Process and Device for Chlorine-Free Shrinkproof Treatment of Wool Raw Material and Article Thereof

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.

1 .- 18 . (canceled) 
     
     
         19 . A shrinkproof treatment method for chlorine-free wool tops or wool products, which comprises the following steps:
 (a) providing chlorine-free wool tops or wool products to be treated, and a shrinkproof treatment agent for chlorine-free wool tops or wool products;   (b) padding the chlorine-free wool tops or wool products to be treated with the shrinkproof treatment agent for n times, thereby obtaining padded wool products, wherein n is a positive integer of 2 to 20;   (c) water washing the padded chlorine-free wool tops or wool products, thereby obtaining water washed chlorine-free wool tops or wool products;   (d) conducting an enzyme inactivation treatment of the water washed chlorine-free wool tops or wool products, thereby obtaining shrinkproof treated chlorine-free wool tops or wool products.   
     
     
         20 . The method according to claim  1 , wherein total time T of the padding treatment of step (b) is ≦15 minutes. 
     
     
         21 . The method according to claim  1 , wherein n is a positive integer of 3 to 15. 
     
     
         22 . The method according to claim  1 , wherein the shrinkproof treatment agent comprises: (a) an optional solvent; (b) a protease; and (c) an organic phosphine compound represented by formula A; and an optional inorganic salt;
   P—(X) 3   A
   
       wherein each X is independently selected from the group consisting of substituted or unsubstituted C 1 -C 10  hydrocarbyl, wherein the term “substituted” refers to one or more substituents selected from the group consisting of —OH, —COOH (carboxy), C 2 -C 8  ester group, —SH, —CN, C 1 -C 3  alkyl, C 1 -C 3  alkoxy;
 and at least one X is a substituted C 1 -C 10  hydrocarbyl having a —OH or COOH substituent; the weight ratio of the protease to the organic phosphine compound is (0.2 to 10): (0.5 to 20); 
 and the protease in the shrinkproof treatment agent is selected from the group consisting of a neutral protease, an alkaline protease, and combinations thereof. 
 
     
     
         23 . The method according to  claim 22 , wherein the organic phosphine compound has the following structure formula:
   P—(R 1 -R 2 ) 3   I
   
       wherein, R 1  is substituted or unsubstituted C 2 -C 8  alkylene; and/or R 2  is selected from the group consisting of —OH, —COOH, C 2 -C 8  ester group, alkali metal, and alkaline earth metal. 
     
     
         24 . The method according to  claim 22 , wherein the organic phosphine compound is selected from the group consisting of tris(3-hydroxypropyl)phosphine, tris(3-carboxypropyl)phosphine, tris(2-hydroxyethyl)phosphine, tris(4-carboxybutyl)phosphine, and combinations thereof. 
     
     
         25 . A shrinkproof treatment device for chlorine-free wool tops or wool products, which comprises:
 a multiple padding apparatus which comprises n independent, continuously arranged padding machines, and every padding machine comprises a soaking tank and a rolling roller, wherein the soaking tank is used for placing a shrinkproof treatment agent for chlorine-free shrinkage treatment and the wool tops or the wool products to be treated are immersed in the treatment agent; and the rolling roller is used for rolling soaked wool tops or wool products, and the wool tops or wool products rolled by a rolling roller upstream enter into the soaking tank and the rolling roller of the padding machine downstream in turn, thereby repeating the soaking and rolling treatment, wherein n is a positive integer of 2 to 20;   a water washing apparatus for water washing the padded wool tops or wool products to form washed wool tops or wool products;   an enzyme inactivation apparatus for alkaline inactivation treatment of residual protease in the washed wool tops or wool products to form an enzyme-inactivated wool tops or wool products;   an optional soft processing apparatus for soft processing the enzyme-inactivated wool tops or wool products to form a softened wool tops or wool products; and   an optional dryer used to dry the softened wool tops or wool products obtained in the previous step.   
     
     
         26 . The shrinkproof treatment device according to  claim 25 , wherein one or more auxiliary padding machines are further set between or behind every padding machine of the multiple padding apparatus, and every auxiliary padding machines independently comprises an auxiliary soaking tank and an auxiliary rolling roller, wherein the auxiliary soaking tank is filled with a protease treatment solution containing no organic phosphine compound and/or an organic phosphine compound treatment liquid containing no protease. 
     
     
         27 . A shrinkproof chlorine-free wool product wherein there is no residual organic chlorine in the wool product and the chlorine-free wool product is chlorine-free treated using the shrinkproof treatment device according to  claim 25 . 
     
     
         28 . A shrinkproof chlorine-free wool product wherein there is no residual organic chlorine in the wool product and the chlorine-free wool product is chlorine-free treated using the method according to  claim 19 . 
     
     
         29 . The shrinkproof chlorine-free wool product according to  claim 28 , wherein the chlorine-free wool product has four or five characteristics selected from the group consisting of:
 (a) after treated by the shrinkproof treatment method, scale layer removal rate of wool surface layer of the treated chlorine-free wool product is 80 to 100% compared with that of the wool product to be treated;   (b) after treated by the shrinkproof treatment method, the absolute value of shrinkage rate of the treated chlorine-free wool product is ≦5%, when it is compared with that of the wool product to be treated, wherein measurement method thereof is TWC.TM31 test method of the International Wool Bureau;   (c) after treated by the shrinkproof treatment method, strength retention of the treated chlorine-free wool product is ≧80% compared with that of the wool product to be treated;   (d) after treated by the shrinkproof treatment method, elongation retention of the treated chlorine-free wool product is ≧75% compared with that of the wool product to be treated;   (e) drip diffusion time of the treated chlorine-free wool product is ≦15 s.   
     
     
         30 . An article, wherein the article comprises the wool product according to  claim 28  or is made of the wool product according to  claim 28 . 
     
     
         31 . A shrinkproof treatment agent for chlorine-free wool tops and wool products, wherein its main components comprise a protease, a water-soluble aliphatic trisubstituted organic phosphine compound, and an inorganic salt; and the water-soluble aliphatic trisubstituted organic phosphine has a structure of P—(R—S) 3 , wherein R is hydrocarbyl containing 1 to 6 carbon, S is hydroxyl or carboxyl and derivatives thereof; and mass concentration thereof is 1 to 10 g/L; the inorganic salt is calcium chloride, and concentration thereof is 0 to 2 g/L. 
     
     
         32 . The shrinkproof treatment agent according to  claim 31 , wherein the trisubstituted organic phosphine is at least one of tris(3-hydroxypropyl)phosphine, tris(3-carboxypropyl)phosphine, tris(2-hydroxyethyl)phosphine and tris(4-carboxybutyl)phosphine. 
     
     
         33 . A continuous processing process for shrinkproof treatment of chlorine-free wool tops and wool products, wherein it comprises following steps:
 1) shrinkproof treatment: wool tops and wool products are arranged, and uniformly transported with a roller into a number of tanks filled with shrinkproof treatment agent and subjected to an alternate soaking and rolling treatment for 3 to 10 times, wherein process conditions comprising: pH of the shrinkproof treatment agent is 7 to 10.5, temperature is 40 to 50° C.; a rolling liquid-containing rate is 60% to 150%; process delivery speed is 3 to 15 m/min, and total time of soaking and rolling is 1 to 5 minutes;   2) water washing: the treated wool tops obtained in the previous step are transported by rolling into one to four water tanks for multiple washing, thereby removing residual biological enzyme activator and enzyme preparation to prevent them from continuously eroding wool;   3) inactivation of protease: the washed wool tops are evenly and quickly passed through a hot water tank filled with hot water having a temperature of 85 to 95° C. or a solution containing 0 to 1 g/L of hydrogen peroxide, thereby inactivating any protease which is not completely washed out;   4) soft treatment: the inactivated wool tops are soaked into a tank filled with a conventional wool smoothing agent or organosilicon softening-agent, and a common soft treatment is conducted to improve feel of wool fabric;   5) dehydration and drying;   
       wherein the shrinkproof treatment agent mainly contains:
 trisubstituted organic phosphine, with a concentration of 1 to 10 g/L; 
 calcium chloride, with a concentration of 0.3 to 2 g/L; 
 protease, with a concentration of 0.5 to 5 g/L; 
 and the rest is water; 
 
       and the trisubstituted organic phosphine is at least one of tris(3-hydroxypropyl)phosphine, tris(3-carboxypropyl)phosphine, tris(2-hydroxyethyl)phosphine and tris(4-carboxybutyl)phosphine. 
     
     
         34 . The process according to  claim 33 , wherein the soaking and rolling treatment or padding treatment is repeated for 3 to 10 times; total time for the padding treatment is between 1 and 5 minutes; and process delivery speed is 3 to 8 m/min. 
     
     
         35 . The process according to  claim 33 , wherein the wool tops are wool or cashmere of 56 to 100 branches.