JPH093772A - Fiber structure and method of manufacturing the same - Google Patents

Abstract

(57) [Summary] [Structure] At least one side of a fiber structure is covered with a cross-linked film of a protein, and the cross-linking of the cross-linked film comprises a γ-carboxamide group which is a glutamine residue of amino acids constituting the protein. Fiber structure which is a bond between ε-amino groups which are lysine residues, and a method for producing a fiber structure in which the surface of the fiber structure is coated with a mixed aqueous solution of a protein to be crosslinked and transglutaminase, and the fiber structure is heat-treated. . [Effect] According to the present invention, due to its high moisture absorptive performance, it is possible to prevent dew condensation and stuffiness when worn in a coated fiber structure, and a clean and mild processing method
You can get a working environment.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a fiber structure.
More specifically, it relates to a fiber structure having excellent hygroscopicity and moisture permeability and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, in the field of wet coating, as a method for improving the moisture absorptivity of a fiber structure in the coating process, the moisture permeability is improved by adjusting the pore size of the film, and the protein etc. in the coating film is improved. Improves hygroscopicity by adding the hygroscopic substance of
Methods have been devised to prevent condensation on the film.

In the field of dry coating,
Since the film itself has almost no moisture absorptivity, in order to impart a moisture absorptive property, a method of adding a hygroscopic substance such as protein to impart a hygroscopic property to the film has been devised.

However, although the moisture absorption and permeation performance can be improved to some extent by adjusting the pore size of the film and the addition of protein, the moisture absorption performance is low because the amount of the hygroscopic substance added is small, and a large amount of dew condensation due to perspiration occurs during actual wear, The current situation is that moisture permeability cannot be reduced and stuffiness cannot be prevented.

In the conventional coating processing field, dimethylformamide is used as a general resin solvent in the wet coating processing, and dimethylformamide, toluene and the like are used in the dry coating processing.

Since such a solvent-based resin is used, migration of the disperse dye to the resin film in the film-forming process and migration pollution caused by the migration become a problem particularly in the coating process for the polyester dyed fiber structure. ing.

Further, the solvent waste liquid or the waste gas discarded in the film forming process is discarded or collected, and the handling of the waste solvent is a big problem at present.

[0008]

According to the present invention, a fibrous structure having excellent moisture absorption and permeation performance, less migration migration since it is water-based and does not use a solvent, and does not require solvent recovery, and the like. It is to provide a simple and low-cost method for producing a fiber structure.

[0009]

The fiber structure of the present invention has the following constitution in order to solve the above problems.

That is, at least one surface of the fiber structure is coated with a cross-linked film of protein, and the cross-linking bond of the cross-linked film is composed of γ-carboxamide group and lysine residue which are glutamine residues of amino acids constituting protein. It is a fiber structure characterized by a bond between certain ε-amino groups.

Further, the method for producing a fiber structure of the present invention has the following constitution in order to solve the above problems.

That is, the method for producing a fiber structure is characterized in that the surface of the fiber structure is coated with a mixed aqueous solution of a protein to be crosslinked and transglutaminase and then the fiber structure is heat-treated.

Further, the method for producing a fiber structure of the present invention has the following constitution.

That is, the fiber structure is characterized in that the surface of the fiber structure is coated with an aqueous solution of the protein to be crosslinked, the protein to be crosslinked is self-gelled, and transglutaminase is allowed to act on the gel of the protein to be heat-treated. Is a manufacturing method.

[0015]

The fiber structure of the present invention will be described in detail below.

In the present invention, at least one surface of the fiber structure is coated with a protein cross-linking film means that at least one surface or both surfaces of the fiber structure are adhered and coated with the protein cross-linking film. Say that.

The cross-linked film of a protein is three-dimensionally formed by condensation-crosslinking a functional group between a γ-carboxamide group which is a glutamine residue of amino acids constituting a protein and an ε-amino group which is a lysine residue. A film formed by a coating with few pinholes that is a structure.

The cross-linking bond of the cross-linking film is the bond between the γ-carboxamide group, which is a glutamine residue of amino acids constituting a protein, and the ε-amino group, which is a lysine residue, of the enzyme used in the present invention ( Transglutaminase), which is a bond formed by the substrate specificity of the enzymatic reaction.

As described above, it becomes possible to exhibit excellent hygroscopicity and moisture permeability by the action of the coating of the protein crosslinked film.

Next, the method for producing the fiber structure of the present invention will be described below.

In the fiber structure of the present invention, the surface of the fiber structure is coated with a mixed aqueous solution of a protein to be crosslinked and transglutaminase and then heat-treated, or a dry coating-like method, or an aqueous solution of the protein to be crosslinked to the surface of the fiber structure. Is coated and then self-gelled, and transglutaminase is allowed to act on the cross-linked protein gel, followed by heat treatment, to produce by a wet coating-like method.

The cross-linked protein used in the present invention is not limited to its origin, and any protein such as plant protein or animal protein can be used.

Examples of the vegetable protein include defatted products of plant seeds and proteins separated therefrom, that is, soybean protein,
Wheat protein or the like can be used.

As animal protein, milk protein (casein, etc.), gelatin, collagen, keratin,
An aqueous solution such as fibroin can be used.

The transglutaminase used in the present invention is an acyltransferase belonging to EC 2.3.2.13, which is dependent on Ca 2+ derived from animals, and does not require Ca 2+ dependence derived from plants or fungi. And the like are preferably used.

The mixed aqueous solution of the protein to be crosslinked and transglutaminase in the dry coating-like system is prepared by adding the amount of transglutaminase necessary for crosslinking the protein to the aqueous protein solution adjusted to pH and protein concentration suitable for the enzymatic reaction. It means an aqueous solution.

From the viewpoint of enzyme reaction rate and film-forming property, the pH suitable for the enzyme reaction is preferably 4 to 11, and more preferably 5 to 8.

From the viewpoint of film-forming property, the protein concentration in the mixed aqueous solution is preferably 2% by weight (hereinafter abbreviated as wt%) or more, more preferably 5% by weight or more.

The amount of transglutaminase required for protein cross-linking is 0.1 for every 1.0 g of protein to be cross-linked.
It is preferable to add more than a unit.

From the stability of the enzyme, an SH protective substance such as dithiothreitol or glutathione may be added to the aqueous solution as appropriate.

If the enzyme to be used is Ca2 + -dependent, it is preferable to add it so that the Ca2 + concentration in the mixed aqueous solution is usually 10 mM.

As the coating, various coating methods used for dry coating such as knife coating and gravure coating can be used for the fiber structure.

The heat treatment promotes the enzymatic reaction in the coated mixed aqueous solution and the reaction due to the increase in the protein concentration by decreasing the water content of the mixed aqueous solution, and at the same time, finally the film is formed. The purpose is to evaporate water.

As the heat treatment method, either a dry heat treatment using dry heat air or a wet heat treatment using dry heat air and steam can be used.

The heat treatment temperature may be a temperature which takes into consideration the progress of the enzyme reaction, the inactivation of the enzyme and the evaporation of water, and is preferably 10 ° C. or higher, and is preferably 30 ° C. or higher in consideration of the process passability and the like.

The fiber structure of the present invention can be obtained by heat treatment for 1 minute to 2 hours depending on the coating clearance and the heat treatment temperature.

The aqueous solution of the protein to be cross-linked in the wet coating-like system means an aqueous protein solution adjusted to have a protein concentration suitable for self-gelling.

The protein concentration suitable for self-gelation is the concentration at which gelation (self-gelation) can be caused by the cohesive force of the protein itself by cooling the aqueous protein solution, and it depends on the type of protein used. different. Generally, the aqueous solution has the lowest concentration that causes self-gelation, but an aqueous protein solution having a concentration of 1.5 to 2 times the lowest self-gelling concentration is preferable.

Knife coating as coating,
A coating method used for dry coating such as gravure coating can be used.

The gelation means gelling on the fiber structure by utilizing the self-gelling ability of the protein provided by the coating.

To act transglutaminase on the protein gel means to immerse the one in which the fiber structure and the protein gel are integrated in a reaction aqueous solution tank in which transglutaminase is dissolved, or to apply a reaction aqueous solution in which transglutaminase is dissolved. Alternatively, it refers to causing a crosslinking reaction of a protein gel by spraying.

From the viewpoint of enzyme reaction rate and film forming property, the pH of the reaction aqueous solution is preferably 4 to 11, and more preferably 5 to 8.

The enzyme concentration is preferably 0.01 units or more per 1 ml of the solution, and more preferably adjusted to 10 units or more.

When the heat treatment is carried out in a reaction aqueous solution tank, the heat treatment temperature means the treatment liquid temperature, preferably a temperature at which gelled protein is not eluted, that is, a range of 10 to 40 ° C., more preferably 20. The temperature is in the range of up to 30 ° C., and even when it is applied or sprayed, the treatment may be performed at the same treatment temperature.

It is preferable to act at this temperature for 1 minute or more, more preferably for 10 minutes or more, and after the reaction,
By evaporating the water, the fiber structure of the present invention is obtained.

In the present invention, since the treatment liquid is a water-based coating system, migration contamination due to the solvent is reduced, and problems such as recovery and disposal of the waste solvent can be solved. The fiber structure in the present invention refers to natural fibers such as wool, silk and cotton, synthetic fibers such as nylon, polyester and acrylic, and those produced by blending, knitting and blending these fibers. Specifically, it is a cloth or the like.

In the case of protein fibers such as wool and silk, and polyamide fibers such as nylon, the terminal amino group thereof also participates in the cross-linking due to the enzymatic reaction, so that the adhesiveness between the fiber and the film is further improved.

[0048]

The present invention will be described in more detail below with reference to Examples and Comparative Examples.

The water vapor permeability and moisture absorption in the examples and the durability of the film were evaluated according to the following methods.

[Moisture Permeability] Calcium chloride was placed in the moisture permeability measuring container until the 9th minute,
The test piece was placed so that the coated surface was on the front side, and further silicone packing was placed on the test piece.

The temperature of the container is 40 ± 2 ° C. and the relative humidity is 90 ±.
It was put in a 2% constant temperature and humidity chamber, left for 1 hour, then the container was taken out, and the weight was immediately measured.

The container was again placed in the constant temperature and humidity chamber, left for 1 hour, then taken out, and the weight was measured immediately.

The moisture permeability was calculated from the weight determined above by the following formula.

Moisture vapor transmission rate (g / m ² · 24 hr) = [(weight−weight) × 24] / S S: moisture vapor transmission area (m ² ) [moisture absorption] Put a test piece in a weighing bottle and cover it. I loaded it half open.

The weighing bottle is placed at a temperature of 20 ± 2 ° C. and a relative humidity of 6
The sample was placed in a constant temperature and humidity chamber of 5 ± 2% and left for 4 hours, then the lid was immediately closed and the weight was measured.

Open the lid of the container half again, and at 110 ° C.,
After drying for an hour, the lid was immediately closed and the weight was measured.

Moisture absorption was calculated by the following formula from the weight obtained by subtracting the weight of the weighing bottle from the weight obtained above.

Moisture absorption (%) = [(weight of test piece when absorbing moisture-
Absolute dry weight) × 100] / absolute dry weight [Durability of coating] The coated coating pieces were placed in hot water (90 ° C) and observed for dissolution.

The following proteins and enzymes were used in the examples.

(1) Protein Commercially available purified gelatin powder (2) Enzyme Transglutaminase (EC 2.3.2.13) Enzyme origin: Actinomycete Streptobert cilium origin Enzyme activity: 1000 units / g The one that was slightly dissolved was marked with Δ, and the one that was significantly dissolved was marked with x.

Example 1 Purified gelatin powder was dissolved in ion-exchanged water to prepare a 30 wt% aqueous solution, and the pH was adjusted to 6. This aqueous solution was heated to 40 ° C. and transglutaminase was added so that 1.25 units per 1 g of protein were added to prepare a coating solution.

A plain woven fabric made of polyester filament yarn with both warp and weft of 75 denier was used as the base fabric, and the coating treatment solution prepared above was applied with a knife coater, followed by incubation at 37 ° C. for 2 hours. . After the incubation, the product was dried at 100 ° C. to deactivate the enzyme to obtain a desired moisture-absorbing and permeable material.

As shown in Table 1, the fiber structure was high in both moisture permeability and moisture absorption and was excellent in film durability.

[0064]

[Table 1] [Example 2] The purified gelatin powder was dissolved in ion-exchanged water, and a 30 wt% aqueous solution was adjusted to pH 6. This aqueous solution was heated to 40 ° C. and transglutaminase was added so that 1.25 units per 1 g of protein were added to prepare a coating solution.

A plain woven fabric made of nylon filament yarn having 70 denier for both warp and weft was used as the base fabric, and the coating solution prepared above was applied with a knife coater, followed by incubation at 37 ° C. for 2 hours. .
After the incubation, the product was dried at 100 ° C. to deactivate the enzyme to obtain a desired moisture-absorbing and permeable material.

The fiber structure had a high water vapor transmission rate and a high water vapor absorption rate and excellent film durability. The results are shown in Table 1.

Example 3 Purified gelatin powder was dissolved in ion-exchanged water to prepare a 30 wt% aqueous solution. This aqueous solution was heated to 40 ° C. to prepare a coating treatment liquid.

Using a plain woven fabric with a polyester filament yarn of 75 denier for both warp and weft as the base fabric,
The coating solution prepared above was applied with a knife coater, and after application, the protein was gelated at room temperature. This fiber structure was subjected to an enzyme treatment by immersing it in a treatment bath having an enzyme concentration of 10 units / ml, a pH of 6, and a bath temperature of 25 ° C. for 30 minutes. After the immersion, the product was dried at 100 ° C. to deactivate the enzyme to obtain the intended moisture-absorbing and permeable material.

The fiber structure was high in both moisture permeability and moisture absorption and was excellent in film durability. The results are shown in Table 1.

[Example 4] A fiber structure was produced in the same manner as in Example 3 except that the treatment bath temperature was 50 ° C.

A product excellent in moisture permeability and hygroscopicity was obtained.

The results are also shown in Table 1.

[Comparative Example 1] A sample was prepared in the same manner as in Example 1 except that the enzyme was not added.

Since no enzyme was added, the fiber structure was inferior in film durability.

The results are also shown in Table 1.

[Comparative Example 2] A sample was prepared in the same manner as in Example 3 except that the enzyme was not added.

Since no enzyme was added, the fiber structure was inferior in film durability.

The results are also shown in Table 1.

[0079]

EFFECTS OF THE INVENTION According to the present invention, it is possible to prevent dew condensation and stuffiness when worn in a fiber structure due to its high moisture absorptivity.

Further, since the water-based coating is used, the problem of migration of disperse dyes to the resin film in the film-forming process particularly in the coating process for polyester dyed fiber structure can be solved, and at the same time, it is discarded in the film-forming process. Since it can solve the problems of solvent waste liquid or waste gas,
Work environment is obtained.

Claims (10)

[Claims] 1. A fiber structure, at least one side of which is coated with a cross-linked film of a protein, and the cross-linking of the cross-linked film is formed by a γ-carboxamide group and a lysine residue which are glutamine residues of amino acids constituting the protein. A fiber structure characterized by a bond between certain ε-amino groups. 2. The fiber structure according to claim 1, wherein the protein is a vegetable protein or an animal protein. 3. A method for producing a fiber structure, which comprises heat-treating the fiber structure after coating the surface of the fiber structure with a mixed aqueous solution of a protein to be crosslinked and transglutaminase. 4. A fiber structure characterized in that the surface of a fiber structure is coated with an aqueous solution of a protein to be crosslinked, the protein to be crosslinked is self-gelled, and transglutaminase is allowed to act on the gel of the protein to be heat-treated. Manufacturing method. 5. A transglutaminase is EC2.3.
5. The method for producing a fiber structure according to claim 3, which is an acyltransferase belonging to 2.13. 6. The method for producing a fiber structure according to claim 3, wherein the aqueous solution of the protein to be cross-linked has a pH of 4-11. 7. The crosslinked protein concentration in the mixed aqueous solution is 2
The method for producing a fiber structure according to claim 3, wherein the content is at least wt%. 8. The method for producing a fiber structure according to claim 3, wherein the heat treatment temperature is 10 ° C. or higher. 9. The method for producing a fiber structure according to claim 4, wherein the aqueous solution of the protein to be crosslinked has a pH of 4 to 11. 10. The method for producing a fiber structure according to claim 4, wherein the heat treatment temperature is 10 to 40 ° C.