WO2016127951A1 - Process and device for chlorine-free shrinkproof treatment of wool raw material and article thereof - Google Patents

Abstract

The present invention relates to a process and a device for chlorine-free shrinkproof treatment of a wool raw material and an article thereof. In particular, the process of the present invention comprises the steps of a chlorine-free shrinkproof treatment, washing with water, protease inactivation, a softening treatment, dehydration, drying and the like, wherein a chlorine-free catalysis system consisting of a protease, a specific organic phosphine compound and the like is selected, removing the scale layer on the surface of wool fibres cooperatively and efficiently and modifying the scale layer so as to improve the shrinkproof performance of wool articles. The process of the present invention can completely replace the chloridisation shrinkproof method in the prior art, and is not only environmentally friendly, but also has low requirements for equipment, can be operated continuously and is suitable for large-scale industrial production.

Description

Process and equipment for chlorine-free shrinkage treatment of wool raw materials and products Technical field

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

Background technique

Wool is an important raw material for the textile industry. It has many excellent properties such as good elasticity, strong hygroscopicity, non-staining, good warmth and soft gloss. As a natural protein fiber, wool is attached with a layer of scales which are mainly composed of keratin proteins and overlap each other. Because of the different friction coefficients in the direction of the scales, the wool fibers will interpenetrate under the repeated action of external force. Entangled, woven, felted and shriveled. Although the fleece has the advantages of beautiful appearance, rich hand feeling softness and good warmth performance, it also makes the wool fabric easy to cause dimensional shrinkage and deformation during the washing process. Therefore, in order to improve the anti-felting performance of the wool textile, in order to improve the dimensional stability of the wool fabric product, the product can achieve the "machine washable" effect, and the surface scale modification of the wool fiber is required from the source.

At present, the main methods for the modification and shrinkage treatment of wool surface scales are: chlorination method, covering method, protease method and the like. The most widely used is the organic halide AOX (which is an absorbable organic halide) produced during the chlorination process, which can seriously pollute the environment.

Chinese patent CN201010605809.9 reported that the method of anti-shrinking and scaling of wool tops by adding potassium permanganate and DCCA as a catalyst to clean water and then introducing chlorine gas, the chlorine gas consumption is reduced on the original basis. 30%. Although this method has improved the traditional chlorination method, it still uses chlorine gas, which still causes serious environmental pollution. The covering method reduces the surface friction effect of the fiber by depositing a resin film on the surface of the wool to fill the gaps on the surface of the wool to smooth the surface of the wool. Although this treatment method can improve the felting property of the fiber to some extent, it will seriously affect the hand feeling of the wool fabric, and there is a general lack of durability. The protease method utilizes the hydrolysis of macromolecular peptide bonds on the surface of wool fibers by protease to partially dissolve the scales and cell membrane complexes of the wool, thereby achieving the purpose of partially or completely removing the scales. The treatment method has the advantages of mild treatment conditions, energy conservation and pollution reduction, and is an environmentally friendly wool anti-felting finishing method. However, the anti-shrinking effect of the treatment of wool by protease alone cannot meet the actual needs at present. Therefore, many of the wools must be pre-treated with proteases for biological modification (for example, with strong oxidizing agent permanganic acid). Potassium or the like is pre-oxidized or pretreated with a chloride solvent). All of the above pretreatment methods have disadvantages such as excessive treatment time, easy deactivation of the enzyme, and difficulty in controlling the treatment conditions.

In addition, although researchers have attempted to develop a chlorine-free shrink-proof treatment process for wool raw materials, they have the following disadvantages: (a) long processing time (cannot be shortened to within 30 minutes while ensuring processing quality); (b) The processing capacity is limited, and it is not suitable for industrial application; (c) The processing quality is large, and it is difficult to obtain a wool processing product with uniform treatment effect. Therefore, in major wool processing countries such as China, there is currently no use of chlorine-free shrinkage treatment to process wool raw materials in actual production.

In summary, there is an urgent need in the art to develop a wool shrink-proof treatment process that is environmentally friendly, simple and easy to control, has a long anti-felting effect, and has high processing efficiency (or fast) and is suitable for mass production.

Summary of the invention

The object of the present invention is to provide a wool shrink-proof treatment process which is environmentally friendly, simple and easy to control, has a long anti-felting effect, and has high processing efficiency (or rapid) and is suitable for mass production.

According to a first aspect of the present invention, there is provided a shrinkage preventing agent for a chlorine-free shrinkage preventing treatment comprising: (a) an optional solvent; (b) a protease; and (c) An organophosphine compound represented by A and optionally an inorganic salt;

P-(X) ₃ A

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

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

The weight ratio of the protease to the organophosphine compound is 0.2-10:0.5-20;

And the protease in the anti-shrinkage 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 descaling/anti-shrinking the wool material and/or the wool product.

In another preferred embodiment, the wool material comprises a wool strip.

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

In another preferred embodiment, the shrink prevention treatment agent further contains a basic compound.

Preferably, 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 hydrogencarbonates, alkaline earth metals. Bicarbonate, or a combination thereof.

In another preferred embodiment, the basic compound is selected from the group consisting of NaOH, KOH, Ca(OH) ₂ , Na ₂ CO ₃ , K ₂ CO ₃ , or a combination thereof.

In another preferred embodiment, the "chlorine-free" means that the shrink-proof treatment agent does not contain an organochlorine compound, and does not include a hypochlorous acid compound selected from the group consisting of a compound containing a ClO ^- ion (root). may be generated ClO ^- ion compound (e.g., chlorine).

In another preferred embodiment, in the shrink-proof treatment agent, the content of the hypochlorous acid compound is ≤ 0.05% by weight, preferably ≤ 0.01% by weight, more preferably ≤ 0.001% by weight, most preferably About 0.

In another preferred embodiment, the anti-shrinkage 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 anti-shrinkage treatment agent is a solid, semi-solid, and can be reconstituted as a treatment liquid by adding a solvent such as water at the time of application.

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

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

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

In another preferred embodiment, the two Xs are the same.

In another preferred embodiment, the three Xs are the same.

In another preferred embodiment, the three Xs are different.

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

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

In another preferred embodiment, the C1-C10 hydrocarbon group includes a C1-C10 alkyl group and a C3-C8 cycloalkyl group.

In another preferred embodiment, when the anti-shrinkage 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:

In another preferred embodiment, the amount (wt) of the protease in the anti-shrinkage treatment agent is less than or equal to (≤) the amount (wt) of the organophosphine compound.

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

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

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

In another preferred embodiment, the water solubility means that the solubility of the organophosphine compound in 100 g of water at 25 ° C is ≥ 0.1 g, preferably ≥ 0.5 g, more preferably ≥ 2 g, such as 0.1-10 g or 0.5-5 g. .

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

P-(R ₁ -R ₂ ) ₃ I

among them,

R ₁ is a substituted or unsubstituted C 2 -C 8 alkylene group (preferably a C 1 -C 6 alkylene group); and/or

R _{2 is} selected from the group consisting of -OH, -COOH, or a C2-C8 ester group, an alkali metal, or an alkaline earth metal.

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

R ₁ is an unsubstituted C1-C6 alkylene group; and/or

R _{2 is} selected from the group consisting of -OH, and -COOH.

In another preferred embodiment, R _{1 is} selected from the group consisting of methylene, ethylene, propylene, butylene, pentylene, hexylene, or a combination thereof.

In another preferred embodiment, the aliphatic organophosphine compound is selected from the group consisting of tris(3-hydroxypropyl)phosphine, tris(3-carboxypropyl)phosphine, tris(2-hydroxyethyl)phosphine, and tri (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 hydrochloride, sulfate, carbonate, hydrogencarbonate, nitrate, nitrite, phosphate, monohydrogen phosphate, dihydrogen phosphate. Salt or a combination thereof.

In another preferred embodiment, the inorganic salt is selected from the group consisting of Mg(NO ₃ ) ₂ , sodium phosphate, calcium hydrogen phosphate, CaCl ₂ , or 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 anti-shrinkage treatment agent further contains a pH buffer.

In another preferred embodiment, the pH buffering agent is present in an amount of from 0.1 to 10 g/, preferably from 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), NaHCO 3 -Na 2} CO 3 buffer, or combinations thereof.

In another preferred embodiment, the shrink prevention treatment agent is in a liquid state at 25 to 80 °C.

In another preferred embodiment, the shrink prevention treatment agent is liquid at a temperature of from 30 to 70 ° C, preferably from 40 to 60 ° C, more preferably from 45 to 55 ° C.

In another preferred embodiment, in the chlorine-free treatment, the processed top is of a size of 10-30 g/m/feet, preferably 20-25 g/m/feet.

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

In a second aspect of the invention, there is provided a shrink-proof treatment apparatus for a chlorine-free wool strip or a wool product, the apparatus comprising:

a multiple padding apparatus comprising n independent, continuously arranged padders, each of the paddings comprising a soaking tank and a rolling roll, wherein the soaking tank is used for placing chlorine-free The shrink-treated shrink-proof treatment liquid so that the wool strip or wool product to be treated is immersed in the treatment liquid; and the rolling roll is used for rolling the soaked wool strip or wool product, and is subjected to an upstream rolling roll After the rolling, the wool strip or the wool product is sequentially entered into the soaking tank and the rolling roll of the downstream padder, thereby repeating the soaking and rolling treatment, wherein n is a positive integer of 2-20;

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

An enzyme inactivating device for alkaline inactivation treatment of residual protease in the washed top or wool product to form an enzyme-inactivated top or wool product;

An optional softening device for softening the enzyme-inactivated tops or wool products to form a softened top or wool product;

An optional dryer for drying the softened tops or wool products obtained in the previous step.

In a third aspect of the invention, there is provided a method for preventing shrinkage of a chlorine-free wool strip or a wool product, comprising the steps of:

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

(b) performing n-padding treatment on the chlorine-free wool strip or wool product to be treated with the anti-shrinkage treatment agent, thereby obtaining a padded wool product, wherein n is a positive integer of 2-20;

(c) subjecting the padded chlorine-free wool strip or wool product to a water washing treatment to obtain a water-washed chlorine-free wool strip or wool product;

(d) subjecting the water-washed chlorine-free wool strip or wool product to an enzyme inactivation treatment to obtain a shrink-free chlorine-free wool strip or wool product.

In another preferred embodiment, n is a positive integer of 3-10.

In another preferred embodiment, treatment may be additionally carried out with a treatment liquid containing only the protease but no the organophosphine compound during and/or after the n-padding treatment.

In another preferred embodiment, the total time T of the padding treatment of the step (b) is ≤ 15 minutes, preferably ≤ 10 minutes, more preferably ≤ 5 minutes, most preferably ≤ 3 minutes.

In another preferred embodiment, the chlorine-free wool strip or wool article to be treated in step (a) is planarized.

In another preferred embodiment, the composition of the wool strip is selected from the group consisting of wool, cashmere, or a combination thereof.

In another preferred embodiment, the wool strip has a size of from 40 to 150, preferably from 40 to 120, more preferably from 56 to 100.

In another preferred embodiment, in the step (b), the temperature of the wetting/rolling operation is 5 to 80 ° C, preferably 10 to 60 ° C, more preferably 25 to 50 ° C, optimally 40. -50 ° C.

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

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

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

In another preferred embodiment, the enzyme inactivation operation can employ conventional inactivation conditions as long as the residual protease is inactivated or substantially inactivated.

In another preferred embodiment, in the method, no hypochlorous acid compound is used.

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

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

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

In another preferred embodiment, the treatment time of the padding in step 2) is from 3 to 1000 s, preferably from 5 to 800 s, more preferably from 8 to 600 s, most preferably from 10 to 300 s.

In another preferred embodiment, the obtained padded wool product obtained in the step 2) has a liquid ratio of 50 to 160% by weight, preferably 60 to 150% by weight, more preferably 80 to 140% by weight.

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

In another preferred embodiment, before each step 2) is repeated, the method further comprises the step of: replacing the shrink-proof treatment liquid.

In another preferred embodiment, in step 3), the water for washing is at a temperature of 10 to 40 ° C, preferably 20 to 30 ° C.

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

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

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

In another preferred embodiment, the water washing time of the step 3) is from 1 to 60 minutes, preferably from 1 to 30 minutes, more preferably from 1 to 10 minutes.

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

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

In another preferred embodiment, the hot water used for hot water inactivation has a temperature of from 85 to 100 ° C, preferably from 90 to 98 ° C, more preferably from 92 to 96 ° C.

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

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

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

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

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

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

In another preferred embodiment, in step 5), the ratio of the amount of the product obtained in step 4) to the softening agent is a conventional ratio.

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

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

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

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

In another preferred embodiment, the softening treatment used in the step 5) has a concentration of the treatment agent of 5 to 100 g/L, preferably 10 to 50 g/L, more preferably 15 to 30 g/L.

In another preferred embodiment, the treatment agent used in the softening treatment of step 5) is selected from the group consisting of wool smoothing agents, wool softening agents, or combinations thereof.

In another preferred embodiment, the drying treatment in the step 6) has a treatment temperature of 60 to 100 ° C, preferably 70 to 90 ° C.

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

In a fourth aspect of the invention, there is provided a shrink-proof, chlorine-free wool product which is free of residual organochlorine.

In another preferred embodiment, the wool product is subjected to the shrink-proof treatment process (method) of the present invention. Anti-shrink processing.

In another preferred embodiment, the wool product is subjected to a shrink-proof treatment using the chlorine-free wool strip or the anti-shrinkage treatment agent of the wool product described in the first aspect of the invention.

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

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

In another preferred embodiment, after treatment by the shrink-proof treatment method, the absolute value of the shrinkage of the treated chlorine-free wool product is ≤10%, preferably ≤8%, compared to the wool product to be treated. Preferably, it is ≤6%, more preferably ≤5%, and most preferably ≤3%, wherein the measuring method is the International Wool Bureau TWC.TM31 test method,

In another preferred embodiment, after treatment by the shrink-proof treatment method, the strength of the treated chlorine-free wool product is maintained ≥80%, preferably ≥82%, more preferably than the wool product to be treated. ≥84%.

In another preferred embodiment, after treatment by the shrink-proof treatment, the elongation of the treated chlorine-free wool product remains ≥70%, preferably ≥75%, compared to the wool product to be treated. Good land ≥ 80%.

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

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

In another preferred embodiment, the article comprises a top, a blanket, and a garment.

In a sixth aspect of the invention, there is provided a use of the anti-shrinkage treatment agent according to the first aspect of the invention, which is used for chlorine-free shrink-proof treatment of tops or wool products.

In a seventh aspect of the invention, there is provided a non-chlorinated wool strip and a shrinkage preventing liquid for a wool product, the main composition thereof being: a protease, a water-soluble aliphatic trisubstituted organic phosphine compound, an inorganic salt; The structure of the aliphatic trisubstituted organophosphine is: P-(RS) ₃ , wherein R: is a hydrocarbon group having 1 to 6 carbons, and S is a hydroxyl group or a carboxyl group and a derivative thereof; the mass concentration thereof is 1 to 10 g/L; The inorganic salt is calcium chloride and its concentration is 0 to 2 g/L.

In another preferred embodiment, the trisubstituted organophosphine is: tris(3-hydroxypropyl)phosphine, tris(3-carboxypropyl)phosphine, tris(2-hydroxyethyl)phosphine, tris(4- At least one of carboxybutyl)phosphines.

In an eighth aspect of the invention, there is provided a continuous processing process for the anti-shrinkage treatment of a chlorine-free wool strip and a wool product, comprising the steps of:

1) Anti-shrinkage treatment: the wool strips and wool products are leveled and transported through the rolls at a uniform speed into a plurality of anti-shrinkage treatment tanks alternately infiltrated and rolled 3-10 times. The process conditions are: the pH of the anti-shrinkage treatment liquid is 7～10.5, the temperature is 40～50°C; the rolling liquid rate is 60%～150%; the process conveying speed is 3～15m/min, and the total infiltration and rolling time is 1-5 minutes;

2) Washing: the above treated wool strips are transferred into 1 to 4 clear water tanks by roll action to perform multiple washings to remove residual biological enzyme activators and enzyme preparations to prevent them from continuing to erode the wool;

3) Inactivation of protease: the washed wool strips are uniformly and quickly passed through a 85-95 ° C hot water tank or a solution containing 0 to 1 g / liter of hydrogen peroxide to inactivate the protease that has not been completely washed;

4) Soft treatment: the inactivated wool strip is soaked in a tank of a conventional wool smoothing agent or a silicone softener, and subjected to a general softening treatment to improve the hand feeling of the wool fabric;

5) dehydration and drying;

The anti-shrinkage treatment liquid mainly comprises:

Trisubstituted organophosphine at a concentration of 1 to 10 g/L

Calcium chloride at a concentration of 0.3 to 2 g/L

Protease at a concentration of 0.5 to 5 g/L

The rest is water

The trisubstituted organic phosphine is: tris(3-hydroxypropyl)phosphine, tris(3-carboxypropyl)phosphine, tris(2-hydroxyethyl)phosphine, tris(4-carboxybutyl)phosphine At least one.

In another preferred embodiment, the soaking and pressing or rolling are repeated 3-10 times; the total time of the soaking treatment is between 1 and 5 minutes; and the process conveying speed is 3-8 meters/minute.

In another preferred embodiment, the wool strip is 56 to 100 pieces of wool or cashmere.

It is to be understood that within the scope of the present invention, the various technical features of the present invention and the various technical features specifically described hereinafter (as in the embodiments) may be combined with each other to constitute a new or preferred technical solution. Due to space limitations, we will not repeat them here.

DRAWINGS

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing the effect of stripping of wool fiber scales according to Example 1 of the present invention.

Fig. 2 is a view showing the effect of stripping of wool fiber scales according to Example 2 of the present invention.

Fig. 3 is a view showing the effect of stripping of wool fiber scales according to Example 3 of the present invention.

Fig. 4 is a view showing the effect of stripping of wool fiber scales according to Example 4 of the present invention.

Fig. 5 is a view showing the effect of stripping of wool fiber scales according to Example 5 of the present invention.

Fig. 6 is a flow chart showing an example of a process of the present invention.

Figure 7 is a schematic illustration of a chlorine free processing apparatus of the present invention.

detailed description

After long-term and intensive research, the inventors have unexpectedly prepared a descaling and shrink-proof process for chlorine-free wool/wool products and corresponding shrink-proof treatment agents and equipment. The process and the shrink-proof treatment liquid of the invention can remove the scale layer on the surface of the wool fiber efficiently and quickly under the condition of no chlorine, and modify the scale layer to To improve the felting properties of wool products and improve product dimensional stability. On this basis, the inventors completed the present invention.

In particular, the present invention provides a continuous processing process for the anti-shrinkage treatment of chlorine-free wool strips and wool products. Including anti-shrinkage treatment, water washing, protease inactivation, soft treatment, dehydration, drying step, according to the characteristics of wool fiber is a protein fiber, the activator and metal salt of protease and water-soluble aliphatic tri-substituted organophosphine structure are selected. The high-efficiency integrated catalytic system composed of nonionic surfactant can synergistically and efficiently remove the scale layer on the surface of the wool fiber, and modify the scale layer to improve the felting performance of the wool product, improve the dimensional stability of the product, and make the fabric have Anti-pilling characteristics and smooth feel. The invention can completely replace the chlorination shrinkage prevention method in the prior art, avoids the environmental pollution caused by the chlorination method, is a clean type treatment process that meets environmental requirements, and has no problem of chlorination pollution. The method has the advantages of small dosage, low cost, simple process, low requirement on equipment, continuous operation, and industrial production.

the term

As used herein, the term "wool stock" includes wool, tops, or semi-finished products that have not been scaled and shrunk. In addition, the term may also include wool raw materials that have not been fully descaled, although subjected to descaling shrinkage treatment.

As used herein, the terms "wool/wool", "wool and/or wool" are used interchangeably and refer to a wool strip, or a wool article, or a combination of the two. The term may include both wool strands/wool articles to be treated, as well as wool strands/wool articles that are processed or treated.

As used herein, the terms "chlorine-free product of the invention", "chlorine-free wool strip/wool product of the invention" are used interchangeably and refer to wool/wool products obtained by the chlorine-free descaling shrink-proof treatment process of the present invention. . Since the chlorine-free descaling shrinkage prevention process of the present invention does not use an organochlorine compound and does not use a hypochlorous acid compound (i.e., a compound containing a ClO-ion or a compound which can generate a ClO-ion), it is safe. Excellent chlorine-free wool products (including wool/wool products).

As used herein, the term "anti-shrinkage agent (or liquid) of the present invention", "descaling anti-shrinkage agent (or liquid) of the present invention", "chlorine-free shrinkage-reducing agent (or liquid)", "chlorine-free descaling" The shrink-proof treatment agent (or liquid) is used interchangeably and refers to a shrink-proof treatment agent (or liquid) of the chlorine-free wool wool/wool product of the present invention.

Anti-shrinkage treatment agent for chlorine-free wool/wool products

The present invention provides a descaling anti-shrinkage treatment agent for the chlorine-free wool wool/wool product of the present invention. The descaling anti-shrinkage treatment agent of the present invention may be in a solid or liquid state. When the chlorine-free shrink-proofing agent of the present invention is in a solid state, the anti-shrinkage treatment liquid of the corresponding chlorine-free wool wool/wool product can be reconstituted by adding water (or an aqueous solvent).

Furthermore, the present invention, wherein the various combinations may have been mixed together (i.e., present in a mixed manner), may also be present in a non-mixed manner, and may be formulated in situ upon use.

In a preferred embodiment, the main components of the anti-shrinkage treatment liquid for a chlorine-free wool strip and a wool product are: a protease, a water-soluble aliphatic trisubstituted organic phosphine compound, an inorganic salt; and the water-soluble aliphatic tri-substituted organic The phosphine structure is: P-(RS) ₃ , wherein R: is a hydrocarbon group having 1 to 6 carbons, S is a hydroxyl group or a carboxyl group and a derivative thereof; the mass concentration is 1 to 10 g/L; and the inorganic salt is calcium chloride. , its concentration is 0 ~ 2g / 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, three (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 refers to a protease having a pH optimum of neutrality (e.g., about 6.8 to 7.0), and its molecular weight is generally 35 to 40 kD. Neutral proteases suitable for use in the present invention include neutral proteases which are commercially available or prepared by conventional methods, such as neutral proteases from microorganisms, Neutrase, or combinations thereof.

In another preferred embodiment, the alkaline protease refers to a protease having an optimum pH of alkaline (e.g., about 9 to 11), and has a molecular weight of generally 26 to 34 kD. Alkaline proteases suitable for use in the present invention include alkaline proteases which are commercially available or prepared by conventional methods, such as alkaline protease from Bacillus licheniformis (molecular weight of about 27,300, which is a serine-type endoprotease), from Streptomyces. Alkaline protease, 2709 alkaline protease, Novo protease, Carsberg protease, and the like.

In the anti-shrinkage liquid of the present invention, the concentration of the protease is generally from 0.1 to 25 g/L, preferably from 0.2 to 10 g/L, more preferably from 0.5 to 5 g/L of the anti-shrinkage liquid. The amount (or concentration) of the protease is generally 1 × 10 ⁴ - 1 × 10 ⁸ U / L of anti-retraction liquid, preferably 5 × 10 ^{4 -} 5 × 10 ⁷ U / L, in terms of International Units (IU). More preferably, it is 1 × 10 ⁵ - 1 × 10 ⁷ U / 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 surfactants (eg, alkylphenol ethoxylates (APEO), fatty acid polyoxyethylene esters (AE), fatty acid methyl esters ethoxylates) A base compound (FMEE)), and a polyol type surfactant (such as sorbitan esters, including Tween and Span), or a combination thereof. Representative examples include: Tween, Span, JFC, or a combination thereof. Representative anionic surfactants include, but are not limited to, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate (SDS), hexadecyl sulfonate, or combinations thereof.

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

Preferably, the pH of the shrink prevention treatment liquid of the present invention is from 7 to 10.5.

In another preferred embodiment, the present invention provides a shrink-proof treatment liquid for a chlorine-free wool strip and a wool product, the main mass composition of which is:

Trisubstituted organophosphine at a concentration of 1 to 10 g/L

Calcium chloride at a concentration of 0 to 2 g/L

Protease at a concentration of 0.5 to 5 g/L

The rest is water.

The anti-shrinkage treatment agent (liquid) of the present invention can directly process the wool strip/wool product, thereby obtaining a deburring and shrink-proof wool strip/wool product.

Compared with the chlorine-containing anti-shrinkage treatment liquid of the prior art, the anti-shrinkage treatment liquid of the present invention does not contain an organochlorine compound, and does not use a hypochlorous acid compound (that is, a compound containing ClO- ions or can generate ClO- ions). a compound such as Cl ₂ ). The organochlorine compound includes DCCA, chloroform, carbon tetrachloride, TCCA, and the like.

In another preferred embodiment, the main components of the chlorine-free wool strip and the anti-shrinkage treatment liquid of the wool product of the present invention are a protease, a water-soluble aliphatic tri-substituted organic phosphine compound and an inorganic salt.

Wherein the water-soluble aliphatic trisubstituted organophosphine structure is: P-(RS) ₃ ,

R: is a hydrocarbon group having 1 to 6 carbons (C), and S is a hydroxyl group (-OH) or a carboxyl group (-COOH) and a derivative thereof. The amount used is 1 g to 10 g/L; the inorganic salt is calcium chloride or the like, and the amount thereof is 0 g/L to 2 g/L.

The trisubstituted organic phosphine is: tris(3-hydroxypropyl)phosphine, tris(3-carboxypropyl)phosphine, tris(2-hydroxyethyl)phosphine, tris(4-carboxybutyl)phosphine At least one.

The protease is a neutral protease, an alkaline protease or the like, and the protease has a concentration of 0.5 g/L to 5 g/L.

The pH of the anti-shrinkage treatment liquid is 7 to 10.5.

In another preferred embodiment, the main mass composition of the anti-shrinkage treatment liquid is:

Trisubstituted organophosphine at a concentration of 1 to 10 g/L

Calcium chloride at a concentration of 0 to 2 g/L

Protease at a concentration of 0.5 to 5 g/L

The rest is water.

Anti-shrinkage treatment method (process) for chlorine-free wool wool or wool products

The invention also provides a shrink-proof treatment method for a chlorine-free wool strip or a wool product, wherein the wool strip/wool product is treated with the chlorine-free descaling anti-shrinkage treatment liquid of the invention, thereby obtaining excellent shrink-proof property. Wool strip/wool products. It should be understood that although the shrink-proof treatment liquid and method of the present invention can sufficiently achieve descaling to obtain a fully descaled wool product, the method of the present invention can also be used to produce incomplete descaling (i.e., partial descaling, as needed). ) wool products.

As shown in FIG. 6, in a preferred embodiment, the present invention provides a continuous processing process for the anti-shrinkage treatment of chlorine-free wool strips and wool products, comprising the following steps:

1) Descaling and shrink-proof treatment: the wool strip/wool product is leveled and conveyed uniformly through the roll into one or more anti-shrinkage treatment tanks, alternately infiltrated and rolled (eg 3-10 times), process conditions The pressure of the anti-shrinkage treatment liquid is 7 to 10.5, and the temperature is 40 to 50 ° C; wherein, the total time of infiltration and rolling is 1 to 5 minutes;

Preferably, the wool strips are flattened side by side through a roll and fed into a plurality of anti-shrinkage treatment liquid tanks for alternately infiltrating and rolling (squeezing) pressure 3-10 times, the process condition is: the pH of the shrink-proof treatment liquid is 7～ 10.5, the temperature is 40 ~ 50 ° C; the rolling liquid rate is 60% ~ 150%; the process conveying speed is 3 ~ 15 m / min (preferably 3-8 m / min), the total infiltration and rolling time 1-5 minute;

2) Washing: The above-mentioned treated wool strips are transferred into 1 to 4 clear water tanks by roll action. Washing multiple times to remove residual bio-enzyme activators and enzyme preparations to prevent them from continuing to attack the wool;

3) Inactivation of protease: the washed wool strip is quickly passed through a 85-95 ° C hot water tank or a solution containing 0.1 to 1 g / liter of hydrogen peroxide to inactivate the protease that has not been completely washed;

4) Soft treatment: the inactivated wool strip is soaked in a tank of a conventional wool smoothing agent or a silicone softener, and subjected to a general softening treatment to improve the hand feeling of the wool fabric;

5) dehydration and drying;

The anti-shrinkage treatment liquid mainly comprises:

Trisubstituted organophosphine at a concentration of 1 to 10 g/L

Calcium chloride at a concentration of 0.3 to 2 g/L

Protease at a concentration of 0.5 to 5 g/L

The rest is water

The trisubstituted organic phosphine is: tris(3-hydroxypropyl)phosphine, tris(3-carboxypropyl)phosphine, tris(2-hydroxyethyl)phosphine, tris(4-carboxybutyl)phosphine At least one.

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

In the present invention, the total time of the soaking and rolling treatment is not particularly limited and is usually from 0.5 to 20 minutes, preferably from 1 to 10 minutes, more preferably from 1 to 5 minutes.

The present invention requires only a very short total time of the wetting/rolling operation because the chlorine-free descaling anti-shrinkage treatment agent of the present invention can perform descaling very efficiently and almost without damage.

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

In a preferred embodiment of the invention, the processing includes:

1) Anti-shrinkage treatment: The stripping treatment of the wool strip by the protease integrated catalytic system. In the case of no tension of each wool strip, the wool strips are flattened side by side through a roll and fed into a high-efficiency catalytic system consisting of protease, water-soluble aliphatic trisubstituted organophosphorus bioenzyme activator and inorganic salt catalyst. The nonionic surfactant acts as an auxiliary penetrant, the pH is 7~10.5, the temperature of the catalytic system is 40-50 °C, and the wool strip is completely saturated (the soaking can be accelerated by the suction roller and the exchange speed of the wool fiber and the surrounding treatment liquid) ), the wool strip is extruded by a roll action, and the liquid ratio is 60% to 150%. After that, it is again transferred into a catalytic system with a temperature of 40 to 50 ° C. After soaking, the wool strip is pressed by the action of the rolls, so that the padding is repeated, and the speed of the process is controlled at 3 to 15 m/min (optional 3-8 m). /min), according to the wool count and product quality requirements, in the same integrated catalytic system treatment liquid and the same treatment conditions, after 1 to 5 minutes and after 3 to 10 times of padding, and finally transmitted to the subsequent correlation Process the tank for continuous automation.

2) Washed. The treated wool strips are transferred into 1 to 4 clear water tanks by roll action for multiple washings to remove residual biological enzyme activators and enzyme preparations to prevent them from continuing to attack the wool.

3) Inactivation of protease. The second step of the washed wool strip is evenly and quickly passed through the boiling water tank or contains A solution of 0 to 1 g/L of hydrogen peroxide. Inactivate the protease that has not been completely washed away.

4) Soft treatment. Soaking the inactivated wool strips in a conventional wool smoothing agent or silicone softener (ie, in a tank softening treatment, a general softening treatment, the softening agent is a hydrogen-containing silicone oil, an amino silicone oil, and a modified silicone oil or their Emulsion) to improve the feel of wool fabrics.

5) Dehydration and drying (conventional methods can be used).

Chlorine-free processing equipment

The invention also provides a chlorine free processing apparatus for use in the method of the invention.

A typical processing device is shown in Figure 7. The device includes:

a multiple padding apparatus 10, the multiple padding apparatus comprising n independent, continuously arranged padders (not shown), each of the paddings comprising a soaking tank and a rolling roll, wherein the soaking tank a shrink-proof treatment liquid for placing a chlorine-free shrink-proof treatment, so that the wool wool or wool product to be treated is immersed in the treatment liquid; and the rolling roller is used for rolling the soaked wool wool or wool product And the wool strip or wool product after being rolled by the upstream rolling roll is sequentially entered into the soaking tank and the rolling roll of the downstream padder, thereby repeating the soaking and rolling treatment, wherein n is a positive integer of 2-20;

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

An enzyme inactivating device 30 for alkaline inactivation treatment of residual protease in the washed top or wool product to form an enzyme-inactivated top or wool product;

An optional softening device 40 for softening the enzyme-inactivated tops or wool products to form a softened top or wool product;

An optional dryer 50 for drying the softened tops or wool products obtained in the previous step.

In another preferred embodiment, the multiple padding device, the water washing device, the enzyme inactivation device, the optional soft processing device, and the optional dryer are sequentially arranged.

In another preferred embodiment, one or more auxiliary padding devices are further provided between or after each of the padding devices of the multiple padding device, and each of the auxiliary padding devices independently includes an auxiliary soaking tank. And an auxiliary rolling roll, wherein the auxiliary soaking tank is provided with a protease treatment solution containing no organic phosphine compound, and/or a protease-free organic phosphine compound treatment liquid.

In another preferred embodiment, the auxiliary soaking tank is an enzyme processing tank.

In another preferred embodiment, the enzyme treatment tank is located after the second, third, fourth or fifth padder.

In another preferred embodiment, wherein n is 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, preferably The ground is 3-15, more preferably 4-10.

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

In another preferred embodiment, each of the padders is sequentially arranged.

In another preferred embodiment, the anti-shrinking treatment agent (or liquid) according to the first aspect of the invention is contained in the soaking tank.

In another preferred embodiment, the soaking tank is a suction drum washing tank.

In another preferred embodiment, the soaking tank is independently provided with or without a heating device or a temperature controlling device.

In another preferred embodiment, each of the heating device or the temperature control device controls the temperature range to 25-80 ° C, preferably 30-70 ° C, more preferably 40-60 ° C, and most preferably 45-55. °C.

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

In another preferred embodiment, each of the water washers contains solvent water.

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

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

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

In another preferred embodiment, the solvent water in the enzyme inactivating device has a temperature of from 85 to 100 ° C, preferably from 90 to 98 ° C, more preferably from 92 to 96 ° C.

In another preferred embodiment, the enzyme inactivating device contains a solution containing H ₂ O ₂ .

In another preferred embodiment, the concentration of the H ₂ O ₂ in the solution contained in the enzyme inactivating device is 0.01-50 g/L, preferably 0.05-30 g/L, more preferably 0.1-10 g/L.

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

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

In another preferred embodiment, the wool softener comprises: a silicone-based 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 wool/wool products

The present invention also provides a shrink-proof, chlorine-free wool/wool product obtained with the chlorine-free shrink-proof treatment process of the present invention with little or no residual organic chlorine.

As used herein, the term "ecoshine" or "ecoshine product" refers to a non-chlorinated chlorine-free product obtained with the chlorine-free shrink-proof treatment process of the present invention with little or no residual organic chlorine. Wool strip/wool products.

The chlorine-free tops or wool products of the present invention (i.e., Evexin products) have excellent properties including, but not limited to:

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

(b) low shrinkage ratio: the absolute value of the shrinkage of the treated wool product is ≤10%, preferably ≤8%, preferably ≤6%, more preferably ≤5, compared to the wool product to be treated. %, optimally ≤ 3%, wherein the measurement method is the International Wool Bureau TWC.TM31 test method.

(c) High strength retention rate: After treatment by the shrink-proof treatment method, the strength of the treated wool product is maintained ≥80%, preferably ≥82%, more preferably ≥ compared to the wool product to be treated 84%.

(d) High elongation retention: after treatment by the shrink-proof treatment method, the elongation of the treated wool product is maintained at ≥70%, preferably ≥75%, compared to the wool product to be treated. Good land ≥ 80%.

(e) Excellent wetting and permeation performance: The drip diffusion time (according to GB/T21655.1-2008) is increased from ≥10 minutes before untreated to ≤10 seconds.

Processing mechanism and advantages

In order to facilitate the understanding of the present invention, the inventors provided the following mechanism. However, it should be understood that the invention is not limited by this mechanism.

The inventors have found that there are some special structures and substances in the scale layer on the surface of the wool, such as cystine and lipids containing disulfide bonds, so that it is difficult for the protease to effectively digest and decompose the surface layer of the scale and the high-sulfur protein therein. However, in the presence of the organophosphine compound of the formula A of the present invention, the multiple padding process of the present invention can effectively change the structure of the scale layer on the surface of the wool, so that proteins such as high sulfur proteins are more easily degraded by proteases, and the other is In terms of maintaining or increasing the viability of the protease, the scaling and shrinkage of the wool can be achieved extremely efficiently and quickly.

In the preferred treatment agent of the present invention, the action of the protease is mainly to degrade the scales on the surface of the wool fiber by hydrolysis; the water-soluble aliphatic trisubstituted organophosphine is rapidly reduced on the one hand by its unique action on the disulfide bond in the wool. The presence of a large number of disulfide bonds and activation of the reaction substrate facilitates the reaction of the protease with the wool macromolecule. On the other hand, it has a good stabilizing effect on the activity of the protease, and can effectively reduce the decrease of the protease activity in the integrated catalytic system. At the same time, the catalytic action of the protease can be further activated, thereby producing a rapid reaction effect. 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 liquid to wet and penetrate as soon as possible on the surface of the wool fiber.

In the process of the present invention, multiple padding or repeated padding is also a necessary condition for achieving a rapid process in the present invention. During the repeated padding process, the rapid contact and action of the protease and the activator with the surface of the wool fiber are forcibly achieved, and the reactants and the hydrolyzed product are also cleaned, which is beneficial to the further progress of the reaction.

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

(1) Environmentally friendly, do not use chlorine-containing organic matter or chlorine. The invention adopts a high-efficiency catalytic system mainly composed of a protease and a water-soluble organic phosphine structure activator as a treatment liquid to sort the wool, and utilizes the synergistic action of the two to achieve continuous processing of the chlorine-free wool filament light shrinkage prevention process, and the process does not occur during the processing. Toxic and harmful substances, fundamentally solve the pollution of chlorinated mercerizing to the environment, in line with the concept of "ecological textile", will not cause environmental pollution

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

(3) High processing efficiency and fast processing speed. Compared with the known protease anti-shrinkage process, the method is fast, and the shrinkage treatment of the wool can be completed in 1 to 5 minutes, and the mechanical properties are guaranteed to be within an acceptable range.

(4) Anti-felting effect lasts.

(5) Suitable for large-scale production. The process of the invention has low requirements on equipment, can be continuously operated, and is beneficial to realize industrial production.

The invention is further illustrated below in conjunction with specific embodiments. It is to be understood that the examples are not intended to limit the scope of the invention. The experimental methods in the following examples which do not specify the specific conditions are usually carried out according to conventional conditions or according to the conditions recommended by the manufacturer. Percentages and parts are by weight unless otherwise stated.

The reagents involved in the examples are not specifically described and are commercially available.

The treatment liquid of the present invention is prepared by weighing a protease, a water-soluble aliphatic trisubstituted organic phosphine compound, an inorganic salt and a surfactant according to a main formula, and is prepared by a general mass concentration (g/L) preparation method. The organic phosphine compounds used were all purchased from Tianjin Binhai Oriental Technology Co., Ltd.

Example 1

In the present embodiment, the wool strip is subjected to a chlorine-free shrink-proof treatment by a continuous process of five-fold padding.

All wool wool strips to be treated, with a specification of 70 pieces. The process includes the following steps:

First tank: padding treatment liquid. The tank is a suction drum (type) washing tank (general device) having a width of 1 m and a volume of 360 liters and having a circumference of one meter. The suction drum tank has an automatic heating device (general device), and the main component is Highly efficient catalytic solution of alkaline protease 3g/L, tris(3-hydroxypropyl)phosphine 3g/L (addition of nonionic surfactant JFC 1g/L), pH 9 (disodium hydrogen phosphate and Sodium dihydrogen phosphate is a pH adjuster and the temperature is controlled at 50 °C.

The wool wool strips are evenly laid flat on the top rollers and fed into the treatment liquid at a speed of 8 m/min to completely wet the wool strips, ensuring that each fiber in the wool strips is evenly and thoroughly treated; The pressure roller pressurizes the wool strip to ensure that the wool strip is about 135%; then the wool strip with the enzyme liquid is passed to the second treatment tank at a speed of 8 meters per minute. It took 15 seconds from the start of the wool strip to the first tank treatment liquid to the entry into the second tank treatment liquid.

Second tank: padding treatment liquid. Same as the first slot.

Third tank: padding treatment liquid. Same as the first slot.

Fourth tank: padding treatment liquid. Same as the first slot.

Fifth tank: padding treatment liquid. Same as the first slot. From the first slot to the end of the fifth slot, the time is 15 seconds x 5 = 75 seconds.

The sixth tank: washed. The wool strip is rolled and rolled to clean the reagents, enzymes and degradation products attached to the surface of the wool fiber, and the water temperature is normal temperature and the pH is 7.0.

Seventh tank: secondary washing. Same as the sixth slot.

The eighth tank: high-temperature water washing, play an enzyme inactivation, to prevent subsequent erosion of wool fiber, temperature 95 ° C, time 15 seconds.

The ninth trough: the conventional soft treatment, softening the wool fiber to achieve a soft effect and improve the hand feeling. The wool strip is then subjected to conventional dewatering and drying (for example, drying process conditions: drying temperature 70-90 ° C, drying time 3-10 minutes).

The speed of the process is 8 m/min, and the treatment liquid is mixed for 5 times. The scale stripping effect of wool fiber treated by this process is shown in Fig. 1.

The wool treated by this process maintained a strength of 85% and an elongation of 83% compared with that before treatment.

After the treatment of the wool, according to the International Wool Bureau TWC.TM31 test method, the 5×5A test result is: -4.86%.

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

Example 2

In the present embodiment, the wool strip is subjected to a chlorine-free shrink-proof treatment by a continuous process of six-fold padding.

All wool wool strips to be treated, with a specification of 56 pieces. The process includes the following steps:

First tank: padding treatment liquid. The tank is a suction drum tank having a width of 1 meter, a volume of 360 liters and a circumference of one meter. The suction drum tank has an automatic heating device containing alkaline protease 3g/L and tris (3-hydroxypropyl group). A highly efficient catalytic solution of phosphine 3g/L with a pH of 10.5 and a controlled temperature of 50 °C.

The wool tops are evenly laid flat on the top rollers and fed into the treatment liquid at a speed of 3.8 m/min to completely wet the wool strips, ensuring that each fiber in the wool strip is uniformly treated thoroughly; The roller pressurizes the wool strip to ensure that the wool strip is 130%; then the wool strip with the enzyme liquid is passed to the second treatment tank at a speed of 3.8 m/min. The time from the entry of the wool strip into the first tank treatment liquid to the entry into the second tank treatment liquid took 31.5 seconds.

Second tank: padding treatment liquid. Same as the first slot.

Third tank: padding treatment liquid. Same as the first slot.

Fourth tank: padding treatment liquid. Same as the first slot.

Fifth tank: padding treatment liquid. Same as the first slot.

The sixth tank: padding treatment liquid. Same as the first slot. From the first slot to the end of the sixth slot, the time is 31.5 seconds x 6 = 189 seconds.

Seventh tank: washed. The wool strip is rolled and rolled to clean the reagents, enzymes and degradation products attached to the surface of the wool fiber, and the water temperature is normal temperature and the pH is 7.0.

Eighth tank: secondary washing. Same as the seventh slot.

The ninth trough: high-temperature water washing, playing an enzyme inactivation, to prevent subsequent erosion of wool fibers, temperature 95 ° C, time 15 seconds.

The tenth trough: the tops are padded with a 20g/L wool softener solution to soften the wool fibers to a softening effect and improve the hand. The softener solution had a temperature of 40 ° C, a pH of 7.0, and a time of 15 seconds. The wool strip is then dehydrated and dried.

The process speed is 3.8 m / min, and the solution is mixed and treated 6 times. The scale stripping effect of wool fiber treated by this process is shown in Fig. 2.

The wool treated by this process maintained a strength of 83% and an elongation of 72% compared with that before the treatment.

After the treatment of the wool, according to the International Wool Bureau TWC.TM31 test method, the 5×5A test result is: -3.82%.

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

Example 3

In the present embodiment, the wool strip is subjected to a chlorine-free shrink-proof treatment by a continuous process of five-fold padding.

All wool wool strips to be treated, with a specification of 90 pieces. The process includes the following steps:

First tank: padding treatment liquid. The tank is a suction drum tank having a width of 1 meter, a volume of 360 liters and a circumference of one meter, and the suction drum tank has an automatic heating device containing alkaline protease 3g/L and tris(3-carboxypropyl). Highly efficient catalytic solution of phosphine 3g/L, anhydrous calcium chloride 0.3g/L (addition of nonionic surfactant JFC 1g/L), pH 8.5 (pH adjusted with appropriate amount of sodium carbonate or sodium hydroxide solution), control The temperature is 50 °C.

The wool tops are evenly laid flat on the top rollers and fed into the treatment liquid at a speed of 3.8 m/min to completely wet the wool strips, ensuring that each fiber in the wool strip is uniformly treated thoroughly; The roller pressurizes the wool strip to ensure that the wool strip is 130%; then the wool strip with the enzyme liquid is passed to the second treatment tank at a speed of 3.8 m/min. The time from the entry of the wool strip into the first tank treatment liquid to the entry into the second tank treatment liquid took 31.5 seconds.

Second tank: padding treatment liquid. Same as the first slot.

Third tank: padding treatment liquid. Same as the first slot.

Fourth tank: padding treatment liquid. Same as the first slot.

Fifth tank: padding treatment liquid. Same as the first slot. From the first slot to the end of the fifth slot, the time is 31.5 seconds x 5 = about 158 seconds.

The sixth tank: washed. a reagent for the adhesion of wool fibers to the surface of the wool fiber by means of a roll of wool, and an enzyme and The degraded product was cleaned, the water temperature was normal temperature, and the pH was 7.0.

Seventh tank: secondary washing. Same as the sixth slot.

The eighth tank: high-temperature water washing, play an enzyme inactivation, to prevent subsequent erosion of wool fiber, temperature 95 ° C, time 15 seconds.

The ninth trough: the tops are padded with a 20g/L wool softener solution to soften the wool fibers to a softening effect and improve the hand. The softener solution had a temperature of 40 ° C, a pH of 6.0, and a time of 15 seconds. The wool strip is then dehydrated and dried.

The speed of the process is 3.8 m / min, and the treatment liquid is mixed for 5 times. The scale stripping effect of wool fiber treated by this process is shown in Fig. 3.

The wool treated by this process has a strength of 81% and an elongation of 80% compared with that before the treatment.

After the treatment of the wool, according to the International Wool Bureau TWC.TM31 test method, the 5×5A test result is: -2.98%.

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

Example 4

In the present embodiment, the wool strip is subjected to a chlorine-free shrink-proof treatment by a continuous process of five-fold padding.

All wool wool strips to be treated, with a specification of 80 pieces. The process includes the following steps:

First tank: padding treatment liquid. The tank is a suction drum tank having a width of 1 meter, a volume of 360 liters and a circumference of one meter. The suction drum tank has an automatic heating device, and is mainly filled with alkaline protease 3g/L and three (2-hydroxyethyl). A high-efficiency catalytic solution of phosphine 3 g/L, anhydrous calcium chloride 0.3 g/L (addition of nonionic surfactant JFC 1 g/L), pH 7.5, and control temperature of 50 °C.

The wool tops are evenly laid flat on the top rollers and fed into the treatment liquid at a speed of 4.5 m/min to completely wet the wool strips, ensuring that each fiber in the wool strip is uniformly treated thoroughly; The roller pressurizes the wool strip to ensure that the wool strip is 130%; then the wool strip with the enzyme liquid is allowed to enter the second treatment tank at a speed of 4.5 meters per minute. The time from the entry of the wool strip into the first tank treatment liquid to the entry into the second tank treatment liquid took 26.7 seconds.

Second tank: padding treatment liquid. Same as the first slot.

Third tank: padding treatment liquid. Same as the first slot.

Fourth tank: padding treatment liquid. Same as the first slot.

Fifth tank: padding treatment liquid. Same as the first slot. From the beginning of the first slot to the end of the fifth slot, the time is 26.7 seconds x 5 = about 134 seconds.

The sixth tank: washed. The wool strip is rolled and rolled to clean the reagents, enzymes and degradation products attached to the surface of the wool fiber, and the water temperature is normal temperature and the pH is 7.0.

Seventh tank: secondary washing. Same as the sixth slot.

The eighth tank: high-temperature washing, playing an enzyme to prevent the subsequent erosion of wool fiber, temperature 95 °C, time 15 seconds.

The ninth trough: the tops are padded with a 20g/L wool softener solution to soften the wool fibers to a softening effect and improve the hand. The softener solution had a temperature of 40 ° C, a pH of 6.0, and a time of 15 seconds. The wool strip is then dehydrated and dried.

The process speed is 4.5 m / min, and the solution is mixed and treated 5 times. The scale stripping effect of wool fiber treated by this process is shown in Fig. 4.

The wool treated by this process maintained a strength of 82% and an elongation of 81% compared with that before the treatment.

After the treatment of the wool, according to the International Wool Bureau TWC.TM31 test method, the 5×5A test result is: -3.56%.

Example 5

In the present embodiment, the wool strip is subjected to a chlorine-free shrink-proof treatment by a continuous process of seven-fold padding.

All wool wool strips to be treated, with a specification of 70 pieces. The process includes the following steps:

First tank: padding treatment liquid. The tank is a suction drum tank having a width of 1 meter, a volume of 360 liters and a circumference of one meter. The suction drum tank has an automatic heating device, and is mainly filled with alkaline protease 2g/L and tris(4-carboxybutyl). Highly catalyzed solution of phosphine 3g/L, anhydrous calcium chloride 0.3g/L (optional: plus nonionic surfactant JFC 1g/L or anionic surfactant), pH 8 and controlled temperature 50 °C.

The wool tops are evenly laid flat on the top rollers and fed into the treatment liquid at a speed of 6 m/min to completely wet the wool strips, ensuring that each fiber in the wool strip is uniformly treated thoroughly; The roller pressurizes the wool strip to ensure that the wool strip is 130%; then the wool strip with the enzyme liquid is passed to the second treatment tank at a speed of 6 m/min. It takes 20 seconds from the start of the wool strip to the first tank treatment liquid to the entry into the second tank treatment liquid.

Second tank: padding treatment liquid. Same as the first slot.

Third tank: padding treatment liquid. Same as the first slot.

Fourth tank: padding treatment liquid. Same as the first slot.

Fifth tank: padding treatment liquid. Same as the first slot.

The sixth tank: padding treatment liquid. Same as the first slot.

The seventh tank: padding treatment liquid. Same as the first slot. From the first slot to the end of the seventh slot, the time is 20 seconds x 7 = 140 seconds.

The eighth tank: washed. The wool strip is rolled and rolled to clean the reagents, enzymes and degradation products attached to the surface of the wool fiber, and the water temperature is normal temperature and the pH is 7.0.

Ninth tank: secondary washing. Same as the eighth slot.

The tenth tank: high-temperature water washing, play an enzyme inactivation, to prevent subsequent erosion of wool fiber, temperature 95 ° C, time 15 seconds.

The eleventh trough: tops padding 20g / L wool softener solution, softening the wool fiber to achieve softness If you improve your feel. The softener solution had a temperature of 40 ° C, a pH of 6.0, and a time of 15 seconds. The wool strip is then dehydrated and dried.

The process speed is 6 m / min, and the bathing solution is 7 times. The scale stripping effect of wool fiber treated by this process is shown in Fig. 5.

The wool treated by this process maintained a strength of 82% and an elongation of 80% compared with that before the treatment.

After the treatment of the wool, according to the International Wool Bureau TWC.TM31 test method, the 5×5A test result is: -3.01%.

Example 6

In the present embodiment, the wool product is subjected to a chlorine-free shrink-proof treatment by a continuous process of quadruple padding.

The product to be treated is a wool product (哔叽). Methods as below:

Four sets of Kroy deepim reaction chambers (each group is 1.5 meters deep, 1.8 meters wide and 0.4 meters thick), and the protease is integrated with catalytic treatment liquid. The main components of the treatment liquid are: alkaline protease 1.8g/L, three (4) - Carboxybutyl) phosphine bio-enzyme activator 3.0g / L, anhydrous calcium chloride 0.3g / L (optionally added non-ionic surfactant JFC1g / L) high-efficiency catalytic solution, pH 7.5, control temperature It is 50 °C. The flat webs to be treated were sequentially transferred into four groups of Kroy deepim reaction chambers, and the four-fold padding treatment was carried out at a constant speed of 6 m/min for 2 minutes, and the liquid ratio between each group was controlled at 100%, followed by water washing, Inactivated, soft, and dried.

After the above treatment, the wool product not only has good shrink-proof performance, especially the wetting and permeation properties, and the drip diffusion time (according to GB/T21655.1-2008) is improved from ≥10 minutes before treatment to ≤ 10 seconds.

Comparative example 1

Soaking treatment

The conventional immersion method is used for descaling and shrink-proof treatment as follows:

The wool strips (70, 20 g) were thoroughly soaked with the soaking treatment solution for 20 minutes or 60 minutes (50 ° C). After the immersion treatment, post treatment (similar to Example 1) was carried out by a conventional method, which included 3 water washings, followed by enzyme inactivation treatment and softening treatment, and finally dehydration and drying.

Among them, the formulation of the soaking treatment solution is as follows: alkaline protease (alkali protease) 3 g / L, nonionic surfactant JFC 1 g / L (pH = 8.5), the solvent is water.

The results showed 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 descaling effect of the wool is basically uniform, but there is still a small amount of wool which is insufficiently descaled. This indicates that the immersion process is not suitable for large-scale production because of its long time-consuming and uneven treatment effect.

Comparative example 2

Soaking-steaming treatment

The present comparative example adopts a conventional batch type, and is subjected to descaling and shrink-proof treatment by a soaking-steaming method. Methods as below:

Wool strips (70, 20 g) were fully soaked with a soaking treatment solution (50 ° C, 120% rolling rate), pre-soaked for about 1 minute, and then steamed (50 ° C) in a steaming box for 25 minutes. The steaming treatment liquid (the composition is the same as the immersion treatment liquid) is added at the 5th, 10th, 15th and 20th minutes. The soaking-steaming process took a total of 26 minutes.

After the soaking-steaming treatment, it was post-treated by a conventional method (similar to Example 1), which included 3 water washings, followed by enzyme inactivation treatment and softening treatment, and finally dehydration and drying.

Among them, the immersion treatment liquid was similar to the padding treatment liquid solution in Example 1, but did not contain tris(3-hydroxypropyl) phosphine. That is, the formula is as follows: alkaline protease (alkali protease) 3g / L, nonionic surfactant JFC1g / L.

result:

After the wool is subjected to the above-mentioned shrink-proof treatment, the sharp corners of the wool surface are substantially completely removed. However, the uniformity is poor, in which the fine wool surface scales are very vague, and the thicker wool scales are thinly cut, indicating that the treatment process has better peeling effect on fine wool scales than coarse wool.

After treatment, the fiber strength was 10.34 cN, the strength retention rate was 83.25%, the elongation was 32.30%, and the elongation retention rate was 64.77%. This indicates that the wool treated by this process can reach the anti-shrinkage requirement, the breaking strength loss is in an acceptable range, but the elongation loss is relatively large.

In addition, the entire soaking-steaming process took up to 26 minutes, and the treatment effect was far less than that of Examples 1-5. In contrast, the total time of multiple padding in Examples 1-5 of the present invention is very low (≤ 5 minutes, more preferably ≤ 3 minutes), and the descaling effect is more uniform, and the shrink-proof property is more excellent.

The outstanding features of the invention are chlorine-free, rapid continuous processing, to completely replace the chlorination shrinkage prevention method, improve the deficiency of the protease biological treatment process alone, improve the protease biological treatment method, and finally achieve the optimized treatment effect and improve the quality of the whole hair product. the goal of.

All documents mentioned in the present application are hereby incorporated by reference in their entirety in their entireties in the the the the the the the the In addition, it should be understood that various modifications and changes may be made by those skilled in the art in the form of the appended claims.

Claims (18)

1. The anti-shrinkage treatment agent for chlorine-free shrink-proof treatment, characterized in that the shrink-proof treatment agent comprises: (a) an optional solvent; (b) a protease; and (c) an organic compound represented by formula A a phosphine compound and optionally an inorganic salt;

   P-(X) ₃ A

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

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

   The weight ratio of the protease to the organophosphine compound is 0.2-10:0.5-20;

   And the protease in the anti-shrinkage treatment agent is selected from the group consisting of a neutral protease, an alkaline protease, or a combination thereof.
2. The anti-shrinkage treatment agent according to claim 1, wherein when the anti-shrinkage treatment agent is an aqueous solution or is reconstituted into an aqueous solution, the pH is 6.5 to 12, preferably 7-11.5, more preferably It is 7.5-10.5.
3. The shrink-proof treatment agent according to claim 1, wherein the organic phosphine compound is a water-soluble aliphatic organophosphine compound.
4. The shrink-proof treatment agent according to claim 1, wherein the organic phosphine compound has the following structure:

   P-(R ₁ -R ₂ ) ₃ I

   among them,

   R ₁ is a substituted or unsubstituted C 2 -C 8 alkylene group (preferably a C 1 -C 6 alkylene group); and/or

   R _{2 is} selected from the group consisting of -OH, -COOH, or a C2-C8 ester group, an alkali metal, or an alkaline earth metal.
5. The anti-shrinkage treatment agent according to claim 1, wherein the organophosphine compound is selected from the group consisting of tris(3-hydroxypropyl)phosphine, tris(3-carboxypropyl)phosphine, and tris(2- Hydroxyethyl)phosphine, tris(4-carboxybutyl)phosphine, or a combination thereof.
6. A shrink-proof treatment device for a chlorine-free wool strip or a wool product, characterized in that the device comprises:

   a multiple padding apparatus comprising n independent, continuously arranged padders, each of the paddings comprising a soaking tank and a rolling roll, wherein the soaking tank is used for placing chlorine-free Shrinking The shrink-proof treatment liquid so that the wool strip or wool product to be treated is immersed in the treatment liquid; and the rolling roll is used for rolling the soaked wool strip or wool product, and rolling by the upstream rolling roll a rear wool strip or wool product that is sequentially passed into a soaking tank and a rolling roll of a downstream padder to repeat the soaking and rolling treatment, wherein n is a positive integer of 2-20;

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

   An enzyme inactivating device for alkaline inactivation treatment of residual protease in the washed top or wool product to form an enzyme-inactivated top or wool product;

   An optional softening device for softening the enzyme-inactivated tops or wool products to form a softened top or wool product;

   An optional dryer for drying the softened tops or wool products obtained in the previous step.
7. The anti-shrinkage treatment apparatus according to claim 6, wherein one or more auxiliary padders are provided between or after each of the padders of said multiple padding apparatus, said auxiliary The padder independently comprises an auxiliary soaking tank and an auxiliary rolling roll, wherein the auxiliary soaking tank is provided with a protease treatment solution containing no organophosphine compound, and/or a protease-free organic phosphine compound treatment liquid.
8. A method for preventing shrinkage of a chlorine-free wool strip or a wool product, comprising the steps of:

   (a) providing a non-chlorinated wool strip or wool product to be treated, and a shrink-proof treatment agent for the chlorine-free wool strip or wool product of claim 1;

   (b) subjecting the chlorine-free wool strip or wool product to be treated to n-padding treatment with the anti-shrinkage treatment agent, thereby obtaining a padded wool product, wherein n is a positive integer of 2-10;

   (c) subjecting the padded chlorine-free wool strip or wool product to a water washing treatment to obtain a water-washed chlorine-free wool strip or wool product;

   (d) subjecting the water-washed chlorine-free wool strip or wool product to an enzyme inactivation treatment to obtain a shrink-free chlorine-free wool strip or wool product.
9. The method according to claim 8, wherein the total time T of the padding treatment of the step (b) is ≤ 15 minutes, preferably ≤ 10 minutes, more preferably ≤ 5 minutes, most preferably ≤ 3 minute.
10. A shrink-proof, chlorine-free wool product characterized in that the wool product has no residual organic chlorine, and the chlorine-free wool product is subjected to chlorine-free treatment by the shrink-proof treatment device according to claim 6. Or chlorine-free treatment by the method of claim 8.
11. The method of claim 10 wherein said chlorine free wool product has 4-5 characteristics selected from the group consisting of:

    (a) after treatment by the shrink-proof treatment method, the scale layer removal rate of the wool surface layer in the treated chlorine-free wool product is 80-100% compared to the wool product to be treated;

    (b) after treatment by the shrink-proof treatment method, the absolute value of the shrinkage of the treated chlorine-free wool product is ≤5%, optimally ≤3%, compared to the wool product to be treated, wherein the measuring method For the International Wool Bureau TWC.TM31 test method,

    (c) after treatment by the shrink-proof treatment method, the strength of the treated chlorine-free wool product is maintained ≥ 80% compared to the wool product to be treated;

    (d) after treatment by the shrink-proof treatment method, the elongation of the treated chlorine-free wool product is maintained ≥75% compared to the wool product to be treated;

    (e) The drip spread time of the treated chlorine-free wool product is ≤ 15 s.
12. An article comprising the wool product of claim 10 or the wool product of claim 10.
13. A use of the shrink-proof treatment agent according to claim 1, which is for use in a chlorine-free shrinkage-proof treatment of a top or wool product.
14. The anti-shrinkage treatment liquid for chlorine-free wool strips and wool products, characterized in that the main components thereof are: protease, water-soluble aliphatic trisubstituted organic phosphine compound, inorganic salt; said water-soluble aliphatic tri-substituted organic The phosphine structure is: P-(RS) ₃ , wherein R: is a hydrocarbon group having 1 to 6 carbons, S is a hydroxyl group or a carboxyl group and a derivative thereof; the mass concentration is 1 to 10 g/L; and the inorganic salt is calcium chloride. , its concentration is 0 ~ 2g / L.
15. The anti-shrinkage treatment liquid according to claim 14, wherein the trisubstituted organic phosphine is tris(3-hydroxypropyl)phosphine, tris(3-carboxypropyl)phosphine, or tris(2-hydroxyl). At least one of ethylphosphine and tris(4-carboxybutyl)phosphine.
16. The invention relates to a continuous processing technology for anti-shrinkage treatment of chlorine-free wool strips and wool products, which comprises the following steps:

    1) Anti-shrinkage treatment: the wool strips and wool products are leveled and transported through the rolls at a uniform speed into a plurality of anti-shrinkage treatment tanks alternately infiltrated and rolled 3-10 times. The process conditions are: the pH of the anti-shrinkage treatment liquid is 7～10.5, the temperature is 40～50°C; the rolling liquid rate is 60%～150%; the process conveying speed is 3～15m/min, and the total infiltration and rolling time is 1-5 minutes;

    2) Washing: the above treated wool strips are transferred into 1 to 4 clear water tanks by roll action to perform multiple washings to remove residual biological enzyme activators and enzyme preparations to prevent them from continuing to erode the wool;

    3) Inactivation of protease: the washed wool strips are uniformly and quickly passed through a 85-95 ° C hot water tank or a solution containing 0 to 1 g / liter of hydrogen peroxide to inactivate the protease that has not been completely washed;

    4) Soft treatment: the inactivated wool strip is soaked in a tank of a conventional wool smoothing agent or a silicone softener, and subjected to a general softening treatment to improve the hand feeling of the wool fabric;

    5) dehydration and drying;

    The anti-shrinkage treatment liquid mainly comprises:

    Trisubstituted organophosphine at a concentration of 1 to 10 g/L

    Calcium chloride at a concentration of 0.3 to 2 g/L

    Protease at a concentration of 0.5 to 5 g/L

    The rest is water

    The trisubstituted organic phosphine is: tris(3-hydroxypropyl)phosphine, tris(3-carboxypropyl)phosphine, tris(2-hydroxyethyl)phosphine, tris(4-carboxybutyl)phosphine At least one.
17. The method according to claim 16, wherein said soaking and pressing or rolling are repeated 3-10 times; the total time of said soaking treatment is between 1 and 5 minutes; and the process conveying speed is 3 -8 m / min.
18. The method of claim 16 wherein said wool strips are from 56 to 100 pieces of wool or cashmere.

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