CN107083684A

CN107083684A - The technique and equipment without chlorine anti-shrinking for raw wool and product

Info

Publication number: CN107083684A
Application number: CN201610086083.XA
Authority: CN
Inventors: 姚金波; 刘建勇; 万忠发; 张伟民; 杨万君
Original assignee: Tianjin Lvyuan Tianmei Science And Technology Co Ltd
Current assignee: Tianjin Lvyuan Tianmei Science And Technology Co Ltd
Priority date: 2016-02-15
Filing date: 2016-02-15
Publication date: 2017-08-22

Abstract

The present invention relates to the technique and equipment without chlorine anti-shrinking for raw wool and product.Specifically, present invention process is included without steps such as chlorine anti-shrinking, washing, albumen enzyme-deactivating, soft treatment, dehydration, drying, wherein from by protease and specific organic phosphine compound etc. constitute without chlorine catalyst system and catalyzing, so as to cooperate with the scale layer for efficiently removing wool surface, it is modified scale layer, so that reaching improves the shrinkproof performance of wool product.Present invention process can replace the shrinkproof method of chlorination of the prior art completely, not only environment-friendly and low for equipment requirements, can continuous operation, suitable large-scale industrialized production.

Description

Process and apparatus for chlorine-free shrink-proof treatment of wool raw material and product

Technical Field

The invention relates to the field of wool product processing, in particular to a process and equipment for chlorine-free shrink-proof treatment of wool raw materials and products, and particularly relates to a continuous processing process and equipment for chlorine-free wool tops and shrink-proof treatment of wool products.

Background

Wool is an important raw material in the textile industry and has many excellent characteristics, such as good elasticity, strong hygroscopicity, less staining tendency, good heat retention and soft luster. Wool is a natural protein fiber, a layer of scale layers which are mainly composed of keratin and are overlapped with each other like fish scales is attached to the surface of the natural protein fiber, and due to different friction coefficients in the forward and reverse scale directions, the wool fibers are mutually interpenetrated, entangled, interwoven and felted under the repeated action of external force to generate fulling. Although the fulling enables the wool fabric to have the effects of beautiful appearance, thick and soft hand feeling and good heat preservation performance, the size of the wool fabric is easy to shrink and deform in the washing process. Therefore, in order to improve the anti-felting property of wool textiles and the dimensional stability of wool textile products and enable the products to achieve the effect of machine washing, the surface scale modification treatment of wool fibers is needed from the source.

At present, the main methods for modifying and shrink-proofing wool surface scales comprise: chlorination, overlay, protease, etc. Most widely, chlorination shrink-proofing treatment organic halide AOX (which is an absorbable organic halide) generated during chlorination treatment severely pollutes the environment.

Chinese patent CN201010605809.9 reports that potassium permanganate and DCCA are added into clean water in the form of catalyst, and then chlorine gas is introduced to carry out shrink-proof and scale-stripping process on wool tops, and the method reduces the chlorine gas consumption by 30% on the original basis. Although the method is an improvement on the traditional chlorination method, the method still uses chlorine gas and still causes serious environmental pollution. The covering method is to deposit a layer of resin film on the surface of wool to fill the scale and gap on the surface of wool so as to smooth the surface of wool and further reduce the surface friction effect of fiber. Although this treatment improves the felting properties of the fibers to some extent, it seriously affects the hand of the wool fabric and is not always durable enough. The protease method is to use the hydrolysis of the peptide bond of macromolecule on the surface of wool fiber by protease to partially dissolve the scales and cell membrane compound of wool, so as to achieve the purpose of partially or completely removing the scales. The treatment method has the advantages of mild treatment conditions, energy conservation, pollution reduction and the like, and is an environment-friendly wool anti-felting finishing method. However, the shrink-proof effect of wool treated with protease alone has not yet met the practical need, and therefore, in many cases, wool is subjected to a biological modification treatment with protease, and the wool is subjected to a pretreatment (for example, a pre-oxidation treatment with a strong oxidizing agent such as potassium permanganate, or a pretreatment treatment with a chloride solvent). The pretreatment methods have the defects of overlong treatment time, easy inactivation of enzyme, difficult control of treatment conditions and the like.

Furthermore, although there have been researchers attempting to develop a chlorine-free shrink-proofing process for wool materials, there are the following disadvantages: (a) the treatment time is long (the treatment quality cannot be reduced to be within 30 minutes); (b) the treatment capacity is limited, and the method is not suitable for industrial application; (c) the treatment quality has large fluctuation, and wool processing products with uniform treatment effect are difficult to obtain. Therefore, in the main wool material processing countries such as China, no chlorine-free shrink-proof treatment process is adopted to process wool materials in actual production at present.

In conclusion, there is an urgent need in the art to develop a wool shrink-proof treatment process which is environment-friendly, simple and controllable in process, durable in shrink-proof effect, high (or rapid) in treatment efficiency, and suitable for mass production.

Disclosure of Invention

The invention aims to provide a wool shrink-proof treatment process which is environment-friendly, simple and easy to control, durable in shrink-proof effect, high (or rapid) in treatment efficiency and suitable for large-scale production.

In a first aspect of the present invention, there is provided a shrink-proofing agent for chlorine-free shrink-proofing treatment, comprising: (a) optionally a solvent; (b) a protease; and (c) an organophosphinic compound represented by formula A and optionally an inorganic salt;

P-(X)₃A

wherein each X is independently selected from the group consisting of: substituted or unsubstituted C1-C10 hydrocarbyl, wherein said substitution refers to having one or more substituents selected from the group consisting of: -OH, -COOH (carboxyl), C2-C8 ester, -SH, -CN, C1-C3 alkyl, C1-C3 alkoxy;

and at least one X is a substituted C1-C10 hydrocarbyl group having a-OH or COOH substituent;

the weight ratio of the protease to the organic phosphine compound is 0.2-10: 0.5-20;

and the protease in the shrink-proof treatment agent is selected from the group consisting of: a neutral protease, an alkaline protease, or a combination thereof.

In another preferred embodiment, the chlorine-free treatment comprises desquamation/shrinkproof treatment of the wool material and/or the wool product.

In another preferred example, the wool material comprises wool tops.

In another preferred embodiment, the weight ratio of the protease to the organophosphinic compound is 0.5-5: 1-10; more preferably 1 to 5: 1-10.

In another preferred embodiment, the shrink-proof treatment agent further contains an alkaline compound.

Preferably, the basic compound is selected from the group consisting of: an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal carbonate, an alkaline earth metal carbonate, an alkali metal bicarbonate, an alkaline earth metal bicarbonate, or a combination thereof.

In another preferred embodiment, the basic compound is selected from the group consisting of: NaOH, KOH, Ca (OH)₂、Na₂CO₃、K₂CO₃Or a combination thereof.

In another preferred embodiment, the "chlorine-free" means that the shrink proofing agent does not contain an organic chlorine compound, nor a hypochloride compound selected from the group consisting of: containing ClO^-Ionic (radical) compound capable of generating ClO^-Ionic compounds (e.g., chlorine).

In another preferred embodiment, the content of the hypochlorous acid compound in the shrink-proof treatment agent is less than or equal to 0.05 wt%, preferably less than or equal to 0.01 wt%, more preferably less than or equal to 0.001 wt%, and most preferably about 0.

In another preferred embodiment, the shrink-proof treatment agent is in a liquid state (i.e., a treatment liquid).

In another preferred embodiment, the solvent is selected from the group consisting of: water or an aqueous solvent.

In another preferred embodiment, the shrink-resistant treatment agent is a solid, semi-solid, and can be reconstituted into a treatment solution by the addition of a solvent (e.g., water) at the time of application.

In another preferred embodiment, the concentration of the organophosphinic compound in the treatment solution (or reconstituted treatment solution) is 1-10g/L, preferably 1.5-10g/L, and more preferably 5-10 g/L.

In another preferred embodiment, the concentration of the protease in the treatment solution (or reconstituted treatment solution) is 0.1-25g/L, preferably 0.2-10g/L, more preferably 0.5-5 g/L.

In another preferred embodiment, the concentration of the inorganic salt in the treatment solution (or reconstituted treatment solution) is 0.01-10g/L, preferably 0.05-5g/L, more preferably 0.1-2g/L

In another preferred embodiment, 2 xs are the same.

In another preferred embodiment, 3 xs are identical.

In another preferred embodiment, 3 xs are different from each other.

In another preferred embodiment, each X is independently selected from the group consisting of: substituted or unsubstituted C1-C6 hydrocarbyl.

In another preferred embodiment, the C1-C10 hydrocarbon group comprises C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl and C3-C8 cycloalkyl.

In another preferred embodiment, the C1-C10 hydrocarbyl groups include C1-C10 alkyl and C3-C8 cycloalkyl.

In another preferred embodiment, when the shrink-proof treatment agent contains one or more components selected from the group consisting of protease, organic phosphine compound, inorganic salt, and surfactant, the content thereof is as follows:

in another preferred embodiment, the amount (wt%) of the protease in the shrink-proofing agent is not more than (≦) the amount (wt) of the organophosphinic compound.

In another preferred embodiment, when the shrink-proof treatment agent is an aqueous solution or reconstituted into an aqueous solution, the pH thereof is 6.5 to 12, preferably 7 to 11.5, more preferably 7.5 to 10.5.

In another preferred embodiment, the protease is an alkaline protease.

In another preferred embodiment, the organic phosphine compound is a water-soluble aliphatic organic phosphine compound.

In another preferred embodiment, the water solubility refers to the solubility of the organophosphinic compound in 100g of water at 25 ℃ being 0.1g or more, preferably 0.5g or more, more preferably 2g or more, such as 0.1 to 10g or 0.5 to 5 g.

In another preferred embodiment, the organophosphinic compound has the formula:

P-(R₁-R₂)₃I

wherein,

R₁is a substituted or unsubstituted C2-C8 alkylene (preferably C1-C6 alkylene); and/or

R₂Selected from the group consisting of: -OH, -COOH, or C2-C8 ester group, alkali metal, or alkaline earth metal.

In another preferred embodiment, in the compounds of formula I,

R₁is unsubstituted C1-C6 alkylene; and/or

R₂Selected from the group consisting of: -OH, and-COOH.

In another preferred embodiment, R₁Selected from the group consisting of: methylene, ethylene, propylene, butylene, pentylene, hexylene, or combinations thereof.

In another preferred embodiment, the aliphatic organophosphinic compound is selected from the group consisting of: tris (3-hydroxypropyl) phosphine, tris (3-carboxypropyl) phosphine, tris (2-hydroxyethyl) phosphine, tris (4-carboxybutyl) phosphine, or a combination thereof.

In another preferred embodiment, the inorganic salt is selected from the group consisting of: a Ca salt, a Mg salt, a Na salt, a Zn salt, an Al salt, a Ba salt, or a combination thereof.

In another preferred embodiment, the inorganic salt is selected from the group consisting of: a hydrochloride, sulfate, carbonate, bicarbonate, nitrate, nitrite, phosphate, monohydrogen phosphate, dihydrogen phosphate, or a combination thereof.

In another preferred embodiment, the inorganic salt is selected from the group consisting of: mg (NO)₃)₂Sodium phosphate, calcium hydrogen phosphate and CaCl₂Or a combination thereof.

In another preferred embodiment, the surfactant is selected from the group consisting of: a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, or a combination thereof.

In another preferred embodiment, the shrink-proof treatment agent further comprises a pH buffering agent.

In another preferred embodiment, the pH buffer is present in an amount of 0.1 to 10g/L, preferably 0.2 to 5 g/L.

In another preferred embodiment, the pH buffer is selected from the group consisting of: disodium hydrogen phosphate-sodium dihydrogen Phosphate Buffer (PBS), NaHCO₃-Na₂CO₃A buffering agent, or a combination thereof.

In another preferred embodiment, the shrink-proof treatment agent is in a liquid state at 25-80 ℃.

In another preferred embodiment, the shrink-proof treatment agent is in a liquid state at the following use temperatures: 30-70 deg.C, preferably 40-60 deg.C, more preferably 45-55 deg.C.

In another preferred embodiment, in said chlorine-free treatment, the treated wool tops are of a size of 10-30 g/m/root wool top, preferably 20-25 g/m/root wool top.

In another preferred embodiment, in the chlorine-free treatment, n wool tops are treated simultaneously in parallel, wherein n is 10 to 100, 20 to 70, preferably 30 to 60.

In a second aspect of the present invention, there is provided a shrink-proofing treatment apparatus for chlorine-free wool tops or wool products, the apparatus comprising:

the multi-padding device comprises n independent padding devices which are continuously arranged, wherein each padding device comprises a soaking tank and a rolling roller, the soaking tank is used for placing shrink-proof treatment liquid for chlorine-free shrink-proof treatment, so that wool tops or wool products to be treated are soaked in the treatment liquid; the rolling rollers are used for rolling soaked wool tops or wool products, and the wool tops or wool products after being rolled by the upstream rolling rollers sequentially enter a soaking groove and rolling rollers of a downstream padding device so as to repeat soaking and rolling treatment, wherein n is a positive integer of 2-20;

a washing device for washing the padded wool tops or wool products to form washed wool tops or wool products;

the enzyme inactivation device is used for carrying out alkaline inactivation treatment on the residual protease in the washed wool tops or wool products to form enzyme-inactivated wool tops or wool products;

optionally a softening device for softening the enzyme-inactivated wool tops or wool products to form softened wool tops or wool products; and

and an optional dryer for drying the soft-treated wool tops or wool products obtained in the previous step.

In a third aspect of the present invention, there is provided a shrink-proof treatment method for chlorine-free wool tops or wool products, comprising the steps of:

(a) providing chlorine-free wool tops or wool products to be treated and the shrink-proof treatment agent for chlorine-free wool tops or wool products according to the first aspect of the invention;

(b) carrying out n-times padding treatment on the chlorine-free wool tops or wool products to be treated by using the shrink-proof treatment agent so as to obtain padded wool products, wherein n is a positive integer of 2-20;

(c) washing the padded chloride-free wool tops or wool products with water to obtain washed chloride-free wool tops or wool products;

(d) and carrying out enzyme inactivation treatment on the washed chlorine-free wool tops or wool products so as to obtain the shrink-proof chlorine-free wool tops or wool products.

In another preferred example, n is a positive integer of 3 to 10.

In another preferred embodiment, during and/or after said n-pad treatment, the treatment with a treatment liquor containing only protease but no said organophosphinic compound may additionally be performed.

In another preferred embodiment, the total time T of the padding treatment of step (b) is less than or equal to 15 minutes, preferably less than or equal to 10 minutes, more preferably less than or equal to 5 minutes, and most preferably less than or equal to 3 minutes.

In another preferred embodiment, the chlorine-free wool tops or wool products to be treated in step (a) are smoothed.

In another preferred embodiment, the wool tops comprise ingredients selected from the group consisting of: wool, cashmere, or a combination thereof.

In another preferred embodiment, the size of the wool tops is 40-150, preferably 40-120, and more preferably 56-100.

In another preferred embodiment, in step (b), the temperature of said infiltration/rolling operation is in the range of 5 to 80 ℃, preferably 10 to 60 ℃, more preferably 25 to 50 ℃, most preferably 40 to 50 ℃.

In another preferred embodiment, in step (b), the total time of the soaking/rolling operation is not particularly limited, and is usually 1 to 20 minutes, preferably 1 to 10 minutes, and more preferably 1 to 5 minutes.

In another preferred embodiment, in step (c), the washing temperature with water is not particularly limited, and is usually 5 to 60 ℃, preferably 10 to 50 ℃, more preferably 20 to 40 ℃, and most preferably 20 to 30 ℃.

In another preferred example, in the step (c), the washing time with water is not particularly limited, and is usually 30 seconds to 120 minutes, preferably 1 minute to 60 minutes, more preferably 2 to 30 minutes.

In another preferred embodiment, the enzyme inactivation may be performed under conventional inactivation conditions, so long as the residual protease is inactivated or substantially inactivated.

In another preferred embodiment, no hypochlorites are used in the process.

In another preferred example, in step 2), the ratio of the volume of the shrink-proof treatment liquid to the weight of the wool product to be treated is not particularly limited as long as the wool top or the wool product to be treated can be soaked.

In another preferred embodiment, in step 2), the number of padding times may be the same or different, preferably the same.

In another preferred embodiment, in step 2), the number of padding times is 3 to 15, preferably 4 to 12, and more preferably 5 to 10.

In another preferred embodiment, the padding in step 2) is performed for 3-1000s, preferably 5-800s, more preferably 8-600s, and most preferably 10-300 s.

In another preferred embodiment, the padded wool product obtained in step 2) has a wet pick up of 50 to 160 wt%, preferably 60 to 150 wt%, more preferably 80 to 140 wt%.

In another preferred embodiment, step 2) is repeated 3-15 times, preferably 4-12 times, more preferably 5-10 times before step 3).

In another preferred embodiment, before repeating step 2), the method further comprises the following steps: and replacing the shrink-proof treatment liquid.

In another preferred embodiment, in step 3), the temperature of the water used for the water washing is 10 to 40 ℃, preferably 20 to 30 ℃.

In another preferred embodiment, the water used for the water washing has a pH of 6.5 to 7.5, preferably 7.

In another preferred example, in step 3), the padded wool product obtained in step 2) is washed with a certain amount of water.

In another preferred embodiment, the number of water washing in step 3) is 1 to 6, preferably 2 to 4.

In another preferred embodiment, the time for washing in step 3) is 1 to 60 minutes, preferably 1 to 30 minutes, and more preferably 1 to 10 minutes.

In another preferred embodiment, step 3) is repeated before step 4), wherein the number of repetitions is 1-6, preferably 2-4.

In another preferred example, in step 4), the inactivation treatment is performed in a manner selected from the group consisting of: hot water inactivation and hydrogen peroxide (H)₂O₂) Inactivation, or a combination thereof.

In another preferred embodiment, the hot water used for the inactivation is at a temperature of 85-100 deg.C, preferably 90-98 deg.C, more preferably 92-96 deg.C.

In another preferred embodiment, the treatment time for hot water inactivation is 5-300s, preferably 8-200s, more preferably 10-100 s.

In another preferred example, in step 4), the treatment time of the hydrogen peroxide inactivation treatment is 5 to 300s, preferably 8 to 200s, and more preferably 10 to 100 s.

In another preferred embodiment, the following steps are optionally included after the step 4):

5) softening the product obtained in the step 4) to obtain the required wool product; and

6) optionally dehydrating and/or drying the product obtained in the previous step to obtain the desired wool product.

In another preferred example, the softening treatment in the step 5) is to soak the product obtained in the step 4) with a softening treatment agent.

In another preferred example, in the step 5), the dosage ratio of the product obtained in the step 4) and the softening treatment agent is a conventional dosage ratio.

In another preferred embodiment, the soaking time of the softening treatment in step 5) in the treatment agent is 5-200s, preferably 8-100s, more preferably 10-50 s.

In another preferred embodiment, the number of softening treatments in step 5) is 1-10, preferably 2-5, and more preferably 3-4.

In another preferred embodiment, the temperature of the treating agent used in the softening treatment in step 5) is 25-65 ℃, preferably 30-50 ℃.

In another preferred embodiment, the pH of the treatment agent used in the softening treatment of step 5) is 5 to 8, preferably 5.5 to 7.5.

In another preferred embodiment, the concentration of the treating agent used in the softening treatment of step 5) is 5-100g/L, preferably 10-50g/L, and more preferably 15-30 g/L.

In another preferred embodiment, the softening treatment in step 5) is performed by using a treating agent selected from the group consisting of: a wool smoothing agent, a wool softening agent, or a combination thereof.

In another preferred embodiment, the temperature of the drying treatment in step 6) is 60-100 ℃, preferably 70-90 ℃.

In another preferred example, in step 6), the drying treatment time at the treatment temperature is 1 to 30 minutes, preferably 3 to 15 minutes.

In a fourth aspect of the invention, there is provided a shrink-resistant chlorine-free wool product which is free of organic chlorine residues.

In another preferred embodiment, the wool product is shrinkproof treated by the shrinkproof treatment process (method) of the invention.

In another preferred embodiment, the wool product is shrink-proof treated with the shrink-proof treatment agent for chlorine-free wool tops or wool products according to the first aspect of the present invention.

In another preferred embodiment, the wool product is chlorine-free treated using the shrink-proof treatment apparatus of the second aspect of the invention.

In another preferred embodiment, after the shrink-proof treatment, the treated chlorine-free wool product has a surface layer of wool having a scale removal rate of 80-100%, preferably 90-100%, more preferably 95-100%, such as 99-100%, compared to the wool product to be treated.

In another preferred embodiment, the treated chlorine-free wool product after treatment with the shrink-proofing treatment has a shrinkage after treatment with the shrink-proofing treatment method of < 10% absolute, preferably < 8% absolute, preferably < 6% absolute, more preferably < 5% absolute, most preferably < 3% absolute, compared to the wool product to be treated, wherein the determination is the International wool Secretariat TWC.TM31 test method,

in another preferred embodiment, the treated chlorine-free wool product after the shrink-proof treatment maintains a tenacity of 80% or more, preferably 82% or more, more preferably 84% or more, compared to the wool product to be treated.

In another preferred embodiment, the elongation of the treated chlorine-free wool product after the shrink-proof treatment is maintained at 70% or more, preferably 75% or more, more preferably 80% or more, compared to the wool product to be treated.

In another preferred embodiment, the treated chlorine-free wool product has a drip diffusion time of 30s or less, preferably 15s or less, more preferably 10s or less.

In a fifth aspect of the invention there is provided an article comprising or consisting of a wool product according to the fourth aspect of the invention.

In another preferred embodiment, the product comprises wool tops, carpets and clothes.

In a sixth aspect of the invention, there is provided the use of an anti-shrink treatment according to the first aspect of the invention for chlorine-free anti-shrink treatment of wool tops or wool articles.

In the seventh aspect of the invention, a shrink-proof treatment fluid for chlorine-free wool tops and wool products is provided, which mainly comprises the following components: protease, water-soluble aliphatic tri-substituted organic phosphine compound and inorganic salt; the structure of the water-soluble aliphatic tri-substituted organic phosphine is as follows: p- (R-S)₃Wherein R is alkyl containing 1-6 carbon atoms, S is hydroxyl or carboxyl and derivatives thereof; the mass concentration of the composite is 1-10 g/L; the inorganic salt is calcium chloride, and the concentration of the inorganic salt is 0-2 g/L.

In another preferred embodiment, the tri-substituted organophosphine is: at least one of tris (3-hydroxypropyl) phosphine, tris (3-carboxypropyl) phosphine, tris (2-hydroxyethyl) phosphine, and tris (4-carboxybutyl) phosphine.

In an eighth aspect of the present invention, there is provided a continuous process for shrink-proofing chlorine-free wool tops and wool products, comprising the steps of:

1) shrink-proof treatment: the wool tops and wool products are arranged flatly and conveyed at a constant speed through rollers to enter a plurality of liquid tanks with shrink-proof treatment to be alternately soaked and rolled for 3-10 times, and the process conditions are as follows: the pH value of the shrink-proof treatment liquid is 7-10.5, and the temperature is 40-50 ℃; the rolling liquid ratio of the belt is 60-150%; the process conveying speed is 3-15 m/min, and the total time of infiltration and rolling is 1-5 min;

2) washing with water: conveying the treated wool tops into 1-4 clear water tanks for washing for multiple times under the action of a roller to remove residual biological enzyme activators and enzyme preparations and prevent the wool from being eroded continuously;

3) inactivation of protease: uniformly and quickly passing the washed wool tops through a hot water tank at 85-95 ℃ or a solution containing 0-1 g/L of hydrogen peroxide, and inactivating the protease which is not completely washed away;

4) softening treatment: soaking the wool tops subjected to inactivation treatment in a groove of a conventional wool smoothing agent or an organic silicon softening agent for general softening treatment to improve the hand feeling of the wool fabric;

5) dehydrating and drying;

the shrink-proof treatment liquid mainly comprises:

the concentration of the tri-substituted organic phosphine is 1-10g/L

Calcium chloride with concentration of 0.3-2 g/L

Protease with a concentration of 0.5-5g/L

The balance of water

The tri-substituted organic phosphine is as follows: at least one of tris (3-hydroxypropyl) phosphine, tris (3-carboxypropyl) phosphine, tris (2-hydroxyethyl) phosphine, and tris (4-carboxybutyl) phosphine.

In another preferred embodiment, the soaking and the extruding or rolling are repeated for 3 to 10 times; the total time of the soaking treatment is 1-5 minutes; the process conveying speed is 3-8 m/min.

In another preferred example, the wool tops are 56-100 counts of wool or cashmere.

It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.

Drawings

FIG. 1 is a diagram showing the scale stripping effect of wool fibers in example 1 of the present invention.

FIG. 2 is a diagram showing the scale stripping effect of wool fibers in example 2 of the present invention.

FIG. 3 is a diagram showing the scale stripping effect of wool fibers in example 3 of the present invention.

FIG. 4 is a diagram showing the scale stripping effect of wool fibers in example 4 of the present invention.

FIG. 5 is a diagram showing the scale stripping effect of wool fibers in example 5 of the present invention.

FIG. 6 is a block flow diagram of one example of a process of the present invention.

FIG. 7 is a schematic view of a chlorine-free treatment apparatus of the present invention.

Detailed Description

The present inventors have conducted extensive and intensive studies for a long time and have unexpectedly prepared a scale-removing and shrink-proofing process for chlorine-free wool tops/wool products and a corresponding shrink-proofing agent and apparatus. The process and the shrink-proof treatment fluid can efficiently and quickly remove the scale layer on the surface of the wool fiber under the chlorine-free condition to modify the scale layer, thereby achieving the purposes of improving the felting property of the wool product and improving the dimensional stability of the product. On this basis, the inventors have completed the present invention.

Specifically, the invention provides a continuous processing technology for shrink-proof treatment of chlorine-free wool tops and wool products. The method comprises the steps of shrink-proof treatment, water washing, protease inactivation, softening treatment, dehydration and drying, wherein according to the characteristic that wool fibers are protein fibers, a high-efficiency integrated catalytic system consisting of an activating agent with a protease and a water-soluble aliphatic tri-substituted organic phosphine structure, metal salt and a nonionic surfactant is selected, and a scale layer on the surface of the wool fibers can be removed synergistically and efficiently to modify the scale layer, so that the felting property of wool products is improved, the size stability of the products is improved, and the fabrics have the anti-pilling property and smooth handfeel. The invention can completely replace chlorination shrinkage-proof method in the prior art, avoids environmental pollution caused by chlorination method, is a clean treatment process meeting environmental requirements, and has no problem of chlorination pollution. The method has the advantages of small reagent dosage, low cost, simple process, low requirement on equipment, continuous operation and realization of industrial production.

Term(s) for

As used herein, the term "wool material" includes wool, wool tops, or semi-finished products thereof that are not scale removed and shrink resistant. In addition, the term may also include wool materials that have not been completely descaled, despite being subjected to a scale and shrink resistant treatment.

As used herein, the terms "wool top/wool product," "wool top and/or wool product" are used interchangeably to refer to either wool top, or wool product, or a combination of both. The term may include both wool tops/wool articles to be treated and during or after treatment.

As used herein, the terms "chlorine-free product of the present invention", "chlorine-free wool tops/wool products of the present invention" are used interchangeably to refer to wool tops/wool products obtained by the chlorine-free scale removal and shrink prevention treatment process of the present invention. The chlorine-free descaling shrink-proof process of the invention does not use organic chlorine compounds and hypochlorous acid compounds (i.e. compounds containing ClO-ions or compounds capable of generating ClO-ions), so that the chlorine-free wool product (including wool tops/wool products) with excellent safety is obtained.

As used herein, the terms "shrink-proofing agent (or liquid) of the present invention", "scale-removing shrink-proofing agent (or liquid) of the present invention", "chlorine-free shrink-proofing treatment (or liquid)", "chlorine-free scale-removing shrink-proofing treatment (or liquid)" are used interchangeably and refer to the shrink-proofing treatment (or liquid) of the chlorine-free wool top/wool product of the present invention.

Shrink-proof treatment agent for chlorine-free wool top/wool product

The invention provides a descaling shrink-proof treatment agent for chlorine-free wool tops/wool products. The scale removal and shrink prevention treatment agent of the present invention may be in a solid state or a liquid state. When the non-chlorine shrink-proof agent of the present invention is in a solid state, it can be reconstituted into a corresponding shrink-proof treatment solution for non-chlorine wool tops/wool products by adding water (or aqueous solvent).

In addition, the present invention, wherein the combinations may be mixed together (i.e., present as a mixture) or may be present as unmixed, is formulated on-site at the time of use.

In a preferred embodiment, the shrink-proof treatment fluid for the chlorine-free wool tops and wool products mainly comprises the following components: protease, water-soluble aliphatic tri-substituted organic phosphine compound and inorganic salt; the structure of the water-soluble aliphatic tri-substituted organic phosphine is as follows: p- (R-S)₃Wherein R is alkyl containing 1-6 carbon atoms, S is hydroxyl or carboxyl and derivatives thereof; the mass concentration of the composite is 1-10 g/L; the inorganic salt is calcium chloride, and the concentration of the inorganic salt is 0-2 g/L.

In the present invention, preferred trisubstituted organophosphines include (but are not limited to): tris (3-hydroxypropyl) phosphine, tris (3-carboxypropyl) phosphine, tris (2-hydroxyethyl) phosphine, tris (4-carboxybutyl) phosphine, or a combination thereof.

In another preferred embodiment, the protease comprises a neutral protease, an alkaline protease, or a combination thereof.

In another preferred embodiment, the neutral protease is a protease with neutral pH optimum (e.g., about 6.8-7.0), and the molecular weight is generally 35-40 kD. Neutral proteases suitable for use in the present invention include commercially available or conventionally prepared neutral proteases, such as neutral proteases from microorganisms, Neutrase, or combinations thereof.

In another preferred embodiment, the alkaline protease is a protease with an alkaline pH optimum (e.g., about 9-11), and the molecular weight is typically 26-34 kD. The alkaline protease suitable for use in the present invention includes alkaline proteases commercially available or prepared by conventional methods, such as alkaline protease derived from Bacillus licheniformis (molecular weight about 27300, endoprotease belonging to the serine type), alkaline protease derived from Streptomyces, 2709 alkaline protease, Novo protease, Carsberg protease, etc.

In the shrink-resistant fluid of the present invention, the concentration of the protease is generally 0.1 to 25g/L, preferably 0.2 to 10g/L, more preferably 0.5 to 5g/L, and the amount (or concentration) of the protease is generally 1 × 10 in terms of International Units (IU)⁴-1×10⁸U/L shrink-proof liquid, preferably 5 × 10⁴-5×10⁷U/L, more preferably 1 × 10⁵-1×10⁷U/L。

In another preferred embodiment, the shrink-proof treatment liquid of the present invention further contains a nonionic surfactant (e.g., JFC) or an anionic surfactant. Representative nonionic surfactants include (but are not limited to): polyoxyethylene type surfactants such as alkylphenol ethoxylates (APEO), fatty acid polyoxyethylene esters (AE), fatty acid methyl ester ethoxylates (FMEE), and polyhydric alcohol 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 dodecylbenzene sulfonate, Sodium Dodecyl Sulfate (SDS), cetyl sulfonate, or a combination thereof.

Generally, the concentration of the surfactant is 0.001 to 1.0 wt% or 0.01 to 10g/L, preferably 0.1 to 2 g/L.

Preferably, the pH value of the shrink-proof treatment liquid is 7-10.5.

In another preferred embodiment, the invention provides a shrink-proof treatment fluid for chlorine-free wool tops and wool products, which mainly comprises the following components in percentage by mass:

the concentration of the tri-substituted organic phosphine is 1-10g/L

Calcium chloride with concentration of 0-2 g/L

Protease with a concentration of 0.5-5g/L

The balance of water.

The shrink-proof treatment agent (liquid) can directly treat wool tops/wool products, thereby obtaining the scale-removed shrink-proof wool tops/wool products.

The shrink-proofing treatment liquid of the present invention does not contain an organic chlorine compound nor a hypochlorous acid-based compound (i.e., a compound containing ClO-ions, or a compound capable of generating ClO-ions such as Cl) as compared with the chlorine-containing shrink-proofing treatment liquid of the prior art₂). The organic chlorine compound comprises DCCA, chloroform, carbon tetrachloride, TCCA and the like.

In another preferred embodiment, the shrink-proof treatment fluid for chlorine-free wool tops and wool products mainly comprises the following components: protease, water-soluble aliphatic tri-substituted organic phosphine compound and inorganic salt.

Wherein the structure of the water-soluble aliphatic tri-substituted organic phosphine is as follows: p- (R-S)₃，

R is a C1-6 alkyl group, and S is hydroxyl (-OH) or carboxyl (-COOH) and its derivatives. The using amount is 1 g-10 g/L; the inorganic salt is calcium chloride and the like, and the dosage of the inorganic salt is 0 g/L-2 g/L.

The protease is neutral protease, alkaline protease and the like, and the concentration of the protease is 0.5 g/L-5 g/L.

The pH value of the shrink-proof treatment liquid is 7-10.5.

In another preferred example, the shrink-proof treatment liquid comprises the following main components in percentage by mass:

the concentration of the tri-substituted organic phosphine is 1-10g/L

Calcium chloride with concentration of 0-2 g/L

Protease with a concentration of 0.5-5g/L

The balance of water.

Shrink-proof treatment method (technology) for chlorine-free wool top or wool product

The invention also provides a shrink-proof treatment method of the chlorine-free wool tops or wool products, wherein the chlorine-free descaling shrink-proof treatment liquid is used for treating the wool tops/wool products, so that the wool tops/wool products with excellent shrink-proof performance are obtained. It should be understood that while the shrink-proofing treatment fluid and method of the present invention is sufficiently effective to achieve scale removal to achieve a fully descaled wool product, the method of the present invention can also be used to produce a non-fully descaled (i.e., partially descaled) wool product, as desired.

As shown in fig. 6, in a preferred embodiment, the present invention provides a continuous processing technology for shrink-proof treatment of chlorine-free wool tops and wool products, comprising the following steps:

1) descaling and shrink-proofing treatment: the wool top/wool product is arranged, leveled and conveyed into one or more liquid tanks with shrink-proof treatment at a constant speed by a roller, and is alternately soaked and rolled (for example, for 3 to 10 times), and the process conditions are as follows: the pH value of the shrink-proof treatment liquid is 7-10.5, and the temperature is 40-50 ℃; wherein the total time of infiltration and rolling is 1-5 minutes;

preferably, the wool tops are leveled side by side and conveyed into a plurality of liquid tanks with shrink-proof treatment at a constant speed through rollers to be alternately soaked and rolled (extruded) for 3-10 times, and the process conditions are as follows: the pH value of the shrink-proof treatment liquid is 7-10.5, and the temperature is 40-50 ℃; the rolling liquid ratio of the belt is 60-150%; the process conveying speed is 3-15 m/min (preferably 3-8 m/min), and the total time of infiltration and rolling is 1-5 min;

3) inactivation of protease: quickly passing the washed wool tops through a hot water tank at 85-95 ℃ or a solution containing 0.1-1 g/L of hydrogen peroxide, and inactivating the protease which is not completely washed away;

5) dehydrating and drying;

the shrink-proof treatment liquid mainly comprises:

the concentration of the tri-substituted organic phosphine is 1-10g/L

Calcium chloride with concentration of 0.3-2 g/L

Protease with a concentration of 0.5-5g/L

The balance of water

In another preferred embodiment, the soaking and rolling operations can be repeated a plurality of times, for example 3-10 times.

In the present invention, 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, more preferably 1 to 5 minutes.

The present invention requires only a very short total time for the soaking/rolling operation because the chlorine-free scale removal shrink prevention treatment of the present invention can remove scale very efficiently with little damage.

In another preferred embodiment, the chlorine-free shrink-proofing process of the present invention is continuous, wherein the conveying speed in the continuous process may be 0.5-20 m/min, preferably 1-10 m/min.

In a preferred embodiment of the present invention, the treatment process comprises:

1) shrink-proof treatment: and (3) carrying out scale stripping treatment on wool tops under the action of a protease integrated catalytic system. Under the condition that each wool top has no tension, the wool tops are flattened side by side, conveyed into a high-efficiency catalytic system composed of protease, a water-soluble aliphatic tri-substituted organic phosphine biological enzyme activator and an inorganic salt catalyst at a constant speed through a roller, or a conventional nonionic surfactant can be added as an auxiliary penetrating agent, the pH value is 7-10.5, the temperature of the catalytic system is 40-50 ℃, after the wool tops are completely soaked (the soaking speed and the exchange speed of wool fibers and surrounding treatment liquid can be accelerated through equipment such as a suction roller), the wool tops are extruded through the roller action, and the liquid carrying rate is 60-150%. And then conveying the wool tops into a catalytic system at the temperature of 40-50 ℃, extruding the wool tops through a roller after soaking, repeatedly padding, controlling the process speed at 3-15 m/min (optionally 3-8 m/min), carrying out padding for 3-10 times in treatment fluid of the same integrated catalytic system under the same treatment condition according to the difference of wool counts and product quality requirements, and finally conveying the wool tops to subsequent related treatment tanks to achieve the continuous automatic effect.

2) And (5) washing with water. And (3) conveying the treated wool tops into 1-4 clear water tanks for washing for multiple times under the action of a roller to remove residual biological enzyme activators and enzyme preparations and prevent the wool from being eroded continuously.

3) And (4) inactivating the protease. And (3) uniformly and quickly passing the wool tops cleaned in the second step through a boiling water tank or a solution containing 0-1 g/L of hydrogen peroxide. To inactivate proteases that are not completely washed away.

4) And (6) softening. The wool tops after inactivation treatment are soaked in a conventional wool smoothing agent or an organic silicon softening agent (namely, in the groove type softening treatment, universal softening treatment is carried out, and the softening agent is hydrogen-containing silicone oil, amino silicone oil, modified silicone oil or emulsion thereof) so as to improve the hand feeling of the wool fabric.

5) Dehydrating and drying (by conventional method).

Chlorine-free treatment equipment

The invention also provides chlorine-free treatment equipment for the method.

A typical processing apparatus is shown in figure 7. The apparatus comprises:

a multiple padding apparatus 10, comprising n independent padding devices (not shown) arranged in series, each padding device comprising a padding tank and a rolling roller, wherein the padding tank is used for placing a shrink-proof treatment liquid for chlorine-free shrink-proof treatment so that wool tops or wool products to be treated are soaked in the treatment liquid; the rolling rollers are used for rolling soaked wool tops or wool products, and the wool tops or wool products after being rolled by the upstream rolling rollers sequentially enter a soaking groove and rolling rollers of a downstream padding device so as to repeat soaking and rolling treatment, wherein n is a positive integer of 2-20;

a washing device 20 for washing the padded wool tops or wool products to form washed wool tops or wool products;

an enzyme inactivation device 30 for performing alkaline inactivation treatment on the residual protease in the washed wool tops or wool products to form enzyme-inactivated wool tops or wool products;

an optional softening device 40 for softening the enzyme-inactivated wool tops or wool products to form softened wool tops or wool products; and

an optional dryer 50 for drying the soft-treated wool tops or wool articles obtained in the previous step.

In another preferred embodiment, the multiple padding apparatus, the water washing apparatus, the enzyme inactivation apparatus, the optional softening treatment apparatus, and the optional dryer are arranged in sequence.

In another preferred example, one or more auxiliary padding devices are further arranged between or behind the padding devices of the multiple padding device, each auxiliary padding device independently comprises an auxiliary padding tank and an auxiliary rolling roller, wherein the auxiliary padding tank is filled with a protease treatment solution without containing organic phosphine compounds and/or an organic phosphine treatment solution without containing protease.

In another preferred example, the auxiliary soaking tank is an enzyme treatment tank.

In another preferred embodiment, the enzyme treatment tank is located after the 2 nd, 3 rd, 4 th or 5 th padding mangle.

In another preferred embodiment, 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, more preferably 4 to 10.

In another preferred embodiment, the shape and size of each padding device may be the same or different.

In another preferred embodiment, the padding machines are arranged in sequence.

In another preferred embodiment, the soaking tank is filled with the shrink-proof treatment agent (or liquid) according to the first aspect of the present invention.

In another preferred example, the immersion tank is a suction drum wash tank.

In another preferred embodiment, the immersion tank is independently provided or not provided with a heating device or a temperature control device.

In another preferred embodiment, each of said heating means or temperature control means controls the temperature in the range of 25-80 ℃, preferably 30-70 ℃, more preferably 40-60 ℃, most preferably 45-55 ℃.

In another preferred embodiment, the water washing device comprises m water washers, wherein m is a positive integer of 1 to 10, preferably 1 to 6, preferably 2 to 4.

In another preferred example, each water scrubber contains solvent water.

In another preferred embodiment, the temperature of the solvent water in each of the water washers is 10 to 40 ℃, preferably 20 to 30 ℃.

In another preferred embodiment, the pH of the solvent water in each of the water washers is 6.5-7.5, preferably 7 ± 0.2.

In another preferred example, the enzyme inactivation device is a high-temperature inactivation tank and/or a hydrogen peroxide inactivation tank.

In another preferred embodiment, the temperature of the solvent water in the enzyme inactivation device is 85-100 ℃, preferably 90-98 ℃, and more preferably 92-96 ℃.

In another preferred embodiment, the enzyme inactivation device contains H₂O₂The solution of (1).

In another preferred embodiment, said H is contained in a solution contained in said enzyme inactivation device₂O₂The concentration of (B) is 0.01-50g/L, preferably 0.05-30g/L, more preferably 0.1-10 g/L.

In another preferred embodiment, the softening treatment device contains a softening treatment agent selected from the group consisting of: a wool smoothing agent, a wool softening agent, or a combination thereof.

In another preferred embodiment, the concentration of the softening agent in the softening device is about 1-50g/L, preferably 2-40g/L, and more preferably 5-25 g/L.

In another preferred example, the wool softener comprises: a silicone softener.

In another preferred embodiment, the silicone-based softener is selected from the group consisting of: silicone oil, hydrogen silicone oil, amino silicone oil, modified silicone oil, or a combination thereof.

Chlorine-free wool top/wool product

The invention also provides shrink-resistant chlorine-free wool tops/wool products obtained by the chlorine-free shrink-proofing process according to the invention, which have little or no organic chlorine residues.

As used herein, the term "etofencin" or "etofencin" product "refers to a shrink-resistant chlorine-free wool top/wool product that is obtained with the chlorine-free shrink-proof treatment process of the present invention with little or no organic chlorine residue.

The chlorine-free treated wool top or wool product of the present invention (i.e., the affin product) has excellent properties, including (but not limited to):

(a) high scale layer removal rate: the treated wool product has a wool top scale removal rate of 80-100%, preferably 90-100%, more preferably 95-100%, such as 99-100%, compared to the wool product to be treated.

(b) Low shrinkage: the absolute value of the shrinkage of the treated wool product compared to the wool product to be treated is less than or equal to 10%, preferably less than or equal to 8%, preferably less than or equal to 6%, more preferably less than or equal to 5%, most preferably less than or equal to 3%, wherein the determination method is the International wool Secretariat TWC.TM31 test method.

(c) High strength retention: after the shrink-proof treatment method is used for treatment, compared with the wool product to be treated, the strength of the treated wool product is kept to be more than or equal to 80%, preferably more than or equal to 82%, and more preferably more than or equal to 84%.

(d) High elongation retention: after the shrink-proof treatment method is used for treatment, compared with the wool product to be treated, the elongation of the treated wool product is kept to be more than or equal to 70%, preferably more than or equal to 75%, and more preferably more than or equal to 80%.

(e) Excellent wetting and permeability properties: the drip diffusion time (GB/T21655.1-2008) is increased from not less than 10 minutes before treatment to not more than 10 seconds.

Mechanism and advantages of treatment

To facilitate an understanding of the present invention, the present inventors provide the following mechanism. However, it is to be understood that the present invention is not limited by this mechanism.

The inventor finds that some special structures and substances, such as cystine containing disulfide bonds, lipids and the like exist in the scale layer on the surface of the wool, so that protease is difficult to effectively digest and decompose the scale surface layer and high-sulfur proteins in the scale surface layer. However, in the presence of the organic phosphine compound shown in the formula A, the multiple padding process can effectively change the structure of a scale layer on the surface of wool, so that proteins such as high-sulfur protein and the like are more easily decomposed by protease, and can maintain or improve the activity of the protease, thereby realizing descaling and shrink prevention of the wool very efficiently and quickly.

In the case of the preferred treating agents of the present invention, the protease acts to degrade the scales on the surface of the wool fibers mainly by hydrolysis; on one hand, the water-soluble aliphatic tri-substituted organic phosphine can quickly reduce a large number of disulfide bonds in scales and activate reaction substrates through the unique effect of the water-soluble aliphatic tri-substituted organic phosphine on disulfide bonds in wool, so that the reaction of protease and wool macromolecules is facilitated, on the other hand, the water-soluble aliphatic tri-substituted organic phosphine has a good stabilizing effect on the activity of the protease, the reduction of the activity of the protease in an integrated catalytic system can be effectively reduced, and meanwhile, the catalytic effect of the protease can be further activated, so that the quick reaction effect is generated. In addition, the main function of the inorganic salt catalyst is to further activate the protease; and the main function of the surfactant is to assist the treatment fluid to be wetted and penetrated on the surface of the wool fiber as soon as possible.

In the process of the present invention, multiple padding or repeated padding is also a necessary condition for realizing a rapid process of the present invention. In the repeated padding process, the rapid contact and action of the protease and the activating agent with the surface of the wool fiber are forcibly realized, and simultaneously, the cleaning of reactants and hydrolysis products is facilitated, and the further proceeding of the reaction is facilitated.

Compared with the prior art, the invention has the following main advantages:

(1) is environment-friendly, and does not adopt chlorine-containing organic matters or chlorine. The invention uses the high-efficiency catalytic system mainly comprising protease and an activator with a water-soluble organic phosphine structure as a treatment solution to finish wool, utilizes the synergistic effect of the protease and the activator to achieve the mercerization shrink-proof continuous processing of the chlorine-free wool tops, does not generate toxic and harmful substances in the treatment process, fundamentally solves the pollution of the chlorinated mercerization to the environment, accords with the concept of ecological spinning, and does not cause environmental pollution

(2) The process is simple and easy to control.

(3) High processing efficiency and high processing speed. Compared with the known protease shrink-proof process, the method is high in speed, can finish shrink-proof treatment of the wool within 1-5 min, and ensures that the mechanical property of the wool is within an acceptable range.

(4) The anti-felting effect is durable.

(5) Is suitable for large-scale production. The process has low requirement on equipment, can be continuously operated and is beneficial to realizing industrialized production.

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are by weight.

The reagents mentioned in the examples are not specifically indicated, and are all commercially available.

The treating fluid is prepared by weighing protease, a water-soluble aliphatic tri-substituted organic phosphine compound, inorganic salt and a surfactant according to the amount of a main formula and preparing by a general mass concentration (g/L) preparation method. The organic phosphine compounds are all produced by Tianjin coastal oriental science and technology limited.

Example 1

In this example, a continuous quintuple padding process was used to perform chlorine-free shrink-proofing on wool tops.

The specification of the whole wool tops to be treated is 70. The process comprises the following steps:

a first groove: and (5) padding the treatment fluid. The tank is a suction drum (type) washing tank (universal device) with the width of 1 meter, the volume of 360 liters and the circumference of one meter, an automatic heating device (universal device) is arranged in the suction drum tank, an efficient catalytic solution mainly comprising 3g/L of alkaline protease (alkali protease) and 3g/L of tris (3-hydroxypropyl) phosphine (adding 1g/L of nonionic surfactant JFC) is filled, the pH is 9 (taking disodium hydrogen phosphate and sodium dihydrogen phosphate as pH regulators), and the temperature is controlled to be 50 ℃.

The wool tops are evenly laid on a leather roller side by side and enter treatment fluid at a constant speed of 8 m/min, so that the wool tops are completely wetted, and the appearance of each fiber in the wool tops is ensured to be evenly and thoroughly treated; pressurizing the wool tops by a pressurizing roller to ensure that the mangling rate of the wool tops is about 135 percent; the wool tops with enzyme solution were then fed into a second treatment tank at a rate of 8 m/min. 15 seconds are consumed from the time when the wool tops enter the first tank treatment liquid to the time when the wool tops enter the second tank treatment liquid.

A second groove: and (5) padding the treatment fluid. As well as the first slot.

A third groove: and (5) padding the treatment fluid. As well as the first slot.

A fourth groove: and (5) padding the treatment fluid. As well as the first slot.

A fifth groove: and (5) padding the treatment fluid. As well as the first slot. From the start of the first slot to the end of the fifth slot, it took 15 seconds × 5 seconds to 75 seconds.

A sixth groove: and (5) washing with water. And (3) rolling and washing the wool tops to clean the reagents, enzymes and degraded products attached to the surfaces of the wool fibers, wherein the water temperature is normal temperature and the pH value is 7.0.

A seventh groove: and (5) washing for the second time. The same as the sixth groove.

An eighth groove: and (3) washing at high temperature to play a role in enzyme inactivation and prevent subsequent wool fibers from being continuously eroded, wherein the temperature is 95 ℃ and the time is 15 seconds.

A ninth groove: the wool fibers are softened by conventional softening treatment to achieve a softening effect and improve hand feeling. Then the wool tops are dehydrated and dried conventionally (for example, the drying process condition is that the drying temperature is 70-90 ℃ and the drying time is 3-10 minutes).

The speed of the process is 8 m/min, and the treatment solution is padded for 5 times. The scale stripping effect of the wool fiber treated by the process is shown in figure 1.

Compared with the wool before treatment, the strength of the wool treated by the process is kept at 85%, and the elongation is kept at 83%.

The wool treated by the process has the following test result of 5 multiplied by 5A according to the test method of TWC.TM31 of International wool Secretarium: -4.86%.

The chlorine content of the treated wool was measured, and as a result, no residual chlorine-containing component (organic matter) was detected.

Example 2

In this example, a continuous process of six-fold padding was used to perform chlorine-free shrink-proofing on wool tops.

The specification of the full-wool tops to be treated is 56. The process comprises the following steps:

a first groove: and (5) padding the treatment fluid. The tank is a suction drum tank with the width of 1 meter, the volume of 360 liters and the circumference of one meter, an automatic heating device is arranged in the suction drum tank, a high-efficiency catalytic solution containing 3g/L of alkaline protease and 3g/L of tris (3-hydroxypropyl) phosphine is filled in the suction drum tank, the pH value is 10.5, and the temperature is controlled to be 50 ℃.

The wool tops are evenly laid on a leather roller side by side and enter the treatment fluid at a constant speed of 3.8 m/min, so that the wool tops are completely wetted, and the appearance of each fiber in the wool tops is ensured to be evenly and thoroughly treated; pressurizing the wool tops by a pressurizing roller to ensure that the mangling rate of the wool tops is 130%; the wool tops with enzyme solution were then fed into a second treatment tank at a rate of 3.8 m/min. 31.5 seconds are consumed from the time when the wool tops enter the first tank treatment liquid to the time when the wool tops enter the second tank treatment liquid.

A third groove: and (5) padding the treatment fluid. As well as the first slot.

A fifth groove: and (5) padding the treatment fluid. As well as the first slot.

A sixth groove: and (5) padding the treatment fluid. As well as the first slot. From the start of the first slot to the end of the sixth slot, it took 31.5 seconds × 6 to 189 seconds.

A seventh groove: and (5) washing with water. And (3) rolling and washing wool tops to clean reagents, enzymes and degradation products attached to the surfaces of the wool fibers, wherein the water temperature is normal temperature, and the PH is 7.0.

An eighth groove: and (5) washing for the second time. The same as the seventh groove.

A ninth groove: and (3) washing at high temperature to play a role in enzyme inactivation and prevent subsequent wool fibers from being continuously eroded, wherein the temperature is 95 ℃ and the time is 15 seconds.

A tenth groove: wool tops are padded with 20g/L wool softener solution, so that wool fibers are softened to achieve a softening effect, and the hand feeling is improved. The temperature of the softening agent solution is 40 ℃, the pH value is 7.0, and the time is 15 seconds. And then dehydrating and drying the wool tops.

The speed of the process is 3.8 m/min, and the treatment solution is padded for 6 times. The scale stripping effect of the wool fiber treated by the process is shown in figure 2.

Compared with the wool before treatment, the strength of the wool treated by the process is kept 83%, and the elongation is kept 72%.

The wool treated by the process has the following test result of 5 multiplied by 5A according to the test method of TWC.TM31 of International wool Secretarium: -3.82%.

Example 3

The specification of the whole wool tops to be treated is 90. The process comprises the following steps:

a first groove: and (5) padding the treatment fluid. The tank is a suction drum tank with the width of 1 meter, the volume of 360 liters and the circumference of one meter, an automatic heating device is arranged in the suction drum tank, a high-efficiency catalytic solution of 3g/L of alkaline protease, 3g/L of tri (3-carboxypropyl) phosphine and 0.3g/L of anhydrous calcium chloride (adding 1g/L of nonionic surfactant JFC) is filled in the tank, the pH value is 8.5 (adjusting the pH value by using a proper amount of sodium carbonate or sodium hydroxide solution), and the temperature is controlled to be 50 ℃.

A third groove: and (5) padding the treatment fluid. As well as the first slot.

A fifth groove: and (5) padding the treatment fluid. As well as the first slot. From the start of the first slot to the end of the fifth slot, the time taken was 31.5 seconds × 5 to about 158 seconds.

A ninth groove: wool tops are padded with 20g/L wool softener solution, so that wool fibers are softened to achieve a softening effect, and the hand feeling is improved. The temperature of the softening agent solution is 40 ℃, the pH value is 6.0, and the time is 15 seconds. And then dehydrating and drying the wool tops.

The speed of the process is 3.8 m/min, and the treatment solution is padded for 5 times. The scale stripping effect of the wool fiber treated by the process is shown in figure 3.

Compared with the wool before treatment, the strength of the wool treated by the process is maintained at 81%, and the elongation is maintained at 80%.

The wool treated by the process has the following test result of 5 multiplied by 5A according to the test method of TWC.TM31 of International wool Secretarium: -2.98%.

Example 4

The specification of the full-wool tops to be treated is 80. The process comprises the following steps:

a first groove: and (5) padding the treatment fluid. The tank is a suction drum tank with the width of 1 meter, the volume of 360 liters and the circumference of one meter, an automatic heating device is arranged in the suction drum tank, a high-efficiency catalytic solution mainly containing 3g/L of alkaline protease, 3g/L of tri (2-hydroxyethyl) phosphine and 0.3g/L of anhydrous calcium chloride (adding 1g/L of nonionic surfactant JFC) is filled, the pH value is 7.5, and the temperature is controlled to be 50 ℃.

The wool tops are evenly laid on a leather roller side by side and enter the treatment fluid at a constant speed of 4.5 m/min, so that the wool tops are completely wetted, and the appearance of each fiber in the wool tops is ensured to be evenly and thoroughly treated; pressurizing the wool tops by a pressurizing roller to ensure that the mangling rate of the wool tops is 130%; the wool tops with enzyme solution were then fed into a second treatment tank at a rate of 4.5 m/min. 26.7 seconds are spent from the entry of the wool tops into the first tank treatment liquid to the entry of the wool tops into the second tank treatment liquid.

A third groove: and (5) padding the treatment fluid. As well as the first slot.

A fifth groove: and (5) padding the treatment fluid. As well as the first slot. Starting from the first slot to the end of the fifth slot, it took 26.7 seconds × 5 to about 134 seconds.

The speed of the process is 4.5 m/min, and the treatment solution is padded for 5 times. The scale-stripping effect of the wool fibers treated by the process is shown in fig. 4.

Compared with the wool before treatment, the strength of the wool treated by the process is kept at 82%, and the elongation is kept at 81%.

The wool treated by the process has the following test result of 5 multiplied by 5A according to the test method of TWC.TM31 of International wool Secretarium: -3.56%.

Example 5

In this example, a continuous process of seven-pad padding was used to perform chlorine-free shrink-proofing on wool tops.

The specification of the full-wool tops to be treated is 70. The process comprises the following steps:

a first groove: and (5) padding the treatment fluid. The tank is a suction drum tank with the width of 1 meter, the volume of 360 liters and the circumference of one meter, an automatic heating device is arranged in the suction drum tank, high-efficiency catalytic solution mainly containing 2g/L of alkaline protease, 3g/L of tri (4-carboxybutyl) phosphine and 0.3g/L of anhydrous calcium chloride (optional: adding 1g/L of nonionic surfactant JFC or anionic surfactant) is filled, the pH value is 8, and the temperature is controlled to be 50 ℃.

The wool tops are evenly laid on a leather roller side by side and enter treatment fluid at a constant speed of 6 m/min, so that the wool tops are completely wetted, and the appearance of each fiber in the wool tops is ensured to be evenly and thoroughly treated; pressurizing the wool tops by a pressurizing roller to ensure that the mangling rate of the wool tops is 130%; the wool tops with enzyme solution were then fed into a second treatment tank at a rate of 6 m/min. It takes 20 seconds from the entry of the wool tops into the first tank treatment liquid to the entry into the second tank treatment liquid.

A third groove: and (5) padding the treatment fluid. As well as the first slot.

A fifth groove: and (5) padding the treatment fluid. As well as the first slot.

A sixth groove: and (5) padding the treatment fluid. As well as the first slot.

A seventh groove: and (5) padding the treatment fluid. As well as the first slot. From the start of the first slot to the end of the seventh slot, it took 20 seconds × 7 to 140 seconds.

An eighth groove: and (5) washing with water. And (3) rolling and washing the wool tops to clean the reagents, enzymes and degraded products attached to the surfaces of the wool fibers, wherein the water temperature is normal temperature and the pH value is 7.0.

A ninth groove: and (5) washing for the second time. The same as the eighth groove.

A tenth groove: and (3) washing at high temperature to play a role in enzyme inactivation and prevent subsequent wool fibers from being continuously eroded, wherein the temperature is 95 ℃ and the time is 15 seconds.

An eleventh groove: wool tops are padded with 20g/L wool softener solution, so that wool fibers are softened to achieve a softening effect, and the hand feeling is improved. The temperature of the softening agent solution is 40 ℃, the pH value is 6.0, and the time is 15 seconds. And then dehydrating and drying the wool tops.

The speed of the process is 6 m/min, and the treatment solution is padded for 7 times. The scale stripping effect of the wool fiber treated by the process is shown in figure 5.

Compared with the wool before treatment, the strength of the wool treated by the process is kept at 82%, and the elongation is kept at 80%.

The wool treated by the process has the following test result of 5 multiplied by 5A according to the test method of TWC.TM31 of International wool Secretarium: -3.01%.

Example 6

In this example, a fourfold pad continuous process was used to perform chlorine-free shrink-proofing on wool products.

The product to be treated is a wool product (serge). The method comprises the following steps:

the method comprises the following steps of padding protease integrated catalytic treatment fluid by using four groups of Kroy deepim reaction boxes (each group is 1.5 m deep, 1.8 m wide and 0.4 m thick), wherein the treatment fluid mainly comprises the following components: 1.8g/L of alkaline protease, 3.0g/L of tri (4-carboxybutyl) phosphine biological enzyme activator and 0.3g/L of anhydrous calcium chloride (and also can be added with nonionic surfactant JFC1g/L) high-efficiency catalytic solution, the pH value is 7.5, and the temperature is controlled to be 50 ℃. Sequentially feeding the serge to be treated into four groups of Kroy deepim reaction boxes, performing quadruple padding treatment for 2 minutes at a constant speed of 6 meters per minute, controlling the liquid carrying rate between each group at 100%, and then performing water washing, inactivation, softening and drying treatment.

After the treatment, the wool product not only has good shrink-proof performance, but also has greatly improved wetting and penetrating performance, and the dripping water diffusion time (according to GB/T21655.1-2008) is improved to be less than or equal to 10 seconds from more than or equal to 10 minutes before the treatment.

Comparative example 1

Treatment by soaking

The descaling shrink-proof treatment is carried out by adopting a conventional soaking method, and the method comprises the following steps:

the wool tops (70 pieces, 20g) were soaked in the soaking solution sufficiently for 20 minutes or 60 minutes (50 ℃). After the soaking treatment, the post-treatment was carried out by a conventional method (similar to example 1) including 3 times of water washing, then enzyme inactivation treatment and softening treatment, and finally dehydration and drying.

Wherein, the formula of the soaking treatment liquid is as follows: 3g/L of alkaline protease (alkali protease), 1g/L of nonionic surfactant JFC (pH 8.5) and water as a solvent.

The results show that when the soaking time was 20 minutes, the descaling of part of the wool was insufficient. When the soaking time is 60 minutes, the desquamation effect of the wool is basically uniform, but the condition that the desquamation of the wool is insufficient exists in a small amount of wool. This indicates that the soaking process is not suitable for mass production due to long time consumption and non-uniform treatment effect.

Comparative example 2

Soaking-steaming treatment

The comparative example uses a conventional batch type, and the descaling and shrink-proof treatment is carried out by a soaking-steaming method. The method comprises the following steps:

wool tops (70 counts, 20g) were thoroughly soaked in a soaking solution (50 ℃, mangle ratio 120%), presoaked for about 1 minute, and then steamed (50 ℃) in a steaming box for 25 minutes, during which steaming solution (same composition as the soaking solution) was replenished at 5, 10, 15 and 20 minutes. The soak-steam treatment took 26 minutes.

After the soaking-steaming treatment, the post-treatment was carried out by a conventional method (similar to example 1) including 3 times of water washing, then enzyme inactivation treatment and softening treatment, and finally dehydration and drying.

The formulation of the soak solution was similar to that of the soak solution of example 1, but the soak solution did not contain tris (3-hydroxypropyl) phosphine. Namely, the formula is as follows: 3g/L of alkaline protease (alkali protease) and 3g/L of nonionic surfactant JFC1 g/L.

As a result:

after the wool is subjected to the shrink-proof treatment, the sharp corners of the scales on the surface of the wool are basically all cut off. But the uniformity is poor, wherein the surface scales of the thinner wool are fuzzy, and the thicker wool scale layer is very thin, which shows that the treatment process has better stripping effect on the fine wool scales than on the thicker wool.

The strength of the treated fiber is 10.34cN, and the strength retention rate is 83.25%; the elongation was 32.30% and the elongation retention was 64.77%. This shows that the wool treated by this process can meet the requirements of shrinkproof, the loss of breaking strength is in acceptable range, but the loss of elongation is relatively large.

Furthermore, the whole soaking-steaming treatment took as long as 26 minutes, and the treatment effect was much inferior to examples 1 to 5. In contrast, the total time for the multiple padding in examples 1 to 5 of the present invention was very low (5 minutes or less, more preferably 3 minutes or less), and the descaling effect was more uniform and the shrinkproof property was more excellent.

The invention has the outstanding characteristics of chlorine-free, rapid and continuous processing, so as to completely replace a chlorination shrink-proof method, improve the defects of a protease biological treatment process used alone, perfect the protease biological treatment method, and finally achieve the purposes of optimizing the treatment effect and improving the quality of the whole wool product.

All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.

Claims

1. A shrink-proofing agent for chlorine-free shrink-proofing treatment, characterized in that the shrink-proofing agent comprises: (a) optionally a solvent; (b) a protease; and (c) an organophosphinic compound represented by formula A and optionally an inorganic salt;

P-(X)₃A

2. The shrink-resistant treatment according to claim 1, wherein the pH of the shrink-resistant treatment is 6.5 to 12, preferably 7 to 11.5, more preferably 7.5 to 10.5 when the shrink-resistant treatment is an aqueous solution or reconstituted into an aqueous solution.

3. The shrink resistant treatment of claim 1 wherein said organophosphinic compound is a water soluble aliphatic organophosphinic compound.

4. The shrink resistant treatment of claim 1 wherein said organophosphinic compound has the formula:

P-(R₁-R₂)₃I

wherein,

5. The shrink resistant treatment of claim 1 wherein said organophosphinic compound is selected from the group consisting of: tris (3-hydroxypropyl) phosphine, tris (3-carboxypropyl) phosphine, tris (2-hydroxyethyl) phosphine, tris (4-carboxybutyl) phosphine, or a combination thereof.

6. An apparatus for shrink-proofing a chlorine-free wool top or wool product, comprising:

7. The shrink-proofing treatment apparatus according to claim 6, wherein one or more auxiliary padding devices are further provided between or after the respective padding devices of said multiple padding apparatus, said respective auxiliary padding devices independently comprising an auxiliary padding tank and an auxiliary rolling roll, wherein said auxiliary padding tank is filled with the organic phosphine compound-free protease treatment solution and/or the organic phosphine compound treatment solution containing no protease.

8. A shrink-proof treatment method of chlorine-free wool tops or wool products is characterized by comprising the following steps:

(a) providing chlorine-free wool tops or wool products to be treated and a shrink-proofing treatment for chlorine-free wool tops or wool products according to claim 1;

(b) carrying out n-times padding treatment on the chlorine-free wool tops or the wool products to be treated by using the shrink-proof treatment agent so as to obtain padded wool products, wherein n is a positive integer of 2-10;

9. The method according to claim 8, wherein the total time T of the padding treatment of step (b) is less than or equal to 15 minutes, preferably less than or equal to 10 minutes, more preferably less than or equal to 5 minutes, most preferably less than or equal to 3 minutes.

10. A shrink-resistant chlorine-free wool product which is free of organic chlorine residues and which has been chlorine-free treated by the shrink-resistant treatment apparatus of claim 6 or by the method of claim 8.