JPH06341067A - Processing agent for fiber structure and processing process - Google Patents

Abstract

PURPOSE:To provide a processing agent which contains a specific water-soluble immobilized enzyme to be utilized in processing such as scouring of fiber structure and can perform uniform and stabilized processing without reduction in fiber strength. CONSTITUTION:When fiber structure made from natural and synthetic fibers is enzymatically treated, water-soluble immobilized enzyme prepared by reaction of an enzyme such as amylase, protease, cellulase, pectitose or the like with a copolymer such as methyl vinyl ether-maleic anhydride copolymer, CMC, ethylene glycol-maleic anhydride copolymer, etc., is used to effect uniform processing such as desizing, scouring or modification. The immobilized enzyme can be recovered and used again to prevent the environmental deterioration with economical advantage.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing an enzyme such as desizing, scouring, and modifying a fiber structure and a treating agent used therefor.

[0002]

2. Description of the Related Art Generally, prior to dyeing and finishing of a fiber structure, a so-called desizing process for removing the sized glue on the warp threads of the fabric, a scouring process for removing unnecessary substances from the fiber structure are generally performed. , Processing such as modification treatment for giving added value to the fiber structure is performed, and such treatment can be performed by chemical reaction using acid, alkali, etc., but the specificity of the reaction, mild reaction conditions Amylase, which usually reacts at a specific site of the fiber structure
It is carried out using enzymes such as protease, cellulase, pectinase, catalase, lipase and hemicellulase.

However, the enzymes used for the above-mentioned processing are biocatalysts derived from microorganisms, animals and plants, and have different working pH, working temperature, stability, etc. Since it is carried out under certain restricted conditions, the selection itself of an enzyme that can sufficiently satisfy the required performance such as the uniformity of enzyme action and the strength retention of the fiber to be treated under such conditions It involves considerable difficulty and has various problems such as the following problems.

That is, for example, among the amylase used in the desizing process, a thermostable enzyme having a high activity at high temperature is known, but even though it is not known, the thermostability at the working temperature is still low. Therefore, there is a disadvantage in that the processing step using the enzyme described above requires a short-time processing. Moreover, in order to exert a sufficient enzyme action and improve the treatment efficiency, it is necessary to strongly move the fiber structure in the treatment bath in the above-mentioned treatment step. This is the case in the case of fiber structures such as rayon and silk. The problem of physical damage such as rubbing occurs, and the problem of felting occurs in the case of wool.

In the scouring step, for example, protease is used to remove sericin from silk, pectinase is used to remove sticking substances from hemp, and lipase is used to remove oil and fat from silk and wool, polyester, polyamide, polyacrylonitrile, silk and wool. Hemicellulases, amylases, proteases, cellulases, etc. are used for desizing after printing of rayon, rayon, cotton cloth, etc., but since the fiber structure after treatment is immediately linked to the product in these treatments, the fiber structure Minimizing damage is an important issue. However, as a solution to the above-mentioned problem, only the selective use of an enzyme that exerts a gentle enzyme action is performed exclusively, and the use of such an enzyme requires a long-time treatment, and a uniform processing treatment is the same as that of the enzyme itself. We are forced to rely on stability.

Further, as the modification treatment, cellulase is applied to cellulosic fibers such as cotton, hemp and rayon for the purpose of improving the texture of the fibers, improving the surface condition and morphology, changing the physical properties and reducing the weight. It is well known that treatments such as treatment and treatment of protein fibers such as wool and silk with a protease have a uniform crystal structure (three-dimensional structure) like chemical fibers. Various physical properties such as fiber structure (morphology and fine structure) differ depending on the situation and history at the time of collection, and in particular, due to the non-uniformity of the surface, a part where enzyme action is difficult occurs and the above modification There is an adverse effect that the treatment is non-uniform.

[0007] As a device for solving the above-mentioned harmful effects and performing a uniform enzyme treatment, for example, salt in an enzyme processing solution,
It is known to add salts such as calcium chloride, stabilizers such as polyethylene glycol, glycerin, casein, polypeptone, lactic acid, etc., and surfactants that do not inhibit enzyme, etc. There is also known a mechanical means for permeating the fiber and a means for pretreating the fiber with a chemical treatment agent to change its structure so that the enzyme acts uniformly.

However, in the method of adding the above-mentioned various stabilizers and the like, there is a disadvantage that the stabilizer used is attached to the fiber structure and excessive cleaning is required for its removal. The mechanical method has the disadvantage of roughening, breaking or rubbing of the fiber surface, and the adoption of the pretreatment method causes new problems such as complicated processes and changes in the physical properties of the fiber. There are drawbacks that arise.

As described above, all of the conventionally known methods for processing the fiber structure with the enzyme still have problems to be solved, and in particular, the homogenization of the effect of the enzyme treatment and the stabilization of the enzyme treatment conditions are attempted. At present, there is a demand in the art for development of means capable of more favorably carrying out the intended processing treatment and preventing the decrease in fiber strength due to excessive enzyme action. In addition, at present, the disposable use of the enzyme agent used in the enzyme processing treatment may cause a deterioration of the environment, and from the standpoint of resource saving, the uneconomical effect of such disposable use is becoming a problem that cannot be ignored. is there.

[0010]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to solve the problems which the above-mentioned conventional enzymatic processing of the fiber structure basically has, and to sufficiently consider the influence on the environment. Therefore, it is to develop a new technique capable of uniformly and sufficiently processing a fiber structure, suppressing brittleness of the fiber, and providing a target processed fiber of good quality.

Another object of the present invention is to provide an enzyme processing technology for the above-mentioned fiber structure, in which the used enzyme can be recovered and reused, whereby environmental deterioration can be suppressed to a minimum, and which is economically advantageous. To do.

[0012]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors on the basis of the above-mentioned objects, it has been found that the use of a water-soluble immobilized enzyme described below can provide a processing agent and a processing method which meet the above-mentioned objects. The present invention has been completed here.

That is, according to the present invention, a treating agent used for enzymatically treating a fiber structure, which is characterized by containing a water-soluble immobilized enzyme, and a treating agent for a fiber structure, and a fiber structure. Provided is a method for processing a fiber structure, which comprises using a processing agent containing a water-soluble immobilized enzyme in the enzymatic processing.

The fiber structures to be treated in the present invention include various fiber structures which are known to be capable of desizing, scouring, modifying and other various kinds of processing with enzymes. To be done. Specific examples thereof include cellulosic fibers such as cotton, hemp and rayon, natural fibers such as protein fibers such as wool and silk, and synthetic fibers such as polyamide, polyester and polyacrylonitrile, or 2 Examples thereof include threads and cloths obtained by using more than one kind.

The processing agent of the present invention requires the use of a water-soluble immobilized enzyme. The enzyme itself that constitutes the water-soluble immobilized enzyme may be any of various substances that are conventionally known to be used for the processing of the fiber structure of this kind with an enzyme. More specifically, for example, amylase, protease, cellulase, pectinase, catalase, lipase, hemicellulase and the like can be exemplified. These enzyme agents can be used alone or in an appropriate combination of two or more kinds belonging to the same kind or different kinds.

The immobilization of the above-mentioned enzyme preparation, that is, the preparation of the water-soluble immobilized enzyme can be carried out by a usual method using various kinds of water-soluble immobilized carriers which are generally known. More specifically, the water-soluble immobilization carrier that can be used here is,
There is no particular limitation as long as it can be selected from water-soluble polymer substances having a property of dissolving in water under a temperature condition of about 0 to 80 ° C., and the polymer substance has a group capable of chemically bonding with a functional group of an enzyme molecule. Typical examples thereof include copolymers of methyl vinyl ether and maleic anhydride, carboxymethyl cellulose, polyethylene glycol, copolymers of methyl ether and maleic anhydride, polyacrylic acid, polyvinyl alcohol, hydroxyethyl starch, acrylic acid. Examples of various synthetic macromolecules such as copolymers of ethylene glycol and maleic anhydride, and natural macromolecules such as poly-L-glutamic acid, collagen, chitosan, alginic acid, casein, water-soluble silk and water-soluble wool it can.

The reaction between the water-soluble immobilized carrier and the enzyme is
It can be easily carried out by mixing both using an appropriate buffer solution so that the pH is in the range of 3 to 11 as necessary. The temperature condition at that time is usually in the range of about 0 to 80 ° C., and the mixing is completed within about 72 hours by a general stirring operation. It is also suitable that the enzyme is usually mixed with the above carrier in a liquid form having a concentration of about 60% or less. The amount of the enzyme to be mixed with the carrier is preferably such that at least one enzyme is carried per molecule of the carrier, thus obtaining the desired water-soluble immobilized enzyme.

The water-soluble immobilized enzyme is one in which a water-soluble immobilized carrier (polymeric substance) and an enzyme molecule are chemically bonded, and the molecular weight thereof is usually tens of thousands depending on the carrier and the type of enzyme used. It can be adjusted arbitrarily within the range of several millions. In any case, this is an enzyme alone, such as amylase,
Compared to the molecular weight of cellulase, which is about 30,000 to 60,000, it is a very high molecule (large molecular size), and the enzyme molecule is bound to the high molecular substance by chemical bonding, so the actual fiber It is less susceptible to heat and pH during processing of the structure, and therefore its stability is markedly improved as compared to the enzyme alone. Such an improvement in stability does not substantially change the action mechanism of each enzyme, particularly for a fiber structure that may cause nonuniform property changes,
There is an advantage that it allows selective application of mild processing conditions by long-term processing. Therefore, the processing conditions can be greatly relaxed, and a wider range can be selected, and more uniform enzyme action can be expressed. It is possible.

Further, the above water-soluble immobilized enzyme has a large molecular size (polymer effect), and the used water-soluble immobilized carrier has new compatibility with the fibrous structure which is a substrate of the enzyme. Since it has, its invasion into the inside of the fiber to be treated is well suppressed, the enzymatic reaction proceeds more gently than the fiber surface exclusively, whereby the strength reduction of the fiber structure due to the destruction of the inside of the fiber is not caused, In addition, the local enzymatic reaction caused by the variation in properties due to damages on the fiber surface is considerably reduced, and a uniform treatment effect can be obtained.

Further, the water-soluble immobilized enzyme used in the present invention is selected from those having a high affinity for a specific fiber as its immobilization carrier, and thus, for example, a mixed fiber structure is used as an object to be treated. In this case, it is also possible that the specific fiber in the mixed fiber can be selectively subjected to an enzymatic action.

The treatment agent of the present invention, which contains the above-mentioned water-soluble immobilized enzyme as an essential component, is usually prepared in a liquid form suitable for a desired processing treatment of a fiber structure to be treated and put into practical use. Such liquid form is generally an aqueous solution for dipping the fiber structure, and the pH and the concentration of the water-soluble immobilized enzyme as an active ingredient are appropriately determined according to the intended processing, and are not particularly limited. Not something. Generally, the pH of the treatment liquid can be in the range of about 4.0 to 10.0, and the concentration of the water-soluble immobilized enzyme can be in the range of about 3.0 to 11.0. Therefore, the above-mentioned treatment liquid is appropriately p if necessary.
An H regulator and a buffer may be added and blended.

Furthermore, the treating agent of the present invention retains a sufficient enzyme activity even after being prepared in the above-mentioned suitable treatment liquid form and used for the intended processing, so that it can be used again for the processing as it is. , For example, acid or acetone suitable for this,
The enzyme can be separated and recovered as a precipitate by adding an organic solvent such as alcohol, or can be concentrated and separated by using an ultrafiltration membrane or the like. The water-soluble immobilized enzyme thus recovered can be used as it is or appropriately. It can be used again as the treating agent of the present invention after the concentration is adjusted by dilution or the like. Regeneration treatment of the water-soluble immobilized enzyme can be performed by various methods well known in the art.

The treatment of the fiber structure using the processing agent of the present invention can be carried out in substantially the same manner as a conventionally known method depending on the purpose of the processing treatment. For example, in the desizing treatment, the concentration of the water-soluble immobilized enzyme is about 0.01 to 50 g / l, the bath temperature is about 30 to 120 ° C., the time is about 1 to 30 minutes, and the bath ratio is about 1: 1 to 1:60. It is desirable to be performed under conditions. Further, the scouring treatment was carried out at a water-soluble immobilized enzyme concentration of about 0.
It is preferable to carry out under conditions of about 01 to 50 g / l, a bath temperature of about 30 to 120 ° C., a time of about 1 to 120 minutes, and a bath ratio of about 1: 1 to 1:60. Immobilized enzyme concentration about 0.01 to 50 g / l, bath temperature about 30 to 12
About 0 ° C, time about 1-240 minutes, bath ratio about 1: 1
It is suitable to carry out under the condition of 1:60. Incidentally, in each of the above treatments, it is of course possible to appropriately add and blend various usual auxiliary agents, pH adjusters and the like, if necessary, in the same manner as in the conventionally known methods.

Further, the processing agent of the present invention can be applied as a pretreatment agent or a posttreatment agent in the bleaching treatment of the fiber structure. For example, when it is used as a pretreatment agent during bleaching with ordinary sodium zincate, it is possible to perfectly prevent the generally recognized decrease in strength during bleaching. Further, when used as a post-treatment agent in bleaching with hydrogen peroxide, for example, the amount of residual hydrogen peroxide that is usually recognized can be significantly reduced. Conditions for use as the pretreatment agent and the posttreatment agent are, for example, generally, a water-soluble immobilized enzyme concentration of about 0.01 to 50 g / l, a bath temperature of about 15 to 90 ° C., and a time of about 1 The conditions of about 120 minutes and a bath ratio of about 1: 1 to 1:60 can be adopted.

[0025]

EXAMPLES Examples will be given below to explain the present invention in more detail, but the present invention is not limited to these. In addition, in each example, “part” means “part by weight”.

[0026]

Example 1 2 parts of a copolymer of methyl vinyl ether and maleic anhydride (manufactured by GANTREZ AN. GAF), 5 parts of amylase (lactose RCSconc, manufactured by Rakuto Kasei Co., Ltd.) and 0.1M phosphate buffer ( pH 6.0) 30 parts at 20 ° C
After stirring for 24 hours, a water-soluble immobilized enzyme was prepared.

5 g of the water-soluble immobilized enzyme obtained above
l, 80 ℃, 10 minutes, after heating the cotton kana-kin 75 ℃,
It was dipped in a bath ratio of 1:50 for 30 minutes, and then washed with water and washed with hot water (90 ° C.) for 2 minutes each and dried.

The treated cloth thus treated did not show iodine coloration due to the dropping of iodine solution, and the glue was completely removed.

Next, cotton kana-kin was soaked in the treatment liquid which had been subjected to the desizing treatment as described above, and desizing treatment was carried out at 75 ° C. for 30 minutes at a bath ratio of 1:15. After that, washing with hot water was carried out in the same manner as above, and iodine solution was added dropwise to the dried treated cloth, iodine coloration was not exhibited, desizing was completed, and the water-soluble immobilized enzyme could be reused.

[0030]

Comparative Example 1 Lactose RCSconc 5 g / l before immobilization used in Example 1 at 80 ° C. for 10 minutes and after heating, cotton kana-kin was immersed in 75 ° C. for 30 minutes at a bath ratio of 1:50. After that, washing with water and washing with hot water (90 ° C.) were performed for 2 minutes each and dried.

The comparative treated cloth thus treated exhibited iodine coloration due to the dropwise addition of iodine solution, and there was residual glue.

Further, cotton kana-kin was soaked in the treatment liquid after the desizing treatment described above, and desizing treatment was carried out at 75 ° C. for 30 minutes at a bath ratio of 1:15. After that, washing with hot water was performed in the same manner as above, and iodine solution was added dropwise to the dried treated cloth to show iodine coloration, and the enzyme solution could not be used repeatedly.

[0033]

Example 2 2 parts of a copolymer of methyl vinyl ether and maleic anhydride (manufactured by GANTREZ AN. GAF), 5 parts of cellulase (Entilon CM-40L, manufactured by Rakuto Kasei Co., Ltd.) and 0.1M phosphate buffer. 20 parts of liquid (pH 6.0)
A water-soluble immobilized enzyme was prepared by stirring at 24 ° C. for 24 hours.

5 g / l of the water-soluble immobilized enzyme obtained above was dissolved in 0.02 M acetate buffer, and the avicelase activity after 20 minutes of incubation was measured to examine the activity before and after immobilization. The results are shown in Table 1 below.

[0035]

[Table 1]

The water-soluble immobilized enzyme obtained above was adjusted to 50 units of avicelase activity and dissolved in a washing machine (5 L volume) at 50 ° C. for 40 minutes at a bath ratio of 1:40 and pH 5.0,
The bleached ramie fabric (Tosco Co., Ltd.) was treated with an enzyme while stirring. After that, washing with water and washing with hot water (70 ° C.) were carried out for 5 minutes each and dried.

The treated cloth thus treated had a weight loss rate of 1.
Tear strength of 890 g at 4% (2400 for untreated cloth)
g).

Next, 200 ml of the liquid obtained by subjecting the ramie fabric to the enzyme treatment was adjusted to pH 3.0 with acetic acid, and the generated precipitate was recovered by centrifugation, and the total amount of the recovered precipitate was adjusted to p.
Dissolve in 200 ml of 0.01M acetate buffer of H5.0,
As a result of subjecting the same ramie fabric to the enzyme treatment as described above, the weight loss rate of the obtained treated cloth was 1.4%, and no decrease in enzyme activity was observed.

[0039]

Comparative Example 2 The enzyme before immobilization in Example 2 was adjusted to 50 units of avicelase activity, dissolved in a washing machine (5 L volume) at 50 ° C. for 40 minutes at a bath ratio of 1:40 and pH 5.0, and bleached. The obtained ramie fabric (Tosco Co., Ltd.) was treated with an enzyme while stirring. After that, wash with water, wash with hot water (70 ℃)
Was dried for 5 minutes each.

The comparative treated cloth thus treated had a weight loss rate of 1.8% and a tear strength of 380 g (the untreated cloth was 240%).
It was 0 g), and a significant decrease in strength was observed.

Next, 200 ml of the liquid obtained by subjecting the ramie fabric to the enzyme treatment was adjusted to pH 3.0 with acetic acid, and the generated precipitate was recovered by centrifugation, and the total amount of the recovered precipitate was adjusted to p.
Dissolve in 200 ml of 0.01M acetate buffer of H5.0,
As a result of subjecting the same ramie fabric to the enzyme treatment as described above, the weight loss rate of the obtained treated cloth was 0.05%, and no enzyme recovery effect was observed.

[0042]

Example 3 The water-soluble immobilized enzyme prepared in the same manner as in Example 2 was adjusted to 400 units of avicelase activity, and 5
The mixture was dissolved in a washing machine (5 L volume) at 0 ° C. for 120 minutes at a bath ratio of 1:20 and pH 5.0, and purified cellulose fabric (Tencel, Courtles) was treated with an enzyme while stirring. After that, washing with water and washing with hot water (70 ° C.) were carried out for 5 minutes each and dried.

The treated cloth thus treated has a weight loss ratio of 2.
Burst strength at 8% [Muren type burst strength tester (Daiei Kagaku Seisakusho Co., Ltd., same below) 1.1kg / c
m ² and no fluff on the fiber surface was observed.
The burst strength of the untreated cloth was 1.5 kg / cm ² .

[0044]

Comparative Example 3 The enzyme before immobilization in Example 2 was adjusted to 400 units of avicelase activity, dissolved in a washing machine (5 L volume) at 50 ° C. for 120 minutes at a bath ratio of 1:20 and pH 5.0, and purified. The cellulose woven fabric (TENCEL, Courtles) was treated with an enzyme while stirring. After that, washing with water and washing with hot water (70 ° C.) were carried out for 5 minutes each and dried.

The comparative treated cloth thus treated had a weight loss rate of 3.0%, a burst strength of 0.8 kg / cm ² , and fluff on the fiber surface.

[0046]

[Example 4] 2 parts of a copolymer of methyl vinyl ether and maleic anhydride (manufactured by GANTREZ AN. GAF), 5 parts of protease (Entilon FAconc., Manufactured by Rakuto Kasei Kogyo Co., Ltd.) and 0.1 M acetate buffer ( pH 4.0) 30 parts at 20 ° C
After stirring for 24 hours, a water-soluble immobilized enzyme was prepared.

A silk fabric (using wild silk thread, manufactured by Kanebo Co., Ltd.) was immersed in a liquid (pH 4.0) adjusted to 50 units of the protease activity (pH 4.0) of the water-soluble immobilized enzyme obtained above, and the temperature was adjusted to 50 ° C. For 120 minutes at a bath ratio of 1:40, followed by washing with hot water (70 ° C.), washing with water and drying.

The treated cloth thus treated had a kneading rate of 18.2% and no reduction in strength was observed.

[0049]

COMPARATIVE EXAMPLE 4 The enzyme used in Example 4 before immobilization had a protease activity adjusted to 50 units (pH 4.
Soak silk fabric (using wild silk thread, manufactured by Kanebo Co., Ltd.) in 0), and
It was treated at 0 ° C. for 120 minutes at a bath ratio of 1:40, then washed with hot water (70 ° C.), washed with water and dried.

The treated cloth thus treated had a kneading rate of 9.9%, and rubbing was recognized on the surface.

[0051]

[Example 5] 2 parts of a copolymer of methyl vinyl ether and maleic anhydride (manufactured by GANTREZ AN. GAF), 5 parts of pectinase (Entilon CP-10, manufactured by Rakuto Kasei Co., Ltd.) and 0.1M acetic acid buffer. (PH 6.5) 30 parts at 20 ° C.
After stirring for 24 hours, a water-soluble immobilized enzyme was prepared.

The pectinase activity (pH 7.0) of the water-soluble immobilizing enzyme obtained above was adjusted to 50 units (pH 6.5) and added to an unpurified linen cloth (100% linen).
(Tosco Co., Ltd.) is immersed and treated at a bath ratio of 1:10 at 50 ° C. for 60 minutes, followed by hot water washing (70 ° C.) and water washing, then sodium chlorite 10 g / l, bath ratio 1: 1
5. Bleaching was performed at a temperature of 90 ° C. for 2 hours.

The whiteness of the treated cloth thus treated [according to a colorimetric color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., the same applies hereinafter) was 90%, and no reduction in strength was observed.

[0054]

Comparative Examples 5 and 6 A solution prepared by adjusting the pectinase activity of the enzyme used in Example 5 before immobilization to 50 units (p
H6.5) is an unpurified linen fabric cloth (100% linen, manufactured by Tosco Co., Ltd.), treated at 50 ° C. for 60 minutes with a bath ratio of 1:10, and then washed with hot water (70 ° C.). , Washed with water, then sodium chlorite 10 g / l, bath ratio 1:15,
Bleaching was carried out at a temperature of 90 ° C. for 2 hours.

The whiteness of the treated cloth thus treated is 89.
%, But the strength decreased to 40% or less before the enzyme treatment.

The unpurified hemp fabric used in Example 5 before the enzyme treatment (100% linen, manufactured by Tosco Co., Ltd.)
Was directly subjected to bleaching for 10 minutes at a sodium chlorite content of 10 g / l, a bath ratio of 1:10, and a temperature of 90 ° C. for 60 minutes twice, and the whiteness and strength of the obtained treated cloth were examined. The whiteness was 78%. Tear strength (diameter) [15% strength reduction was observed with an Elemendorff fabric tear tester (manufactured by Daiei Kagaku Seimitsu Seisakusho Co., Ltd.).

[0057]

Example 6 1 part of a copolymer of methyl vinyl ether and maleic anhydride (manufactured by GANTREZ AN. GAF), 2 parts of catalase (Entilon OL-50, manufactured by Rakuto Kasei Co., Ltd.) and 0.1M phosphate buffer. 30 parts of liquid (pH 7.0) at 20 ° C
After stirring for 24 hours, a water-soluble immobilized enzyme was prepared.

2 g / l of the water-soluble immobilized enzyme obtained above
1 kg of cotton thread using a cheese dyeing machine, NaOH (solid type) 4 g / l, H ₂ O ₂ (35%) 10 g / l, Apiagen AG-824 (Apiagen AG-824, manufactured by Rakuto Kasei Kogyo Co., Ltd.) 0 0.5 g / l, bath ratio 1: 5, 6 at 100 ° C
Add after treatment for 0 minutes, adjust the temperature to 50 ° C, then add 1 more
After running for 0 minutes, the bleaching process of the cotton yarn was completed.

By the above treatment operation, the treated cotton yarn had a whiteness of 90%, no H ₂ O ₂ residue was observed, and 0.2 ppm H ₂ O ₂ residue was observed in the bleaching effluent. .

[0060]

Comparative Example 7 Catalase 2 g / l used in Example 6 before immobilization was mixed with 1 kg of cotton thread using a cheese dyeing machine and Na.
OH (solid type) 4 g / l, H ₂ O ₂ (35%) 10 g /
1, Apiagen AG-824 0.5 g / l, bath ratio 1:
5, add after treatment at 100 ℃ for 60 minutes, temperature 50 ℃
After the adjustment, the operation was continued for 10 minutes to complete the bleaching process of the cotton yarn.

By the above treatment operation, the treated cotton yarn had a whiteness of 90%, but residual H ₂ O ₂ was observed, and 20 ppm or more of H ₂ O ₂ was observed in the bleaching effluent. It was

[0062]

Example 7 1 part of a copolymer of methyl vinyl ether and maleic anhydride (manufactured by GANTREZ AN. GAF), 2 parts of lipase (Entilon LA-13, manufactured by Rakuto Kasei Co., Ltd.) and 0.1M phosphate buffer. 30 parts of the liquid (pH 7.0) was stirred at 20 ° C. for 48 hours to prepare a water-soluble immobilized enzyme.

5 g of the water-soluble immobilized enzyme obtained above, 1 g of sodium carbonate, 4 g of Apiagen AG-85 and 1 k of water
100g of unrefined wool is dipped in 40g of liquid at 40 ℃
Enzyme treatment was performed for a period of time, followed by washing with hot water (40 ° C.) and washing with water for 5 minutes each and drying.

The treated wool thus obtained was immersed in ethanol for 4 hours to extract oil and fat, and 1 g of extract was obtained.

[0065]

Comparative Example 8 100 g of unrefined wool was dipped in a solution of 5 g of the lipase used in Example 7 before immobilization, 1 g of sodium carbonate, 4 g of Apiagen AG-85 and 1 kg of water, and 40
Enzyme treatment was performed at ℃ for 48 hours, and then washed with hot water (40
C.) and water washing for 5 minutes each, and dried.

The treated wool thus obtained was immersed in ethanol for 4 hours to extract oil and fat, and 12 g of extract was obtained.

[0067]

[Example 8] The same treatment as in Example 7 was carried out by using unscoured cotton cotton instead of unscoured wool.

The treated cotton cotton thus obtained was immersed in ethanol to extract oil and fat.
0.2 g of extract was obtained.

[0069]

Comparative Example 9 In Comparative Example 8, the same treatment was carried out by using unscoured cotton cotton instead of unscoured wool.

The treated cotton cotton thus obtained was immersed in ethanol to extract oil and fat.
1.6 g of extract was obtained.

[0071]

Example 9 2 g of water-soluble immobilized enzyme prepared in Example 7
Dichloroisocyanuric acid (DCC
A) 1 g was added and 10 g of refined wool yarn was dipped in a liquid adjusted to pH 4.0 to obtain a bath ratio of 1:20 and a temperature of 20 ° C.
Immersion treatment was performed for 60 minutes. Then, it was washed with water and washed with hot water and dried.

The treated wool yarn thus obtained had a glossy and soft texture.

[0073]

Comparative Example 10 In Example 9, 1 g of DCCA was added to a solution in which 2 g of the enzyme before immobilization was dissolved, and the pH was adjusted to 4.
10 g of the purified wool yarn was dipped in the liquid adjusted to 0, and the dipping treatment was performed at a bath ratio of 1:20 and a temperature of 20 ° C. for 60 minutes, followed by washing with water, washing with hot water, and drying.

The treated wool yarn thus obtained had a dull but dull texture.

[0075]

Example 10 and Comparative Example 11 The water-soluble immobilized enzyme prepared in Example 2 was adjusted to 400 units of avicelase activity, 50 ° C., 120 minutes, bath ratio 1:20, pH 5.0.
Dissolve in a washing machine (5 L capacity) with a cotton fabric (scouring bleach)
Was treated with enzyme while stirring.

Further, the same treatment was carried out using the above-mentioned unfixed enzyme.

Table 2 below shows the results of comparing the tear strengths of the thus-obtained treated cloths at six points.

[0078]

[Table 2]

From the above Table 2, it can be seen that the treatment using the water-soluble immobilized enzyme of the present invention has less variation in strength as compared with the treatment using the unimmobilized enzyme, and a uniform processing treatment can be performed. It is clear that we have obtained.

[0080]

[Example 11] Water-soluble immobilized enzyme 5 prepared in Example 2
The enzyme treatment of the scoured cotton cloth was carried out for 60 minutes, 120 minutes, 240 minutes and 1440 minutes using g / l at a temperature of 40 ° C. and a bath ratio of 1:20, respectively.

Then, the treated liquid was filtered through a 100-mesh glass filter, acetone was added until the filtrate became cloudy, and the mixture was centrifuged, and the viscous clear liquid which had settled was diluted with water again and acetone was added again. Sedimentation was performed and the sediment was obtained by centrifugation.

Further, the precipitate was dissolved in a small amount of water and freeze-dried to obtain a dried product.

Table 3 below shows the results of measuring the avicelase activity and examining the enzyme recovery rate of the dried product obtained by the above operation for each treatment time.

[0084]

[Table 3]

From Table 3 above, it is possible to recover 86.6% of the enzyme even from the solution after the enzyme treatment for 1440 minutes, which indicates that the solution of the present invention has a high activity after the treatment. It is clear that the enzyme can be recovered very easily and that the recovered enzyme has a high stability.

[0086]

Example 12 The water-soluble immobilized enzyme prepared in Example 2 was adjusted to an avicelase activity of 3 × 10 ⁴ units, and 5
0 ° C, 30 minutes, bath ratio 1:20, pH 5.0, polishing stone 1
It was dissolved in a washer machine (600 L capacity) using 00 kg and subjected to enzyme treatment while rotating the desizing-completed jeans pants.

Further, the same treatment was carried out using the above-mentioned unfixed enzyme.

The results of comparing the tear strengths of the jeans pants (treated cloth) thus obtained are shown in Table 4 below.
Shown in.

[0089]

[Table 4]

In Table 4, ⊚ indicates good, ∘ indicates normal, and x indicates bad.

From Table 4 above, according to the present invention, the decolorizing property and the texture are improved, and the treated cloth is excellent in the strength retention as compared with the conventional processing treatment of this kind using the unfixed enzyme. It can be seen that this treatment of the present invention is more effective.

[0092]

Example 13 An enzyme was immobilized by the following method using a water-soluble polymer using polyethylene glycol (abbreviated as PEG) as a carrier.

That is, 1 g of PEG (molecular weight: about 5500) having a carboxyl group as a reactive terminal group was added to 20 ml of 0.1M acetate buffer adjusted to pH 5, and stirred,
To this, add 200 mg of water-soluble carbodiimide and add 1 more.
Stir for 5 minutes, then add 2.5 g of cellulase agent and add 4
The mixture was stirred for 16 hours under the condition of ° C to obtain a water-soluble polymer-immobilized cellulase.

The water-soluble immobilized enzyme thus obtained was allowed to act on the scoured cotton yarns, respectively, using the case of unfixed cellulase having the same avicelase activity as a control, and the results of observation of strength and elongation and fiber surface were observed. Were compared.

The results (weight reduction rate and strength) are shown in Table 5.

From Table 5, it can be said that the strength reduction of the cotton yarn is suppressed to a low level even though the weight reduction action of the cotton yarn by the water-soluble polymer-immobilized cellulase is large. Therefore, as in the case of the immobilized cellulase treatment using the methyl vinyl ether maleic anhydride copolymer as a carrier, as compared with the non-immobilized cellulase, the softness of the fiber is further reduced while suppressing the decrease in strength and elongation. It became possible to withdraw.

As a result of observing the fiber surface with a scanning electron microscope, the damage caused on the fiber surface was smaller with the immobilized cellulase-treated yarn.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] May 20, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction content]

The immobilization of the above-mentioned enzyme preparation, that is, the preparation of the water-soluble immobilized enzyme can be carried out by a usual method using various kinds of water-soluble immobilized carriers which are generally known. More specifically, the water-soluble immobilizing carrier that can be used here can be selected from water-soluble polymer substances having a property of dissolving in water under a temperature condition of about 0 to 80 ° C. There is no particular limitation as long as it has a group capable of chemically bonding to a functional group. Typical examples thereof include copolymers of methyl vinyl ether and maleic anhydride, carboxymethyl cellulose, polyethylene glycol, copolymers of methyl ether and maleic anhydride, polyacrylic acid, polyvinyl alcohol, hydroxyethyl starch, acrylic acid. and copolymers of various or synthetic polymer substance of maleic acid, poly -L - glutamic acid, collagen, chitosan, alginic acid, casein, water-soluble silk, natural polymeric substance such as water-soluble wool It can be illustrated.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction content]

Furthermore, the water-soluble immobilized enzyme, and which have a large molecular size (polymer effect), the parent sum with respect to a fiber structure soluble immobilization pellets was utilized as a substrate for the enzyme Since it has, its invasion into the fiber to be treated is well suppressed, the enzymatic reaction proceeds more gently than the fiber surface exclusively, and thereby the strength decrease of the fiber structure due to the destruction of the fiber is not caused, In addition, the local enzymatic reaction caused by the variation in properties due to damages on the fiber surface is considerably reduced, and a uniform treatment effect can be obtained.

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0024

[Correction method] Change

[Correction content]

Further, the processing agent of the present invention can be applied as a pre-treatment agent or post-treatment agent in the bleaching treatment of the fiber structure. For example, if used as a pretreatment agent in the bleaching with normal nitrous salt periodate soda, the generally accepted are reduced strength can be excellently prevented during bleaching. Further, when used as a post-treatment agent in bleaching with hydrogen peroxide, for example, the amount of residual hydrogen peroxide that is usually recognized can be significantly reduced. Conditions for use as the pretreatment agent and the posttreatment agent are, for example, generally, a water-soluble immobilized enzyme concentration of about 0.01 to 50 g / l, a bath temperature of about 15 to 90 ° C., and a time of about 1 The conditions of about 120 minutes and a bath ratio of about 1: 1 to 1:60 can be adopted.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction content]

The treated cloth thus treated has a weight loss ratio of 2.
[Measurement by Myu alkarylene type burst strength tester (Daiei Kagaku Seiki Seisakusho), hereinafter the same] burst strength at 8% 1.1 kg / c
m ² and no fluff on the fiber surface was observed.
The burst strength of the untreated cloth was 1.5 kg / cm ² .

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0056

[Correction method] Change

[Correction content]

Further, the unpurified hemp fabric before enzyme treatment used in Example 5 (100% linen, manufactured by Tosco Co., Ltd.) was directly applied with sodium chlorite at 10 g / l and a bath ratio of 1: 1.
Bleaching was carried out twice for 60 minutes at a temperature of 90 ° C. for 0 minutes, and the whiteness and strength of the obtained treated cloth were examined. Whiteness 78%, tear strength (diameter) [Elemendorff Tear Tester
Seiki Seisakusho)), the same applies hereinafter].

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0095

[Correction method] Change

[Correction content]

The results (weight loss rate and strength) are shown in Table 5.

[Table 5]

 ─────────────────────────────────────────────────── --- Continuation of the front page (72) Inventor Kyohei Kamiko 2-4, Nishiki, Kaizuka City, Osaka Prefecture 3-204 Azure Nishikinohama 3-204 (72) Inoue Hayashi, 60, Oyamashitauchikawaramachi, Kita-ku, Kyoto-shi, Kyoto Prefecture (72) Inventor Hiroshi Yoneyama 21 at 1019 Sawa, Kaizuka City, Osaka Prefecture (72) Inventor Makoto Tsuda 2-3-10-10-101, Suehirocho, Izumiotsu City, Osaka Prefecture (72) Inventor Akito Tsuchiya Koga-gun, Shiga Prefecture Nishimachi Chuo 5-1-1116

Claims (2)

[Claims] 1. A processing agent for use in enzymatic processing of a fiber structure, which comprises a water-soluble immobilized enzyme and is a processing agent for a fiber structure. 2. A method for processing a fiber structure, which comprises using a processing agent containing a water-soluble immobilized enzyme in enzymatically processing the fiber structure.