Abstract:
An anti-pilling processing method of protein-base fiber materials, which comprises contacting said protein-base fiber materials with a treating liquid at a pH ranging from 2.0 to 8.0, said treating liquid comprising a crosslinking agent selected from the groups consisting of a compound having both of a glycidyl group and a vinyl group, a compound having at least two glycidyl groups, a compound having at least two vinyl groups, and a glycidyl methacrylate compound as a crosslinking agent, wherein said protein-base fiber is crosslinked by said compound.

Description:
FIELD OF THE INVENTION  
         [0001]    The present invention relates to an anti-pilling processing method of protein-base fiber materials for imparting pilling resistance to protein-base fiber materials such as, for example, wool, silk, and animal fibers. The present invention also relates to protein-base fiber materials having a pilling resistance using the processing method.  
         BACKGROUND OF THE INVENTION  
         [0002]    Woven and knitted fibers utilizing protein-base fiber materials such as merino type wool, angora, cashmere, alpaca, mohair, camel, lamb wool, etc., have excellent heat retaining properties and stretching properties. These fibers also have enriched hygroscopicity, water repellency, strong shape recovering power without shape crumbling, and elasticity. Consequently, they are suitable as fiber materials for clothes and have been industrially widely produced.  
           [0003]    However, in general, in woven and knitted products of protein-base fiber materials, cellulose-base fibers, etc., there is a problem when the fibers are subjected to friction or impact when worn. The micro fibers entangle with each other or with single fibers to form complicated entaglements or pilling which spoil the appearance of cloth products prepared from such fibers. Pilling also causes trouble in the handling the cloth product. Therefore, the pilling treatment becomes necessary and hand washing becomes necessary when the product is washed.  
           [0004]    Thus, with respect to protein-base fiber materials, it has been reported that processing methods for preventing felting and shrink resistance result in a slight anti-pilling effect. Various anti-pilling processing methods for cellulose-base fibers have been proposed.  
           [0005]    With respect to protein-base fiber materials, however, a by-product pilling has not been reduced to a pilling resistance of class 5 in the pilling test, JIS L1076.  
           [0006]    Processing methods suitable for cellulose-base fibers, when simply applied to the protein-base fiber materials, result in protein-base fiber deterioration by the treating liquid.  
         SUMMARY OF THE INVENTION  
         [0007]    The present invention has been made in view of the above-described problems in the related art. The object of the invention is to provide an anti-pilling processing method that obtains excellent pilling resistance without spoiling the feel of the protein-base fiber materials. A further object of the invention is to provide protein-base fiber materials having pilling resistance prepared by the above-described method.  
           [0008]    For attaining the above-described objects, the anti-pilling processing method of the invention is as follows: a compound having both of a glycidyl group and a vinyl group, a compound having at least two of either one of the above-described groups, or a glycidyl methacrylate compound are used as a crosslinking agent in a crosslinking reaction in which the pH of a treating liquid containing the above-described crosslinking agent is controlled to be in the range of from 2.0 to 8.0.  
           [0009]    The use of such a crosslinking reaction in the anti-pilling processing method of the invention yields excellent pilling resistance in the protein-base fiber materials, and cloth products without deterioration of the protein-base fiber materials.  
         DETAILED DESCRIPTION OF THE INVENTION  
         [0010]    In the anti-pilling processing method of the invention the protein-base fiber materials are contacted with a treating liquid which contains a compound having both a glycidyl group and a vinyl group, a compound having at least two of either one of these groups, or a glycidyl methacrylate compound. This compound is used as a crosslinking agent. The crosslinking reaction is carried out by controlling the pH of the treating liquid to be within the range of from 2.0 to 8.0.  
           [0011]    The protein-base fiber material may be a single spun or a mixed spun fiber. If the material contains protein-base fibers such as, for example, wool, silk, animal wool, etc., as the main constituent, composite fibers containing so-called synthetic fibers may be used.  
           [0012]    In the case of animal fibers, it is more desirable to use a material made of, as the main constituent, off-scale fibers, wherein flaky scales are removed. This is because when the off-scale fibers are used, the reactivity of the treatment of the invention is improved. The anti-pilling effect is stabilized, and additionally shrink resistance may be improved.  
           [0013]    In the anti-pilling processing method of the invention, a compound having both of a glycidyl group and a vinyl group, a compound having at least two of either one of the groups, or a glycidyl methacrylate compound is used as a crosslinking agent. That is, the crosslinking agent is one of (1) a compound having both of a glycidyl group and a vinyl group, (2) a compound having at least two glycidyl groups, (3) a compound having at least two vinyl groups, and (4) a glycidyl methacrylate compound.  
           [0014]    Also, in the anti-pilling processing method of the invention, the crosslinking reaction is carried out by maintaining the pH of the treating liquid to the range of from 2.0 to 8.0. When the pH of the treating liquid is in the range described above, the protein-base fiber material is not deteriorated.  
           [0015]    There is no particular restriction on the method of controlling the pH of the treating liquid. For example, when the pH is adjusted to the acidic side formic acid can be used, and when the pH is adjusted to the weak-alkaline side, soda ash can be used.  
           [0016]    The amount of the crosslinking agent, which is added to the treating liquid in the invention, is in the range of usually from 3 to 80% by weight, and preferably from 3 to 20% by weight based on the amount of the fiber material, and the bath ratio can be in the range of, for example, 1:9 to 24. Also, if necessary, from 0.03 to 1% by weight of a catalyst may be added to the treating liquid to improve the efficiency of the crosslinking reaction.  
           [0017]    There are no particular restrictions on the reaction conditions of the crosslinking reaction. However, to improve the reaction efficiency, it is desirable to increase the temperature to from 100 to 105° C. while sufficiently stirring the treating liquid in a treatment bath and to carry out a heat treatment at the temperature for from 1 to 3 hours. After completing the crosslinking reaction at the temperature, water washing and soaping may be carried out. The resultant fiber material of the invention will have pilling resistance.  
           [0018]    The concentration of the treating liquid, the bath ratio, the catalyst, and the reaction conditions of the crosslinking reaction can be changed according to the kind and the processing purpose of the protein-base fiber material outside of the temperatures and times above-described. The fiber material of the invention may be of any type such as cottons, yarns, raw stocks, textiles, knitted products, etc. The anti-pilling processing method of the invention can be applied to any type of woven or knitted product, such as yarns or semi-finished products. 
       
    
    
     EXAMPLES  
       [0019]    The anti-pilling processing method and the protein-base fiber materials of the invention are also described in the following examples. The invention is not limited to the following examples.  
       Example 1  
       [0020]    A cheese roll of 500 g per one yarn of off-scale wool yarns of 1/48 count subjected to a scouring treatment is mounted on a cheese dyeing machine for 1 kg test, and water of room temperature is added to the treatment bath such that the bath ratio becomes 1:18.  
         [0021]    While circulating water in the treatment bath, allyl glycidyl ether is added in an amount of 19% by weight to the weight of the fibers as a crosslinking agent.  
         [0022]    Then, 2-2′azobis(2-amidinopropane) di-hydrochloride of 0.3% by weight to allyl glycidyl ether is added as a catalyst.  
         [0023]    By adding formic acid to the above-described treating liquid, the pH of the treating liquid is adjusted to 3.2.  
         [0024]    Thereafter, the treating liquid is circulated, the temperature is gradually raised to 100° C., and the treating liquid is maintained at this temperature for 3 hours. The pH at the end of the reaction is 3.2.  
         [0025]    After a slow cooling treatment, the treating liquid is removed, water washing is repeated three times, and then hot water washing is carried out at 60° C. for 10 minutes. Thereafter, water washing is carried out three times and a softening treatment is applied for 15 minutes at 45° C. to finish the processing treatment.  
         [0026]    The yarns thus obtained were knitted plain to obtain a protein-base fiber material. Using the fabric of Example 1, a pilling test using JIS L1076 ICI type test machine, pilling resistance was evaluated. A very excellent pilling resistance was obtained as shown in Table 2 below.  
       Example 2  
       [0027]    A cheese roll of 500 g per one yarn of off-scale wool yarns of 1/48 count subjected to a scouring treatment is mounted on a cheese dyeing machine for 1 kg test, and water of room temperature is added to the treatment bath such that the bath ratio becomes 1:18.  
         [0028]    While circulating water in the treatment bath, glycidyl methacrylate is added in an amount of 5% by weight to the weight of the fibers as a crosslinking agent.  
         [0029]    By adding formic acid to the above-described treating liquid, the pH of the treating liquid is adjusted to 2.0.  
         [0030]    Thereafter, the treating liquid is circulated, the temperature is gradually raised to 100° C., and the treating liquid is maintained at this temperature for 3 hours. The pH at the end of the reaction is 2.0.  
         [0031]    After a slow cooling treatment, the treating liquid is removed, water washing is repeated three times, and then hot water washing is carried out at 60° C. for 10 minutes. Thereafter, water washing is carried out three times, and a softening treatment is applied for 15 minutes at 45° C. to finish the treatment.  
         [0032]    The yarns thus obtained were knitted plain, and the pilling test described in Example 1 was conducted. A very excellent pilling resistance was obtained as shown in Table 2 below.  
       Example 3  
       [0033]    A cheese roll of 500 g per one yarn of off-scale wool yarns of 1/48 count subjected to a scouring treatment is mounted on a cheese dyeing machine for 1 kg test, and water of room temperature is added to the treatment bath such that the bath ratio becomes 1:18.  
         [0034]    While circulating water in the treatment bath, ethylene glycol dimethacrylate is added in an amount of 5% by weight to the weight of the fibers as a crosslinking agent.  
         [0035]    By adding formic acid to the above-described treating liquid, the pH of the treating liquid is adjusted to 3.0.  
         [0036]    Thereafter, the treating liquid is circulated, the temperature is gradually raised to 100° C., and the treating liquid is maintained at this temperature for one hour. The pH at the end of the reaction is 3.0  
         [0037]    After a slow cooling treatment, the treating liquid is removed, water washing is repeated three times, and then hot water washing is carried out at 60° C. for 10 minutes. Thereafter, water washing is carried out three times, and a softening treatment is applied for 15 minutes at 45° C. to finish the treatment.  
         [0038]    The yarns thus obtained were knitted plain, and the pilling test described in Example 1 was conducted. A very excellent pilling resistance was shown as in Table 2 below.  
       Example 4  
       [0039]    A cheese roll of 500 g per one yarn of off-scale wool yarns of 1/48 count subjected to a scouring treatment is mounted on a cheese dyeing machine for 1 kg test, and water of room temperature is added to the treatment bath such that the bath ratio becomes 1:18.  
         [0040]    While circulating water in the treatment bath, ethylene glycol diglycidyl ether is added in an amount of 12% by weight to the weight of the fibers as a crosslinking agent.  
         [0041]    By adding formic acid to the above-described treating liquid, the pH of the treating liquid is adjusted to 4.2.  
         [0042]    Thereafter, the treating liquid is circulated, the temperature is gradually raised to 100° C., and the treating liquid is maintained at this temperature for 3 hours. The pH at the end of the reaction is 4.2.  
         [0043]    After a slow cooling treatment, the treating liquid is removed, water washing is repeated three times, and then hot water washing is carried out at 60° C. for 10 minutes. Thereafter, the yarns are dyed to black by an ordinary dyeing condition, and a softening treatment is carried out.  
         [0044]    The yarns thus obtained were knitted plain, and the pilling test described in Example 1 was conducted. A very excellent pilling resistance was shown as in Table 2 below.  
       Example 5  
       [0045]    A cheese roll of 500 g per one yarn of off-scale wool yarns of 1/48 count subjected to a scouring treatment is mounted on a cheese dyeing machine for 1 kg test, and water of room temperature is added to the treatment bath such that the bath ratio becomes 1:18.  
         [0046]    While circulating water in the treatment bath, ethylene glycol diglycidyl ether is added in an amount of 12% by weight to the weight of the fibers as a crosslinking agent.  
         [0047]    Aluminum chloride is added to the treating liquid as a catalyst in an amount of 1% by weight to the amount of ethylene glycol diglycidyl ether. In this case, the pH of the treating liquid was 7.4.  
         [0048]    Thereafter, the treating liquid is circulated, the temperature is gradually raised to 100° C., and the treating liquid is maintained at this temperature for 2 hours. The pH at the end of the reaction is 7.4.  
         [0049]    After a slow cooling treatment, the treating liquid is removed, water washing is repeated three times, and hot water washing is carried out at 60° C. for 10 minutes. Thereafter, the yarns are dyed to black by an ordinary dyeing condition, and a softening treatment is carried out.  
         [0050]    The yarns thus obtained were knitted plain and the pilling test described in Example 1 was conducted. A very excellent pilling resistance was shown as in Table 2 below.  
       Example 6  
       [0051]    A cheese roll of 500 g per one yarn of off-scale wool yarns of 1/48 count subjected to a scouring treatment is mounted on a cheese dyeing machine for 1 kg test, and water of room temperature is added to the treatment bath such that the bath ratio becomes 1:18.  
         [0052]    While circulating water in the treatment bath, ethylene glycol diglycidyl ether is added in an amount of 12% by weight to the weight of the fibers as a crosslinking agent.  
         [0053]    Then, 100 g/liter of Glauber&#39;s salt is added.  
         [0054]    By adding soda ash to the above-described treating liquid, the pH of the treating liquid is adjusted to 8.0.  
         [0055]    Thereafter, the treating liquid is circulated, the temperature is gradually raised to 100° C., and the treating liquid is maintained at this temperature for 2 hours. The pH at the end of the reaction is 8.0.  
         [0056]    After a slow cooling treatment, the treating liquid is removed, water washing is repeated three times, and then hot water washing is carried out at 60° C. for 10 minutes. Thereafter, the yarns are dyed to black by an ordinary dyeing condition, and a softening treatment is carried out.  
         [0057]    The yarns thus obtained were knitted plain, and the pilling test described in Example 1 was conducted. A very excellent pilling resistance was shown as in Table 2 below.  
       Comparative Example 1  
       [0058]    A cheese roll of 1 kg per one yarn of off-scale wool yarns of 1/48 count subjected to a scouring treatment was dyed to an ordinary black dye color using a cheese dyeing machine for 1 kg test, and then was subjected to a softening treatment for 15 minutes at 45° C. The yarns thus obtained were knitted plain to prepare a fabric.  
       Comparative Example 2  
       [0059]    A cheese roll of 500 g per one yarn of off-scale wool yarns of 1/48 count subjected to a scouring treatment is mounted on a cheese dyeing machine for 1 kg test, and water of room temperature is added to the treatment bath such that the bath ratio becomes 1:18.  
         [0060]    While circulating water in the treatment bath, glycidyl methacrylate is added in an amount of 5% by weight to the weight of the fibers as a crosslinking agent.  
         [0061]    By adding sodium hydroxide to the above-described treating liquid, the pH of the treating liquid is adjusted to 11.7.  
         [0062]    Thereafter, the treating liquid is circulated, the temperature is gradually raised to 100° C., and the treating liquid is maintained at this temperature for 3 hours. The pH at the end of the reaction is 11.7.  
         [0063]    After a slow cooling treatment, the treating liquid is removed, water washing is repeated three times, and then hot water washing is carried out at 60° C. for 10 minutes. Thereafter, water washing is carried out three times, and a softening treatment is applied for 15 minutes at 45° C. to finish the treatment.  
         [0064]    Preparation of a fabric was attempted using the yarns thus obtained. However, since the yarns were deteriorated and their strength was lowered, a fabric could not be prepared.  
         [0065]    Characteristics and conditions of Examples 1 to 6 and Comparative Examples 1 and 2 are summarized in Table 1. The test results are summarized in Table 2.  
         [0066]    The crosslinking agent “allyl glycidyl ether” used in Example 1 is an example as a compound having one glycidyl group and one vinyl group, the crosslinking agent “ethylene glycol dimethacrylate” used in Example 3 is as a compound having two vinyl groups, the crosslinking agent “ethylene glycol glycidyl ether” used in Examples 4 to 6 is as a compound having two glycidyl groups. The purities of the crosslinking agents used in the examples were almost 100%.  
                                                 TABLE 1                                           pH of           Crosslinking Agent Added to       Treating           Treating Liquid   Pattern   Liquid                                    Example 1   Allyl glycidyl ether   2   3.2       Example 2   Glycidyl methacrylate   4   2.0       Example 3   Ethylene glycol dimethacrylate   3   3.0       Example 4   Ethylene glycol diglycidyl ether   1   4.2       Example 5   Ethylene glycol diglycidyl ether   1   7.4       Example 6   Ethylene glycol diglycidyl ether   1   8.0       Comparative   —   —   6.8       Example 1       Comparative   Glycidyl methacrylate   —   11.7       Example 2                                                  
 
         [0067]    [0067]                                       TABLE 2                           (Using JIS L1076 ICI type test machine)                Pilling Test Results                            Example 1   Class 5           Example 2   Class 5           Example 3   Class 5           Example 4   Class 5           Example 5   Class 5           Example 6   Class 5           Comparative Example 1   Class 2           Comparative Example 2   —                        
         [0068]    As shown in Table 2, the protein-base fiber materials of Examples 1 to 6 have excellent pilling resistance. The pilling test results by JIS L1076 method of each are class 5. Also, as shown in Examples 1 to 6, since in the processing method of the invention, the pH of each treating liquid is adjusted to the range of from 2.0 to 8.0, the protein-base fiber materials are not deteriorated as in Comparative Example 2. Therefore, these fiber materials have sufficient practical usable properties.  
         [0069]    The anti-pilling processing method of the invention yields an excellent pilling resistance to the protein-base fiber materials without spoiling the feel of the protein-base fiber materials. Also, since in the anti-pilling processing method of the invention, the pH of the treating liquid is adjusted to the range of from 2.0 to 8.0, the fibers are not deteriorated by the treating liquid.  
         [0070]    The processing method of the invention yields the excellent pilling resistance far greater than the slight pilling resistance obtained as a by-product of other processing methods aimed at preventing felting and shrink resistance. The functional properties of a protein-base fiber material processed according to the present invention are improved. These materials can be used not only as general cloth materials but also in stockings and clothes for sports, etc., which are liable to pilling damage. Also, since the anti-pilling processing method of the invention does not require specific equipment and the crosslinking agents used are relatively inexpensive, the method of the invention is also economical and practical.