temperature was 95 °C and time was 15 seconds.
  • the ninth tank conventional soft treatment.
  • the wool fiber were softened to achieve soft effect and to improve the feel.
  • the wool tops were subjected to conventional dehydration and drying (for example: drying process conditions: drying temperature was 70 to 90 °C, and drying time was 3 to 10 minutes).
  • the process speed was 8 m/min, and number of padding in the treatment liquid was 5 times in total. After treated by this process, the scale stripping effect of the wool fiber was shown in Figure 1 .
  • the strength retention of the wool treated by this process was 85% and elongation retention thereof was 83%, compared with those of the untreated wool.
  • the wool treated by this process had a 5 ⁇ 5A test results of -4.86%.
  • Chlorine content of the treated wool was measured, and no residual chlorine component (organic substance) was detected.
  • the wool tops were subjected to a chlorine-free shrinkproof treatment using a continuous process having six-multiple padding.
  • the wool tops were evenly arranged side by side on the roller and uniformly transported into the treatment liquid at a speed of 3.8 m/min, so that the wool tops were completely wet to ensure that the surface of every fiber of the wool tops was evenly and thoroughly treated; and then the wool tops were squeezed by the pressure roller to ensure that the liquid-containing rate of the wool tops was 130%.
  • the wool tops containing the enzyme fluid entered into the second treatment tank at a speed of 3.8 m/min. It took 31.5 seconds from the time when the wool tops entered into the first tank treatment liquid to the time when the wool tops entered into the second tank treatment liquid.
  • the second tank padding treatment solution. They are the same as those for the first tank.
  • the third tank padding treatment solution. They are the same as those for the first tank.
  • the fourth tank padding treatment solution. They are the same as those for the first tank.
  • the fifth tank padding treatment solution. They are the same as those for the first tank.
  • the seventh tank water washing.
  • the wool tops were rolling washed by rolling, so that the reagents, enzymes and degraded products attached on the surface of the wool fiber were cleaned.
  • the water temperature was room temperature, and pH was 7.0.
  • the eighth tank the second water washing. They are the same as those for the seventh tank.
  • the ninth tank water washing at high temperature. It played a role of enzyme inactivation, so as to prevent subsequent continuous erosion of wool fibers. Temperature was 95 °C and time was 15 seconds.
  • the tenth tank The wool tops were padded in a solution containing 20g/L of wool softener, and the wool fiber were softened to achieve soft effect and to improve the feel. Temperature of the softener solution was 40 °C, and pH thereof was 7.0, and time was 15 seconds. Afterwards, the wool tops were subjected to dehydrate and dry.
  • the process speed was 3.8 m/min, and number of padding in the treatment liquid was 6 times in total. After treated by this process, the scale stripping effect of the wool fiber was shown in Figure 2 .
  • the strength retention of the wool treated by this process was 83% and elongation retention thereof was 72%, compared with those of the untreated wool.
  • Chlorine content of the treated wool was measured, and no residual chlorine component (organic substance) was detected.
  • the wool tops were subjected to a chlorine-free shrinkproof treatment using a continuous process having five-multiple padding.
  • the wool tops were evenly arranged side by side on the roller and uniformly transported into the treatment liquid at a speed of 3.8 m/min, so that the wool tops were completely wet to ensure that the surface of every fiber of the wool tops was evenly and thoroughly treated. Then the wool tops were squeezed by the pressure roller to ensure that the liquid-containing rate of the wool tops was 130%. Afterwards, the wool tops containing the enzyme fluid entered into the second treatment tank at a speed of 3.8 m/min. It took 31.5 seconds from the time when the wool tops entered into the first tank treatment liquid to the time when the wool tops entered into the second tank treatment liquid.
  • the second tank padding treatment solution. They are the same as those for the first tank.
  • the third tank padding treatment solution. They are the same as those for the first tank.
  • the fourth tank padding treatment solution. They are the same as those for the first tank.
  • the sixth tank water washing.
  • the wool tops were rolling washed by rolling, so that the reagents, enzymes and degraded products attached on the surface of the wool fiber were cleaned.
  • the water temperature was room temperature, and pH was 7.0.
  • the seventh tank the second water washing. They are the same as those for the sixth tank.
  • the eighth tank water washing at high temperature. It played a role of enzyme inactivation, so as to prevent subsequent continuous erosion of wool fibers. Temperature was 95 °C, and time was 15 seconds.
  • the ninth tank the wool tops were padded in a solution containing 20g/L of wool softener, and the wool fiber were softened to achieve soft effect and to improve the feel. Temperature of the softener solution was 40 °C, and pH thereof was 6.0, and time was 15 seconds. Afterwards, the wool tops were subjected to dehydrate and dry.
  • the process speed was 3.8 m/min, and number of padding in the treatment liquid was 5 times in total. After treated by this process, the scale stripping effect of the wool fiber was shown in Figure 3 .
  • the strength retention of the wool treated by this process was 81% and elongation retention thereof was 80%, compared with those of the untreated wool.
  • Chlorine content of the treated wool was measured, and no residual chlorine component (organic substance) was detected.
  • the wool tops were subjected to a chlorine-free shrinkproof treatment using a continuous process having five-multiple padding.
  • the wool tops were evenly arranged side by side on the roller and uniformly transported into the treatment liquid at a speed of 4.5 m/min, so that the wool tops were completely wet to ensure the surface of every fiber of the wool tops was evenly and thoroughly treated; and then the wool tops were squeezed by the pressure roller to ensure that the liquid-containing rate of the wool tops was 130%.
  • the wool tops containing the enzyme fluid entered into the second treatment tank at a speed of 4.5 m/min. It took 26.7 seconds from the time when the wool tops entered into the first tank treatment liquid to the time when the wool tops entered into the second tank treatment liquid.
  • the second tank padding treatment solution. They are the same as those for the first tank.
  • the third tank padding treatment solution. They are the same as those for the first tank.
  • the fourth tank padding treatment solution. They are the same as those for the first tank.
  • the sixth tank water washing.
  • the wool tops were rolling washed by rolling, so that the reagents, enzymes and degraded products attached on the surface of the wool fiber were cleaned.
  • the water temperature was room temperature, and pH was 7.0.
  • the seventh tank the second water washing. They are the same as those for the sixth tank.
  • the eighth tank water washing at high temperature. It played a role of enzyme inactivation, so as to prevent subsequent continuous erosion of wool fibers. Temperature was 95 °C, and time was 15 seconds.
  • the ninth tank the wool tops were padded in a solution containing 20g/L of wool softener, and the wool fiber were softened to achieve soft effect and to improve the feel. Temperature of the softener solution was 40 °C, and pH was 6.0, and time was 15 seconds. Afterwards, the wool tops were subjected to dehydrate and dry.
  • the process speed was 4.5 m/min, and number of padding in the treatment liquid was 5 times in total. After treated by this process, the scale stripping effect of the wool fiber was shown in Figure 4 .
  • the strength retention of the wool treated by this process was 82% and elongation retention thereof was 81%, compared with those of the untreated wool.
  • the wool treated by this process had a 5 ⁇ 5A test results of -3.56%.
  • the wool tops were subjected to a chlorine-free shrinkproof treatment using a continuous process having seven-multiple padding.
  • the wool tops were evenly arranged side by side on the roller and uniformly transported into the treatment liquid at a speed of 6 m/min, so that the wool tops were completely wet to ensure the surface of every fiber of the wool tops was evenly and thoroughly treated. Then the wool tops were squeezed by the pressure roller to ensure that the liquid-containing rate of the wool tops was 130%. Afterwards, the wool tops containing the enzyme fluid entered into the second treatment tank at a speed of 6 m/min. It took 20 seconds from the time when the wool tops entered into the first tank treatment liquid to the time when the wool tops entered into the second tank treatment liquid.
  • the second tank padding treatment solution. They are the same as those for the first tank.
  • the third tank padding treatment solution. They are the same as those for the first tank.
  • the fourth tank padding treatment solution. They are the same as those for the first tank.
  • the fifth tank padding treatment solution. They are the same as those for the first tank.
  • the sixth tank padding treatment solution. They are the same as those for the first tank.
  • the eighth tank water washing.
  • the wool tops were rolling washed by rolling, so that the reagents, enzymes and degraded products attached on the surface of the wool fiber were cleaned.
  • the water temperature was room temperature, and pH was 7.0.
  • the ninth tank the second water washing. They are the same as those for the eighth tank.
  • the tenth tank water washing at high temperature. It played a role of enzyme inactivation, so as to prevent subsequent continuous erosion of wool fibers. Temperature was 95 °C, and time was 15 seconds.
  • the eleventh tank the wool tops were padded in a solution containing 20g/L of wool softener, and the wool fiber were softened to achieve soft effect and to improve the feel. Temperature of the softener solution was 40 °C, and pH thereof was 6.0, and time was 15 seconds. Afterwards, the wool tops were subjected to dehydrate and dry.
  • the process speed was 6 m/min, and number of padding in the treatment liquid was 7 times in total. After treated by this process, the scale stripping effect of the wool fiber was shown in Figure 5 .
  • the strength retention of the wool treated by this process was 82% and elongation retention thereof was 80%, compared with those of the untreated wool.
  • the wool treated by this process had a 5 ⁇ 5A test results of -3.01%.
  • the wool products were subjected to a chlorine-free shrinkproof treatment using a continuous process having four-multiple padding.
  • the products to be treated were wool products (serge). Method was as follows:
  • Descaling shrinkproof treatment was conducted by using a conventional soaking method, and the method was as follows:
  • This comparative example adopted a conventional batch type method, and descaling shrinkproof treatment was conducted by using a soaking-steaming method.
  • Method was as follows:
  • Example 2 After soaking-steaming treatment, it was subjected to a post-treatment (similar to that in Example 1) by using a conventional method, which included water washing for three times, followed by enzyme inactivation treatment and soft treatment, and then followed by dehydration and drying.
  • a conventional method which included water washing for three times, followed by enzyme inactivation treatment and soft treatment, and then followed by dehydration and drying.
  • the formulation of the soaking treatment liquid was similar to that of the padding treatment solution in Example 1 except that tris(3-hydroxypropyl)phosphine was not contained. That is, the formulation was as follows: alkaline protease 3g/L, nonionic surfactant JFC 1g/L.
  • the fiber strength was 10.34cN
  • the strength retention rate was 83.25%
  • the elongation rate was 32.30%
  • the elongation retention rate was 64.77%. This indicated that the wool treated by this process could meet the shrinkproof requirement, and the loss of rupture strength was in the acceptable range, but the elongation loss was relatively high.
  • the present invention is characterized in that a chlorine-free and rapid continuous processing is provided to completely substitute chlorination shrinkproof method so as to improve the shortcomings when protease biological treatment process is used alone. It also improves the protease biological treatment method, and finally achieves the goal of the optimal treatment effect and improves the quality of the whole wool product.

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JP2018506661A (ja) 2018-03-08
CN105986484B (zh) 2018-05-29
AU2016218638A1 (en) 2017-09-21
WO2016127951A1 (fr) 2016-08-18

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