JPH08302575A - Dyeable fiber and its production - Google Patents

Abstract

PURPOSE: To obtain a dyeable fiber capable of being dyed with a dye for protein-based fibers and suppressing a fibrillation caused by wearing or washing, by forming the coated layer of a specific enzyme protein on the surface of a fiber and a cross-linking the coated layer. CONSTITUTION: This dyeable fiber is obtained by immersing a fiber in an acidic or a neutral solution containing an enzyme protein such as cellulase-based protein having >=10000, preferably 20000-300000 molecular weight, forming the coated layer of the enzyme protein by imparting 3-15mg/m<2> enzyme protein on the surface of the fiber, conducting a cross-linking treatment using a cross- linking agent such as glutaraldehyde, then washing sufficiently and drying.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dyed fiber which can be easily dyed by a simple operation and which is less likely to be fibrillated after washing and has less dull color, and a method for producing the dyed fiber.

[0002]

2. Description of the Related Art Dyeing means that when a fiber is placed in an aqueous dye solution at a certain temperature, the dye diffuses from the water into the fiber, the amount of the dye in the dye bath gradually decreases, and after a certain time, the equilibrium is reached. It means that the dye stays in the fiber and does not fall off even if it is taken out of the dye bath and washed with water.

The important points in this dyeing are the diffusibility of the dye into the fiber and the property of preventing the dye from falling off, which are influenced by the affinity between the fiber and the dye.

However, there are many kinds of fibers in the present age, such as natural fibers and chemical fibers depending on the type of raw material, and cellulose type, protein type, polyester type, polyacrylonitrile type, etc. depending on the composition and structure. Further, with the recent multifunctionalization of fibers, not only single fibers but also mixed-spun products and composite products made of various fibers have been put on the market. Therefore,
The dye for the fiber must be selected directly from various types such as acidic, basic, mordant, disperse and reactive dyes in order to ensure the affinity, and the dyeing method must be devised.

That is, the dye and dyeing method must be changed for each fiber, and in addition to complicated operations, the yield is low,
It was not industrially advantageous. On the other hand, in the case of cellulosic fibers such as cotton and hemp, and regenerated cellulosic fibers such as rayon and tencel, the surface of monofilaments becomes split when subjected to physical force such as wearing and washing after dyeing (fibrillation). ),
For this reason, color change (dullness) may occur due to fiber fluffing.

[0006]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a dyed fiber which does not require selection of various dyes and dyeing methods and which is prevented from fibrillation and color dullness and a method for producing the dyed fiber. is there.

[0007]

In view of such circumstances, the present inventors believe that the above problems can be solved by providing a coating layer that is adsorbed on the surface of every fiber and is dyed well. As a result of diligent research, enzyme proteins have high adsorptivity for all fibers, and if a coating layer is formed on the fiber surface and further treated with a cross-linking agent, a robust coating layer is formed, and a dye is dyed on this. It was found that a dyed fiber in which fibrillation due to wearing, washing and the like and color dullness are suppressed can be obtained by wearing the dyed fiber, and the present invention has been completed.

That is, according to the present invention, a coating layer composed of an enzyme protein cross-linked with a cross-linking agent is formed on the surface of a single fiber,
The present invention also provides a dyed fiber characterized by being dyed with a dye.

The present invention also provides a method for producing the above-mentioned dyed fiber, which comprises dyeing a fiber having a coating layer made of an enzyme protein cross-linked with a cross-linking agent formed on the surface of a single fiber. Is.

The enzyme protein applied to the present invention means a generic name of proteins having a specific structure for having a catalytic action. In other words, whether or not the catalytic function is expressed,
All proteins that have a structure for catalysis are applicable. The origin of the enzyme protein differs depending on the organism to be produced, and there are animal origin, plant origin, and microbial origin, but in the present invention, enzyme proteins of all origins can be used.

Examples of such enzyme proteins include hydrolases, lilases, oxidorectases, ligases, transferases and immelases, all of which can be used. Among these, it is preferable to use hydrolases, and it is particularly preferable to use peptidases such as protease, glucosidases such as cellulase and amylase, and esterases such as lipase.

The molecular weight of the enzyme protein is preferably 10,000 or more, more preferably 20,000 to 300,000.

The enzyme proteins may be used alone or in combination of two or more. Further, in the present invention, even if a protein other than the enzyme protein is mixed in the protein diluted solution described below, the enzyme protein is preferentially adsorbed on the surface of the single fiber of the fiber due to the adsorptivity of the enzyme protein, It is not necessary to use purified and expensive enzyme protein.

The fiber used as a raw material in the present invention is not limited by the kind or structure thereof, and may be natural cellulose fiber or chemical fiber. Here, the natural cellulose fiber is a natural fiber containing cellulose such as cotton and hemp as a basic unit, and also includes pretreated fibers obtained by mercerizing cotton with NaOH, KOH, LiOH or the like, or treating with liquid ammonia or the like. Be done. Further, the chemical fiber means a regenerated fiber and a synthetic fiber, examples of the regenerated fiber include viscose rayon, cupra, and tencel, and the synthetic fiber includes polyester, acrylic, nylon, vinylon, polypropylene, polyethylene, and the like. Examples thereof include polyvinyl chloride, vinylidene, polyurethane and benzoate. Further, the form of the fiber is not particularly limited, such as raw yarn, woven fabric and non-woven fabric,
Further, a blended product may be used.

In the present invention, in order to form a coating layer of the enzyme protein on the surface of the monofilament, it is first immersed in a solution containing the above enzyme protein. The solvent used here has a pH of 1-10.
The acidic buffer solution, the neutral buffer solution or the weak alkaline buffer solution can be used, among which the acidic or neutral buffer solution is preferable. The enzyme protein is diluted with such a solvent and at the same time the pH of the solution is adjusted. The diluted solution is preferably adjusted to an acidic or neutral range of pH 3 to 8 depending on the adsorption condition of the enzyme protein to the fiber. The temperature of the diluted solution is
The temperature is preferably 60 ° C. or lower at which the protein does not undergo thermal denaturation, and particularly when an enzyme that hydrolyzes fiber, such as cellulase that hydrolyzes cellulosic fiber such as cotton and rayon, is used, its catalytic property (degradability) is 0 to suppress
It is preferably carried out at a low temperature of -5 ° C. The ionic strength of the diluted solution is preferably 0.01 or more from the viewpoint of the concentration capable of maintaining the pH buffering ability of the buffer solution, and is particularly preferably 0.05 to
It is preferably 0.2. When immersing the fiber in the dilute solution of the enzyme protein, it is preferable to shake or stir the solution in order to increase the adsorption efficiency of the enzyme protein.

In the present invention, since the coating layer (adsorbed protein layer) is formed on the surface of the single fiber by adsorbing the enzyme protein, the concentration of the enzyme protein in the diluted solution may be low.
Adsorption amount of enzyme protein to single fiber is 3 per fiber surface area
It is preferable to adjust it so as to be ˜15 mg / m ² .

The time for immersing the fiber in the dilute solution of the enzyme protein can be set to reach the adsorption equilibrium. The immersion is preferably carried out under the conditions of Langmuir-type adsorption isotherm showing monomolecular adsorption in the relationship between the enzyme protein concentration in the aqueous solution and the protein adsorption amount on the fiber. When determining the adsorption equilibrium time of enzyme protein or plotting the adsorption isotherm, measure the change in protein concentration in the solution caused by adsorption to the fiber, and measure the amount of protein in the aqueous solution (enzyme concentration) before and after adsorption and the treated fiber The adsorption amount can be roughly calculated from the amount and the specific surface area of the fiber by the following formula (1).

In the present invention, the amount of protein in the aqueous solution is determined by using the Lowry method (DC-protein / assay method; manufactured by BIO-RAD), which is the most representative protein quantification method, and a calibration curve for bovine serum albumin is used. The converted value is calculated as The specific surface area of the fiber is calculated by the BET multipoint method by krypton adsorption. The amount of adsorption per surface area of fiber is expressed in mg / m ² .

[0019]

[Equation 1]

Here, W: amount of fiber used (g), V: amount of enzyme solution (l), X _A : enzyme concentration before adsorption (g / l), X _B : enzyme concentration after adsorption (g / l) ), S: specific surface area of the fibers used (m ² / g).

After the enzyme protein is adsorbed on the fiber, a crosslinking treatment is carried out using a crosslinking agent. The cross-linking agent applied to the present invention,
There is no particular limitation as long as it is mainly reactive with a functional group in a protein and causes cross-linking by a reaction between protein molecules and within a protein molecule. For example, “Shinsei Chemistry Laboratory 1 Protein IV Structure-Function Relationship 13
Chapter Cross-link, P207-254 (Tokyo Kagaku Dojin)
And "Biochemistry Experimental Method 13 Chemical Modification of Proteins (2) VI
Known cross-linking agents described in "Chapter Cross-linking Reaction, P81-113, Satoku Ohno (Society Press Center)" can be used. Among them, aldehyde compounds, epoxy compounds, isocyanate compounds and the like are highly reactive and can be preferably used. A wide variety of conventionally known aldehyde compounds can be used, and examples thereof include formaldehyde and dialdehydes such as glyoxal, malonaldehyde, and glutaraldehyde. As the epoxy compound, ethylene glycol, polyethylene glycol, propylene glycol,
Polyglycol, glycerin, sorbitol, polyglycerol, pentaerythritol, tris (2-hydroxyethyl), isocyanurate, trimethylolpropane, neopentyl glycol, phenol ethylene oxide, lauryl alcohol ethylene oxide mono- and polyglycidyl ether, epoxy group Including coupling agents. These epoxy compounds are used by dissolving them in water, but when the solubility is low, it is preferable to dissolve them in a small amount of an organic solvent such as dioxane or a mixed solvent of isopropyl alcohol and water. Examples of the isocyanate compound include toluene diisocyanate, diphenylmethane diisocyanate, hexanemethylene diisocyanate, isophorone diisocyanate, and naritaline diisocyanate.
Examples thereof include compounds having two or more isocyanate groups in the molecule. It is preferable that these isocyanate compounds are dissolved in a known organic solvent capable of cross-linking with a protein, for example, chloroform, hexane, toluene or the like.

Further, it is preferable to add a catalyst for enhancing the reactivity with the functional group in the protein together with the crosslinking agent. Such catalysts include neutral salts of alkali metals, such as sodium fluoride, sodium chloride, sodium bromide, sodium nitrate, sodium sulfate, sodium acetate, sodium nitrite, sodium thiocyanate, and sodium thionitrate. To be

The cross-linking treatment can be carried out in the same solution without drying the fibers after adsorbing the enzyme protein, or by transferring it to another solution. Further, it can also be performed on fibers that have been pulled out of the solution and dried. The concentration of the cross-linking agent varies depending on the functional group equivalent (molecular weight / number of functional groups), but the total number of moles of the functional group may be calculated from the amount of adsorbed protein per fiber weight, and the amount of the cross-linking agent used may be determined accordingly. . The temperature of the catalyst for carrying out the crosslinking reaction is preferably set depending on the crosslinking agent used, and the pH of the solution is preferably changed from weakly acidic to weakly alkaline.

Further, it is necessary to carry out the cross-linking under the condition that the adsorbed state which is the previous stage is not damaged. For example, an aldehyde compound (crosslinking agent) can easily react with an amino group in a protein at room temperature, and can form a crosslink in an adsorbed state. On the other hand, the epoxy compound (crosslinking agent) is placed under conditions such as heating or heating in order to accelerate the reaction with the amino group and the carboxyl group in the protein. The protein may be heat-denatured by heating or heating. Therefore, it is necessary to pay attention to the temperature conditions, but there is no problem if the temperature is such that the uniformity of the protein coating layer on the surface of the single fiber is not lost. After the treatment with the cross-linking agent, washing with water and washing with hot water are thoroughly performed according to a conventional method.

The coated fiber thus obtained may be dyed and dyed by a conventional method.

The dye used for dyeing may be any dye as long as it dyes protein fibers such as wool and silk. Examples thereof include direct dyes, acid dyes, basic dyes, mordant dyes, acidic mordant dyes, vat dyes, and reactive dyes.

When dyeing, a dye aqueous solution having a predetermined concentration is used and the bath ratio is appropriately selected. Sufficient dyeing is performed only with a simple dye aqueous solution, but various dyeing assistants may be used in combination if necessary. The temperature may be determined according to the characteristics of the dye used, and the dyeing time may be appropriately determined according to the temperature. After dyeing, soaping is performed if necessary.

In the case of printing, usually, a dye and a paste are mixed and a color paste adjusted to an appropriate viscosity is printed on the fiber and dried, and then heat treated with relatively moist steam and soaping is performed.

The enzyme activity of the coating layer composed of the enzyme protein which is cross-linked by the cross-linking agent on the surface of the monofilament of the fiber is as follows: the fiber having the coating layer is used for clothing (wearing) or for other purposes. When used, it preferably has no activity at the time of use. Most of the enzymatic activity is usually lost in the crosslinking step.

[0030]

INDUSTRIAL APPLICABILITY The method of the present invention can be applied to dyeing any fiber, and any dye can be adopted as long as it is a dye used for protein fibers. Therefore, a blended product can be dyed with one dye per bath, which is industrially advantageous.

Further, the dyed fiber of the present invention suppresses fibrillation caused by wearing and washing, and has less dullness of color.

[0032]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1 As enzyme proteins, cellulase produced by Bacillus (Microtechnical Research Article No. 1485), cellulase produced by Trichoderma (Meiselaser TP-60, manufactured by Meiji Seika Co., Ltd.), Bacillus The amylase to be produced (Mikori Kenjoyori No. 10886) was ammonium sulfate precipitated, dialyzed and freeze-dried.

The fiber is a plain weave cotton (Washing Science Association 112
5 thin cloth) and plain weave polyester (Asahi Kasei Palace) are used to remove the oil, and chloroform: methanol = 1:
Soxhlet extraction at 1 was performed for 6 hours.

The specific surface area of the fiber was calculated by the BET multipoint method by krypton adsorption. High-precision fully automatic adsorption device BELSORP36 manufactured by Nippon Bell Co., Ltd.
By using krypton (purity 99.995).
%), Dead volume of helium (purity 99.999%), adsorption temperature 77K, measurement range of relative pressure 0.01 to 0.35 (measurement pressure / saturated vapor pressure of adsorbed gas), equilibration time for each relative pressure. The specific surface area based on the BET multimolecular adsorption theory was calculated by adsorption at an isothermal time of 180 seconds. As a result, the cotton fabric is 0.638 m ² / g and the polyester fabric is 0.205.
It was m ² / g.

The buffer used was 100 mM acetic acid-sodium acetate buffer (pH 5.0), and the ionic strength was adjusted to 0.1.

First, the protein was diluted in a buffer solution, and the protein concentration was adjusted to a range of 0 to 1 g / l in terms of the bovine serum albumin conversion value of the protein quantitative value by the Lowry method. 50 g of fibers was added to 1 liter of this solution, and the temperature of the solution was adjusted to 5 ° C., and the fibers were immersed while shaking until equilibrium adsorption was reached.

As a result of plotting the adsorption isotherm (FIGS. 1 and 2), the maximum equilibrium adsorption amount was as shown in Table 1 below.

[0039]

[Table 1]

As the cross-linking agent, an aldehyde-based cross-linking agent glutaraldehyde (about 5% solution, Wako Pure Chemical Industries, first grade)
Or represented by the following formula (1), the average molecular weight is about 1000,
An epoxy-based cross-linking agent having an average epoxy equivalent of 172, polyglycerol polyglycidyl ether (Denacol EX-
521, manufactured by Nagase Kasei Co., Ltd.) was diluted in an acetic acid-sodium acetate buffer solution to 100 mM, and 50 g of the fiber to which the enzyme protein was adsorbed was added to 1 liter of the cross-linking agent dilution solution and immersed.

[0041]

Embedded image

2 if a glutaraldehyde solution is used
The mixture was shaken at 0 ° C. for 1 hour to carry out a crosslinking reaction. Denacol E
When the X-521 solution was used, the reaction was carried out by heating within 20 minutes from 20 ° C to 90 ° C and shaking for 1 hour. After the crosslinking treatment, the fibers were thoroughly washed with water and dried.

Cellulase produced by Bacillus is adsorbed on a cotton cloth, and after reaching an adsorption equilibrium, the product crosslinked with glutaraldehyde is the product of the present invention 1, Denacol EX-5.
The product crosslinked at 21 was designated as Product 2 of the present invention. After crosslinking, it was thoroughly washed with water and dried.

Cellulase produced by Bacillus was adsorbed on a polyester cloth, and after reaching the adsorption equilibrium, the product crosslinked with glutaraldehyde was invented product 3, and the product crosslinked with Denacol EX-521 was invented product 4. did. After crosslinking, it was washed with water and dried.

A cotton cloth which did not adsorb and crosslink the enzyme protein was designated as Comparative Product 1 and a polyester cloth was designated as Comparative Product 4.

Cellulase produced by Bacillus was adsorbed on a cotton cloth, reached an adsorption equilibrium, washed thoroughly with water and dried to obtain Comparative Product 2. After reaching the adsorption equilibrium, 9
Comparative product 3 was heated at 0 ° C. for 1 hour. Similarly, cellulase produced by Bacillus was adsorbed on a polyester cloth, and after reaching the adsorption equilibrium, the product was washed thoroughly with water and dried to obtain Comparative product 5. After reaching the adsorption equilibrium, 9
Comparative product 6 was heated at 0 ° C. for 1 hour.

(Dyeing test) These fibers were dyed with a direct dye or an acid dye. Dyeing with a direct dye is carried out by adding 5% of Congo Red (special grade Wako Pure Chemical Industries, Ltd.) (to fiber) to a sodium sulfate, 15 g / l dyeing bath at a bath ratio of 1:20 and stirring at a temperature of 90 ° C. for 1 hour. It was done by doing. Then, it was washed with water and dried.

For dyeing with an acid dye, orange II (first grade, manufactured by Wako Pure Chemical Industries, Ltd.) 5% (to fiber), sodium sulfate 10% (to fiber), sulfuric acid 5% (to fiber) and a bath ratio of 1:20.
Dyeing bath, the cloth was put at room temperature, the temperature was 70 ° C. for 30 minutes, and the dyeing was carried out for 1 hour while stirring. Then, it was washed with water and dried.

The dyeability is evaluated according to the following criteria.
The visual evaluation was performed by 5 evaluators. The results are shown in Table 3.

[0050]

[Table 2] Judgment Criteria for Evaluation ○: Good dyeing. Δ: Slightly dyed. X: Not dyed.

[0051]

[Table 3]

It can be seen from Table 3 that the cotton fibers are dyed directly with the dye but not with the acid dye. On the other hand, by adsorbing and cross-linking enzyme proteins to form a coating layer, cotton fibers could be dyed well with an acid dye. Polyester fibers are not dyed with direct dyes or acid dyes,
It was possible to dye well with both dyes by adsorbing and cross-linking the enzyme protein to form a coating layer. Similar staining results were obtained with cellulase produced by Trichoderma spp. And amylase produced by Bacillus spp.

Example 2 Plain weave cotton / polyester blend (cotton: polyester =
35:65) and the dyeability was examined in the same manner as in Example 1. Cellulase produced by Bacillus is adsorbed on cotton / polyester blended fabric, and after reaching adsorption equilibrium, the product crosslinked with glutaraldehyde is present product 5, and the product crosslinked with Denacol EX-521 is present product 6. did. After crosslinking, it was thoroughly washed with water and dried.

Comparative cotton 7 was a cotton / polyester blended fabric that did not adsorb and crosslink the enzyme protein. Cellulase produced by Bacillus is adsorbed on a cotton / polyester blended fabric, reached adsorption equilibrium, washed thoroughly with water and dried as Comparative product 8, and after reaching adsorption equilibrium, 9
Comparative product 9 was heated at 0 ° C. for 1 hour. The dyeability test results are shown in Table 4.

[0055]

[Table 4]

In general, cotton fibers are dyed with direct dyes, but not with acid dyes. Polyester fiber does not dye directly with acid dyes. In the cotton / polyester blended fabric of the comparative product, the polyester is not dyed with the direct dye, so that the polyester portion becomes white and frost-like dyeing occurs. But adsorbing enzyme protein,
By cross-linking, it can be seen that the polyester could be dyed directly with the dye, and the entire blend could be dyed well. Further, although the mixed dye cannot be dyed with an acid dye, it can be dyed well by adsorbing and crosslinking the enzyme protein.

Similar staining results were obtained with cellulase produced by Trichoderma and amylase produced by Bacillus.

Example 3 Fibers obtained by adsorbing and cross-linking an enzyme protein on the surface of a single fiber of cotton to form a coating layer were used for clothing and were prevented from fluffing (generation of fibrils) during washing and color change ( Dull)
The preventive effect was investigated.

The fabrics dyed with Congo red used in Examples 1 and 2 of the present invention and Comparative Products 1, 2 and 3 were evaluated for fibril generation and color change due to washing.

For washing, a model detergent (Table 5) was used, and the detergent was dissolved in tap water to a concentration of 0.0833% (w / v). Shizu Gozen
After washing with Hitachi for 12 minutes and rinsing for 5 minutes, dehydration and drying were performed. This washing process was repeated 5 times.

[0061]

[Table 5]

In order to evaluate the occurrence of fibrils, the surface of the single fiber of the cloth was observed with a scanning electron microscope and judged according to the following criteria. For the observation, a cloth sample was subjected to a sputtering treatment with platinum palladium, and an electron emission electron microscope (FE-S) was used.
EM, S-4000, manufactured by Hitachi) at an acceleration voltage of 5 kV.

[0063]

[Table 6] Criteria for occurrence of fibrils 1. No fibril formation was observed on the surface of the single fiber. 2. A slight fibril formation is seen on the surface of the single fiber. 3. Fibrils are generated on the surface of the single fibers, but the fibrils are not entangled between the single fibers. 4. Fibrils are entangled between single fibers.

FIG. 3 shows a photograph corresponding to the criterion for fibril generation. Further, the color change due to the washing of dyeing was evaluated by visual judgment and judged according to the following criteria.

[0065]

[Table 7] Color Change Judgment Criteria: Equivalent to the dyed state before washing. Δ: Slightly inferior to the dyed state before washing. X: Significantly inferior to the dyed state before washing (dullness occurs).

[0066]

[Table 8]

The dyeability of the cotton fiber with the direct dye is such that the dye is easily detached from the fiber by washing and fibrils are generated, resulting in a dull color. On the other hand, it can be seen that the formation of fibrils can be reduced and the dullness of color can be suppressed by adsorbing and cross-linking the enzyme protein to form a coating layer on the surface of the single fiber.

[Brief description of drawings]

FIG. 1 is a diagram showing adsorption isotherms of enzyme proteins.

FIG. 2 is a diagram showing adsorption isotherms of enzyme proteins.

FIG. 3 is a photograph showing criteria for determining the occurrence of fibrils.

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[Procedure amendment]

[Submission date] June 6, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction content]

Examples of such enzyme proteins include hydrolases, lyases, oxidorectases, ligases, transferases and immelases, all of which can be used. Among these, it is preferable to use hydrolases, and it is particularly preferable to use peptidases such as protease, glucosidases such as cellulase and amylase, and esterases such as lipase.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction content]

After the enzyme protein is adsorbed on the fiber, a crosslinking treatment is carried out using a crosslinking agent. The cross-linking agent applied to the present invention,
There is no particular limitation as long as it is mainly reactive with a functional group in a protein and causes cross-linking by a reaction between protein molecules and within a protein molecule. For example, “Shinsei Chemistry Laboratory 1 Protein IV Structure-Function Relationship 1
Chapter 3 Cross-linking, P207-254 (Tokyo Kagaku Dojin) and "Biochemical Experimental Method 13 Chemical Modification of Proteins (2)" VI Cross-linking Reaction, P81-113, Motonori Ohno (Society Publishing Center) Known cross-linking agents described in, for example, can be used. Among them, aldehyde compounds, epoxy compounds, isocyanate compounds and the like are highly reactive and can be preferably used. A wide variety of conventionally known aldehyde compounds can be used,
Examples thereof include formaldehyde and dialdehydes such as glyoxal, malonaldehyde and glutaraldehyde. As the epoxy compound, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, glycerin, sorbitol, polyglycerol, pentaerythritol, tris (2-hydroxyethyl), isocyanurate, trimethylolpropane, neopentyl glycol, phenol ethylene oxide, And mono- and polyglycidyl ethers of lauryl alcohol ethylene oxide, and epoxy group-containing coupling agents. These epoxy compounds are used by dissolving them in water, but when the solubility is low, it is preferable to dissolve them in a small amount of an organic solvent such as dioxane or a mixed solvent of isopropyl alcohol and water. Examples of the isocyanate compound include compounds having two or more isocyanate groups in one molecule such as toluene diisocyanate, diphenylmethane diisocyanate, hexanemethylene diisocyanate, isophorone diisocyanate, and naphthalene diisocyanate. It is preferable that these isocyanate compounds are dissolved in a known organic solvent capable of cross-linking with a protein, for example, chloroform, hexane, toluene or the like. ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] August 25, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Figure 3

[Correction method] Change

[Correction content]

FIG. 3 is a scanning electron microscope (SEM) photograph showing criteria for fibril generation.

Claims (8)

[Claims] 1. A dyed fiber characterized in that a coating layer made of an enzyme protein crosslinked with a crosslinking agent is formed on the surface of a single fiber, and a dye is dyed. 2. The dyed fiber according to claim 1, wherein the enzyme protein has a molecular weight of 10,000 or more. 3. The dyed fiber according to claim 1, wherein the coating amount of the enzyme protein is 3 to 15 mg / m ² per fiber surface area. 4. The method for producing a fiber according to claim 1, wherein the fiber having a coating layer made of an enzyme protein cross-linked with a cross-linking agent on the surface of the single fiber is dyed with a dye. 5. The means for forming the coating layer is to immerse the fiber in a solution containing the enzyme protein to adsorb the enzyme protein on the surface of the monofilament of the fiber, and then crosslink the enzyme protein with a crosslinking agent. The manufacturing method according to claim 4. 6. The method according to claim 5, wherein the solution containing the enzyme protein is acidic or neutral. 7. The method according to claim 4, wherein the enzyme protein has a molecular weight of 10,000 or more. 8. The method according to any one of claims 4 to 7, wherein the enzyme protein coating layer has a fiber surface area of 3 to 15 mg / m ² .