JPH0967777A - Fiber treating agent and treatment of fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To maintain fiber improving effect by an enzyme and to prevent reduction in strength of the fiber by treating the fiber with a treating agent containing an immobilized enzyme. SOLUTION: Methacrylic acid, divinylbenzene and methyl methacrylate are subjected to emulsion polymerization in a water system to prepare a dispersion of fine particles of a water-insoluble polymer having 0.02-10μm, preferably 0.05-5μm particle diameter. The dispersion is mixed with an enzyme such as cellulase to prepare an immobilized enzyme-containing fiber treating agent. Plural cotton yarns cut into fixed length are bundled, both the ends are tied and the bundled yarns are immersed in methanol over night, dried under reduced pressure and treated with the treating agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a fiber desizing, refining,
The present invention relates to a fiber treatment agent and a fiber treatment method with an enzyme used for processing, texture improvement and the like.

[0002]

2. Description of the Related Art In recent years, enzymatic reactions have come to be used in various industrial fields, and particularly in the field of fibers, enzymatic treatment is widely carried out in order to improve the texture and feel. Conventionally, most of the enzymes used for treating fibers are those in a state of being soluble in a solution, and usually enzymes such as amylase, protease, cellulase, pectinase, catalase, lipase and hemicellulase. It is carried out using. However, although these enzyme treatments have many effects such as degumming, refining, processing, and texture improvement of the fiber, there is a problem that the fiber strength is remarkably reduced due to excessive enzyme treatment, and the fiber strength is maintained while maintaining the enzyme treatment effect. It was previously impossible to maintain.

For example, JP-A-6-341067 discloses a water-soluble immobilizing enzyme, specifically, an immobilizing enzyme such as amylase immobilized on a copolymer of water-soluble polymer methyl vinyl ether and maleic anhydride. It has been disclosed to treat the fibers with oxidising enzymes. According to this method
Compared to the use of non-immobilized enzyme, desizing, refining, modification, etc. of fiber structure can be performed uniformly and stably, and further, reduction of fiber strength can be prevented, environmental degradation and uneconomical It is also stated that can be solved. However, according to this method, a satisfactory effect is not obtained in terms of preventing the strength of the yarn or the cloth from being lowered.

[0004]

The present invention has been made in order to solve the above-mentioned conventional technical problems, and provides a fiber treating agent capable of preventing the strength of fibers from decreasing while maintaining the effect of enzyme treatment. And a fiber treatment method.

[0005]

According to the study of the present inventor, the above-mentioned object of the present invention can be achieved by a fiber treating agent containing an enzyme immobilized on polymer fine particles having a specific particle diameter. Was found.

According to the present invention, there is provided a fiber treatment agent containing an enzyme immobilized on water-insoluble polymer particles (hereinafter referred to as "immobilized enzyme"). Further, according to the present invention, there is provided a fiber treatment method characterized by treating fibers in the presence of a fiber treatment agent containing an enzyme immobilized on water-insoluble polymer particles. Less than,
The present invention will be described in more detail.

In the present invention, the polymer fine particles on which the enzyme is immobilized can be produced by various methods. That is, the polymer fine particles can be produced by, for example, obtaining a polymer by emulsion polymerization, dispersion polymerization, suspension polymerization, or solution polymerization, and then depositing the polymer. The polymerization method and the precipitation method are not particularly limited as long as fine particles having a predetermined average particle diameter in the present invention can be obtained.

The average particle size of the fine polymer particles in the present invention is in the range of 0.02 to 10 μm, preferably 0.05 to 5 μm.
The range is 5 μm. With polymer particles smaller than 0.02 μm, the effect of preventing reduction in strength of the fiber is small because the difference with the unimmobilized enzyme is small, and with an average particle size larger than 10 μm, the enzyme treatment of the fiber takes a considerably long time. Therefore, an economic problem occurs. In addition,
The average particle diameter here is calculated from the weight average. When the enzyme is immobilized on the agglomerated fine particles to be used as a fiber treating agent, it is determined from the size of the primary particles constituting the fiber treating agent from an electron micrograph. The polymer particles used in the present invention can be easily washed by some treatment and removed from the fibers. Therefore, the glass transition temperature of the polymer constituting the particles is made higher than the treatment temperature, or internal cross-linking is prevented to prevent fusion to the fiber, or conversely, a low molecular weight compound is easily removed by washing with a solvent, It is preferable to control the pH or the temperature after the enzyme treatment to dissolve the particles so that they can be easily washed and removed.

Specific examples of the monomer forming the polymer fine particles of the present invention include aromatic monovinyl monomers such as styrene, ethylvinylbenzene, α-methylstyrene, fluorostyrene and vinylpyridine; butyl acrylate, 2-ethylhexyl acrylate, β-methacryloyloxyethyl hydrogen phthalate,
Acrylic ester monomers such as N, N'-dimethylaminoethyl acrylate; 2-ethylhexyl methacrylate, methoxydiethylene glycol methacrylate, methoxy polyethylene glycol methacrylate,
Methacrylic acid ester monomers such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, N, N′-dimethylaminoethyl methacrylate; conjugated diene monomers such as butadiene and isoprene; vinyl ester monomers such as vinyl acetate; 4-methyl-1-
Examples include pentene and other α-olefins.

Preferred combinations of monomers include a combination of at least one mono- or dicarboxylic acid and at least one aldehyde group-containing monomer, and a combination of at least one mono- or dicarboxylic acid and at least one crosslinkable monomer. And so on.

Monomers having functional groups, for example, mono- or dicarboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid or acid anhydride group-containing monomers; 2-acryloyloxyethyl-2-hydroxy Ethylphthalic acid, 2-hydroxy-
Ester group-containing monomers such as 3-phenoxypropyl acrylate, 2-hydroxyethyl methacrylate, glycidyl acrylate and glycidyl methacrylate;
Examples thereof include amide group-containing monomers such as N-methylolacrylamide, acrylamide, methacrylamide, and methylenebisamide; cyano group-containing monomers such as acrylonitrile and methacrylonitrile; and aldehyde group-containing monomers such as acrolein and methacrolein.
It may also be a sulfonate group-containing monomer such as sodium styrene sulfonate. Further, if necessary, a crosslinkable monomer such as divinylbenzene, ethylene glycol dimethacrylate or trimethylolpropane trimethacrylate can be used. These are used alone or in combination of two or more

For the polymerization of the above polymer fine particles, usually,
A polymerization initiator is used. The polymerization initiator is not particularly limited as long as it can be used in emulsion polymerization or suspension polymerization, for example, persulfate initiators such as potassium persulfate, sodium persulfate and ammonium persulfate; azobisisobutyro Azo initiators such as nitrile; peroxides such as hydrogen peroxide and organic peroxides can be used alone or in combination with various reducing agents such as ascorbic acid.

In emulsion polymerization or suspension polymerization, a surfactant or suspension protective agent is generally used in order to enhance the stability of the polymerization reaction system. Examples of the surfactant include dodecylbenzene sulfonate, dodecyl sulfate, lauryl sulfate, dialkyl sulfosuccinate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene alkyl propenyl phenyl ether sulfate, and formalin of naphthalene sulfonic acid. Examples thereof include anionic surfactants such as condensates. Here, examples of the salt include sodium salt, ammonium salt, potassium salt and the like.

Furthermore, it is also possible to use nonionic surfactants such as polyoxyethylene nonyl phenyl ether, polyethylene glycol monostearate, polyoxyethylene alkylpropenyl phenyl ether and sorbitan monostearate. It is also possible to use a generally known reactive emulsifier such as sodium naphthalenesulfonate alone or in combination with the above-mentioned surfactant.

As the suspension protective agent, for example, water-soluble polymers such as polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, sodium polyacrylate and hydroxypropyl cellulose can be preferably used. These may be used alone or in combination.

On the other hand, it is also possible to form fine polymer particles by polymerizing the polymer by solution polymerization or the like and then precipitating the polymer in the form of fine particles from the solvent by controlling pH, temperature and the like. According to this method, the enzyme can be immobilized on the polymer in a dissolved state in advance, and then the polymer can be deposited in the form of fine particles. Further, it is also possible to impart a functional group to the surface of the polymer fine particles by a chemical treatment, for example, after obtaining polymer fine particles having an epoxy group, the addition of an amino group by treatment with ammonia, methylamine or the like, or sulfurous acid. The sulfone group can be imparted by treating with sodium hydrogen, sulfuric acid or the like.

As the enzyme that can be used in the present invention, an effective enzyme may be selected depending on the type of fiber to be treated and the purpose. Specifically, for example, aminopeptidase, chymotrypsin, papain, urokinase, urease,
Amidase, asparaginase, protease, glucose phosphatase, amylase, chitinase, lysozyme, cellulase, invertase, pectinase,
Hydrolases such as lipase, ribonuclease, various restriction enzymes (endodeoxyribonuclease); isomerases such as lysine racemase, UDP galactose epimerase, glucose isomerase, lactase racemase, lysine aminomutase; glycine methyltransferase, transketolase, lysine acetyl Transferase such as transferase, glutamyl transferase, phosphorylase, hexokinase, phosphoglyceromutase, glutamate aminotransferase, aspartate aminotransferase, leucine aminopeptidase, creatine phosphokinase;
Alcohol dehydrogenase, aldehyde dehydrogenase, fumarate reductase, lactate dehydrogenase, glucose dehydrogenase, alcohol oxidase, amino acid oxidase, nicotinate dehydrogenase, hydroxylamine oxidase, glutathione dehydrogenase , Cytochrome c
Redox enzymes such as oxidase, catalase, peroxidase, lipoxygenase, superoxide dismutase, etc .; ornithine decarboxylase, lysine decarboxylase, enolase, lyases such as tryptophan synthetase, adenylate cyclase, tRNA synthetase, acetyl CoA synthetase, glutamine. A ligase such as synthetase can be mentioned. Preferred enzymes include cellulase,
Examples include protease.

The binding between the enzyme and the polymer fine particles is achieved by the covalent bonding method or the ionic bonding method. Bonding by the covalent bonding method is carried out by the carboxyl group, amino group,
This can be achieved by a reaction between an epoxy group, an aldehyde group, a hydroxyl group, chlorine, a sulfhydryl group, etc. and a carboxyl group, an amino group, a hydroxyl group, a sulfhydryl group, etc. of the enzyme, and the reaction method can be any method. good. For example, if the peptide method is used, the carboxyl group on the surface of polymer particles is converted to a derivative such as azide, chloride, or isocyanate, and this is reacted with the amino group of the enzyme, or a method such as carbodiimide reagent or Woodward reagent K is used. An example is a method of reacting a carboxyl group, an amino group or the like on the surface of fine particles with a carboxyl group, an amino group or the like of an enzyme using a condensation reagent. Further, in the alkylation method, there is a method of activating the particle surface with a halogenated acetyl derivative, a triazinyl derivative, a halogenated methacryl derivative or the like, and then reacting it with an amino group of an enzyme, a phenolic hydroxyl group or a thiol group,
There is also a method in which the amino group on the particle surface and the amino group of the enzyme are bound to each other by a crosslinking agent such as glutaraldehyde or hexamethylene diisocyanate to react.

A particularly preferred method is a method in which an aldehyde group or an epoxy group is introduced into the polymer particles in advance so that the amino group of the enzyme reacts with the polymer particles only by mixing the enzyme. The ratio of the immobilized enzyme to the polymer particles varies depending on the particle system of the polymer particles, the purity of the enzyme, etc., but is usually 0.5 to 50% by weight, preferably 1 to 20% by weight, based on the polymer particles. .

The material of the fiber to be treated in the method of the present invention is not particularly limited as long as it is a fiber which is decomposed by the enzyme used, and specifically,
Natural fibers such as cotton, wool and silk, these natural fibers and various synthetic fibers such as polyester, nylon, acrylic,
Examples thereof include blended fibers with vinyl chloride and rayon, recycled fibers of the above natural fibers, and the like. The form of the fibers to be treated may be various fabrics such as woven and knitted fabrics and non-woven fabrics in addition to fibrous substances. These fibers can be degreased with alcohol or the like before contacting with the immobilized enzyme.

The conditions such as the ratio of the immobilized enzyme to the fiber, the treating time of the fiber and the treating temperature are not particularly different from the conditions in the usual enzyme treatment of the fiber, but generally, they are appropriately adjusted depending on the kind of the enzyme used. For example, the pH is 3-1
The concentration in the immobilized enzyme treatment solution is usually 0.1 to 10% by weight, preferably 0.5 to 5% by weight. The processing temperature is about 0 to 80 ° C., and the processing time is 48 hours or less. The fibers that have been treated with the immobilized enzyme are washed with a buffer solution having a pH that allows the immobilized polymer particles to be easily desorbed from the fibers or completely dissolves them. For example, fine polymer particles having a carboxy group may be washed with water having a pH of 7 or higher. If necessary, it can be washed with a solvent such as toluene, acetone or alcohol.

The pH of the immobilized enzyme solution can be adjusted by any existing method. To make it acidic, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and boric acid; acetic acid and citric acid are used. Organic acids such as acids, oxalic acid and lactic acid can be used, while alkaline alkali metals such as sodium hydroxide and potassium hydroxide; ammonia; amines such as ethanolamine can be used. In addition, in pH adjustment,
If a high concentration of acid or alkali is used, the enzyme may be locally deactivated, so it is preferable to adjust the concentration at about 0.1 to 2N.

[0023]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited thereto. In the examples, the particle size measurement, fiber weight loss rate and tensile strength reduction rate are values measured or calculated by the following methods or definitions.

Particle size measuring method : The average particle size of the polymer fine particles is measured by directly measuring 500 particles by a transmission or scanning electron microscope photograph (if the particles are not spherical, the long diameter and the short diameter are measured). The diameter was measured and the average value thereof was calculated.

Fiber weight loss rate (%) : 100-[(cotton yarn dry weight after enzyme treatment) / (cotton yarn dry weight before enzyme treatment) × 100] Fiber tensile strength reduction rate (% ); 100- [ (Tensile strength after treatment with immobilized enzyme) / (Tensile strength before treatment with immobilized enzyme)
× 100] The tensile strength is measured by a tensile tester (NRM-2010J-C
W, manufactured by Fudo Kogyo Co., Ltd., temperature 20 ° C, humidity 6
5%, gripping interval 10 cm, and pulling speed 5 cm / min.

Example 1 (1) Synthesis of Immobilized Enzyme 20 g of methacrylic acid, 30 g of divinylbenzene, 50 g of methyl methacrylate, 1000 g of distilled water and 20 g of sodium lauryl sulfate were placed in a 2 liter autoclave and heated to 70 ° C. and then used as a polymerization initiator. Potassium persulfate was added and polymerized for 4 hours. The polymerization conversion rate was 96%, and a transparent emulsion was obtained. When measured with a transmission electron microscope, the particle size of the polymer particles was 0.03 μm, and the coefficient of variation was 6%, indicating a relatively uniform particle size distribution. The polymer particles were mixed with 2% by weight of sodium hydroxide and adjusted water to obtain a polymer particle dispersion having a solid content concentration of 5% by weight and pH = 5.

After taking 10 ml of the above polymer fine particle dispersion and adding 50 μl of 20 wt% water-soluble carbodiimide, 0.5 ml of cellulase (Tricoderma reesei, Sigma) dissolved at a concentration of 5 wt% in an acetate buffer of pH 5 was added. An immobilized cellulase was prepared by reacting at 4 ° C. for 2 hours.

(2) Fiber treatment Cotton yarn was cut into a length of 30 cm, 10 fibers were bundled, both ends thereof were tied, both ends were immersed in methanol overnight, and then dried in a vacuum dryer for 7 hours to prepare a sample for enzyme treatment. did. This cotton thread bundle was placed in a 15 ml test tube, and 20 units of the above-mentioned immobilized enzyme adjusted to pH 5 with an acetate buffer was added as an enzyme (1
The unit is carboxymethyl cellulose as a substrate, pH
5, the amount of enzyme that produces 1 μmol / hour of glucose at a temperature of 37 ° C.), and was shaken at 55 ° C. and 160 times / minute for 8 hours. After completion of the reaction, remove the cotton thread from the reaction solution and
It was washed twice with a mol / L phosphate buffer solution (pH = 7), washed three times with pure water and twice with methanol, and then dried under reduced pressure for 7 hours. The weight and tensile strength of the fiber before and after the treatment with the immobilized enzyme were measured, and the weight loss and the tensile strength reduction rate were calculated. Table 1 shows the results.

Example 2 (1) Synthesis of immobilized enzyme 60 g of methacrylic acid and 40 g of methyl methacrylate
Was dissolved in 200 g of methanol, 0.5 g of azobisisobutyronitrile was added as a polymerization initiator, and polymerization was carried out at 70 ° C. for 8 hours. The polymerization conversion rate was 98%. Next, after adding 20 g of sodium hydroxide and 400 g of water, methanol was removed by distillation under reduced pressure to obtain an aqueous solution. Then 1
The polymer was precipitated by adding normal hydrochloric acid to pH = 4 to obtain polymer fine particles, and then adjusted water was added to obtain a polymer fine particle dispersion having a solid content concentration of 10% by weight. The obtained polymer fine particles were aggregated, but the primary particles had a particle diameter of 0.25 μm as measured by a scanning electron microscope. Cellulase (Tricoderma reesei, manufactured by Sigma) in which 10 g of the above polymer fine particle dispersion was taken and dissolved in a pH 4 acetate buffer at a concentration of 5% by weight
0.5 ml was added and mixed. 20% by weight in the mixture
An immobilized enzyme was prepared by adding 50 μl of water-soluble carbodiimide and reacting at 4 ° C. for 2 hours.

(2) Fiber treatment A cotton thread was cut into a length of 30 cm, 10 pieces were bundled, both ends thereof were tied, both ends thereof were immersed in methanol overnight, and then weighed for 7 hours in a vacuum dryer to obtain a sample for enzyme treatment. And This cotton thread bundle was put into a 15 ml test tube and the pH was adjusted to 4 with acetate buffer.
20 units of the above-mentioned micronized immobilized cellulase prepared as described above was added as an enzyme, and the mixture was shaken at 55 ° C and 160 times / min for 8 hours. After completion of the reaction, remove the cotton thread from the reaction solution and
It was washed twice with a mol / L phosphate buffer solution (pH = 7), washed three times with pure water and twice with methanol, and then dried under reduced pressure for 7 hours. Then, the weight reduction rate and the tensile strength reduction rate were measured in the same manner as in (2) of Example 1, and the results are shown in Table 1.

Example 3 (1) Synthesis of Immobilized Enzyme 60 g of methacrylic acid and 40 g of acrolein were dissolved in 150 g of methanol, 0.5 g of azobisisobutyronitrile as a polymerization initiator was added, and polymerization was carried out at 70 ° C. for 8 hours.
The polymerization conversion rate was 88%. Then, 20 g of sodium hydroxide and 400 g of water were added, and then methanol and residual monomers were removed by distillation under reduced pressure to obtain a polymer aqueous solution of pH = 7. Cellulase (Tricoderma reesei, manufactured by Sigma) dissolved in a phosphate buffer of pH 7 at a concentration of 5% by weight was taken in an amount of 10 g of the obtained polymer aqueous solution.
ml was added and mixed at 4 ° C. for 2 hours to immobilize cellulase on the polymer. After that, 1N hydrochloric acid was added to pH = 4.
After that, the polymer is precipitated to obtain fine polymer particles, and then adjusted water is added to obtain a solid content concentration of 10
The weight percent was the immobilized enzyme. The obtained immobilized enzyme was aggregated, but the particle size of the primary particles was 0.15 μm as measured by a scanning electron microscope.

(2) Fiber treatment Cotton yarn was treated in the same manner as in (2) of Example 2 except that the immobilized enzyme obtained in (1) of Example 3 was used. Then, the weight reduction rate and the tensile strength reduction rate of the cotton yarn were measured in the same manner as in (2) of Example 1, and the results are shown in Table 1.

Comparative Example 1 Cotton yarn was treated in the same manner as in (2) of Example 1 except that 20 units of non-immobilized free cellulase were used instead of the immobilized enzyme in Example 1 (2). . Then, the weight reduction rate and the tensile strength reduction rate of the cotton yarn were measured in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 2 A water-soluble immobilized enzyme was prepared in the same manner as in (1) of Example 1 except that water-soluble polyacrylic acid having a molecular weight of 30,000 was used in place of the polymer particles in Example 1 (1). It was created. Then, the cotton yarn was treated with an enzyme in the same manner as in Example 1 (2). The weight reduction rate and the tensile strength reduction rate of the treated cotton yarn were measured in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 3 A cotton yarn was used in the same manner as in Example 3 except that the fiber was treated in the state of a water-soluble immobilized enzyme having a pH of 7 instead of adding 1 N hydrochloric acid to precipitate fine particles. After enzymatic treatment, the tensile test was conducted and the results are shown in Table 1. When the water-soluble immobilized cellulase is used, the effect of preventing the cellulase from penetrating into the inside of the fiber is insufficient, and it is considered that the tensile strength is lowered.

Example 4 (1) Synthesis of Immobilized Enzyme Instead of using 0.5 ml of cellulase dissolved at a concentration of 5% by weight in an acetate buffer of pH 5 was dissolved in a phosphate buffer of pH 7 at a concentration of 5% by weight. An immobilized enzyme was prepared in the same manner as in (1) of Example 1 except that 2 ml of a neutral protease (Amanoprotease N Amano Pharmaceutical Co., Ltd.) was used.

(2) Fiber treatment The refined wool yarn was cut into 30 cm lengths, bundled in groups of 5 and tied at both ends, immersed in methanol overnight, dried in a vacuum dryer for 7 hours, and then treated with an enzyme. It was used as a sample. This wool yarn bundle was put in a 15 ml test tube, and 10 units of the immobilized protease prepared above to pH 7 with a phosphate buffer was used as an enzyme (1 unit was made of casein as a substrate,
7, the amount of enzyme producing tyrosine of 1.0 μmol / min at 37 ° C.) was added, and the mixture was shaken at 55 ° C. and 160 times / min for 2 hours. After the reaction is completed, take out the wool yarn bundle from the reaction solution,
Twice with 0.1 mol / L phosphate buffer (pH = 7),
After washing 3 times with pure water and 2 times with methanol, it was dried under reduced pressure for 7 hours. Then, the weight reduction rate and the tensile strength reduction rate of the wool yarn were measured in the same manner as in (2) of Example 1, and the results are shown in Table 1.

Comparative Example 4 Wool in the same manner as in (4) of Example 4 except that 10 units of non-immobilized free neutral protease were used in place of the immobilized enzyme in (2) of Example 4. The yarn bundle was processed. Then, the weight reduction rate and the tensile strength reduction rate of the wool yarn were measured in the same manner as in Example 1 (2), and the results are shown in Table 1.

[0039]

[Table 1]

[0040]

EFFECTS OF THE INVENTION According to the present invention, a fiber treating agent is provided which has an excellent feature that the reduction of the tensile strength after the treatment is small while maintaining the fiber modifying effect such as the texture by the enzyme treatment. The fiber treatment method used is provided.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kenya Makino 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (2)

[Claims] 1. A fiber treatment agent comprising an enzyme immobilized on water-insoluble polymer fine particles. 2. A fiber treatment method comprising treating a fiber in the presence of a fiber treatment agent containing an enzyme immobilized on water-insoluble polymer fine particles.