JPH08127976A - Fiber dyeing method - Google Patents

Abstract

PURPOSE: To provide a dyeing method at a normal temperature capable of readily controlling a shade of color by using a fiber subjected to specific treatment. CONSTITUTION: A fiber such as a synthetic fiber, regenerated fiber or natural fiber, for example, is immersed in a keratin solution extracted from wool and keratin is adsorbed on the fiber. Disulfide bond of keratin is reduced by using dithiothreitol. On the other hand, a mixed solution of phosphoric acid containing peroxidase is reacted with N-succinimidyl-2-(2-pyridyldithio) propionate (SPDP) to give an enzyme solution containing an end disulfide bond. Then the reduced fiber is immersed in the solution to give a peroxidase-immobilized fiber. Then, the peroxidase-immobilized fiber is immersed in an aqueous solution of a reduced form of dye (e.g. vat dye) to be insolubilized by oxidation and hydrogen peroxide at a normal temperature and dyed.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a dyeing method, and more particularly to a fiber dyeing method.

[0002]

2. Description of the Related Art The vat dyeing method is known as one of fiber dyeing methods. In the vat dyeing method, the fiber is immersed in an aqueous solution of a reductant of a dye that becomes insoluble by oxidation, and the fiber is exhausted with the reductant. Then, the fibers that have exhausted the reductant are immersed in an oxidizing agent in a separate bath for oxidation treatment. By the oxidation treatment, the reductant is oxidized and insolubilized and fixed to the fiber. This dyes the fibers.

[0003]

In the conventional vat dyeing method described above, the reductant of the dye exhausted to the fiber remains water-soluble before the oxidation treatment and is not fixed to the fiber. Therefore, the reductant of the dye easily falls off from the fiber before the oxidation treatment. In particular, the hydrophobic fiber is difficult to vat dye because the dye reductant does not easily penetrate into the interior, and thus the dye reductant is likely to fall off. In order to prevent this, it is necessary to perform high-temperature treatment when the fiber is immersed in the dye solution so that the reductant of the dye is completely exhausted by the fiber.

In the conventional dyeing method, since the shade of the color is determined by the amount of the dye reductant exhausted to the fiber, the concentration of the dye solution is adjusted according to the intended shade of the color. There is a need. An object of the present invention relates to a fiber dyeing method, which can be processed at room temperature and in which the shade of color can be easily adjusted.

[0005]

The fiber dyeing method of the present invention includes the following steps. ◎ A step of preparing fibers on which peroxidase is immobilized. ◎ A step of immersing the fiber in which the peroxidase is immobilized in an aqueous solution of a hydrogen peroxide and a reductant of a dye which becomes insoluble by oxidation.

In such a fiber dyeing method, peroxidase is immobilized on the fiber by, for example, a disulfide bond. ******** The fiber dyeing method of the present invention will be described step by step. First, a fiber on which peroxidase is immobilized is prepared.

The type of fibers to which the present invention can be applied is not particularly limited, and synthetic fibers such as polyester fibers and polyamide fibers, recycled fibers such as rayon, and natural fibers such as cotton, wool and silk can be exemplified. The fibers may be short fibers or long fibers, and may be monofilaments or multifilaments. Furthermore, the state of the fibers may be thread-like or cloth-like.

Peroxidase must be immobilized on the above fibers. Here, peroxidase is a general term for enzymes that can reduce hydrogen peroxide in the presence of an electron-donating compound and oxidize the electron-donating compound. As a method for immobilizing peroxidase on the above-mentioned fibers, known methods such as a physical adsorption method, a chemical bonding method and an entrapping method can be applied. When immobilized by physical adsorption method, thoroughly wash the fiber treated with peroxidase,
It is necessary to use the fiber in which the peroxidase is not completely removed in the dyeing step described later. This is because if the peroxidase is dropped into the dye liquor described below, insolubilization of the reductant of the dye contained in the dye liquor proceeds.

Examples of the chemical bonding method include an ionic bonding method and a covalent bonding method. Here, as the covalent bond method,
Method of forming Schiff base by aldehyde group of fiber and amino group of peroxidase, converting carboxylic acid of fiber to acid chloride and reacting with sodium azide, and reacting with amino group of peroxidase to form amide bond Azide coupling method, bromocyan reaction with hydroxyl group of fiber and binding amino group of peroxidase to it, bromocyan activation method, peroxidase and carbodiimide are simultaneously reacted with amino group or carboxylic acid group of fiber to form amide bond Various methods such as the carbodiimide activation method can be applied.

As a comprehensive method, a method of coating fibers with a binder resin mixed with an enzyme is possible. However, according to such a comprehensive method, it is necessary to devise a microporous structure that allows the reduced form of the dye and hydrogen peroxide to pass through. Further, since the contact efficiency between the reductant of the dye and hydrogen peroxide and peroxidase is lowered, a long-term treatment is required in the dyeing treatment step described later.

Among the above-mentioned physical adsorption method, chemical bonding method and encapsulation method, the chemical bonding method is preferable. According to the chemical bonding method, the contact efficiency between the dye solution and the peroxidase can be increased, and a strong bond between the fiber and the dye can be realized. In addition, unnecessary peroxidase can be easily removed after staining. In the present invention, as a method for immobilizing peroxidase and fibers,
A new immobilization method different from the above-mentioned chemical bonding method may be adopted. This chemical bonding method is a method of immobilizing peroxidase and fibers by a disulfide bond.

In this chemical bonding method, first, the fibers are coated with a polymer layer. The polymer used here is a polymer capable of forming a disulfide bond with peroxidase. Examples of such a polymer include pomaly having a thiol group. Specifically, natural polymers mainly composed of proteins such as keratin, synthetic polymers such as polyester resins or polyurethane resins copolymerized with ethylenedithiol, radical-polymerizable monomers or polycondensable monomers having disulfide bonds are used. Examples thereof include those obtained by reducing the disulfide bond portion of the graft-copolymerized synthetic polymer to convert it into a thiol group.

The method of coating the fiber with such a polymer is not particularly limited. For example, dipping or dispersing the fiber in a solution or dispersion of a polymer having a thiol group,
A method of physically adsorbing a polymer on the fiber surface can be used. When the fibers are in the form of cloth, a general covering method such as putting or coating can be adopted. If the fiber is coated with a polymer that can form thiol groups upon reduction, such polymer is coated on the fiber by the methods described above. Then, the coated polymer is reduced to convert the disulfide bond contained in the polymer into a thiol group. As the reducing agent for reducing the polymer, a general reducing agent can be used, but it is preferable to select it in consideration of heat resistance, acid resistance and alkali resistance of the polymer. Generally, it is preferable to use a borate buffer solution of dithiothreitol (DTT), which can be reduced under a condition of being relatively neutral at room temperature.

Next, peroxidase is disulfide-bonded to the fiber coated with the polymer having a thiol group as described above. The disulfide bond between the polymer-coated fiber and peroxidase is achieved by an S—S exchange reaction between the non-crosslinked disulfide bond contained in the peroxidase and the thiol group contained in the polymer layer of the polymer-coated fiber.

By the way, the non-crosslinking disulfide bond contained in peroxidase means that the polypeptide chain does not form a closed ring structure due to the disulfide bond.
That is, it means a disulfide bond formed at the end of a polypeptide chain, a disulfide bond possessed by cystine in an amino acid sequence, or the like. In general, enzyme proteins are cross-linked by disulfide bonds between cysteine residues at distant positions in the amino acid sequence in order to fix the higher-order structure. It is possible to utilize the disulfide bond maintaining the higher order structure in the S-S exchange reaction as described above, but in most cases, the disulfide bond is present inside the enzyme molecule. It is difficult to carry out an SS exchange reaction with the thiol groups of the polymer layer coated on the fiber. Even if such an S-S exchange reaction could be realized, the higher-order structure of the enzyme protein would change,
Often the enzyme activity is lost or diminished. Therefore, the non-bridging disulfide bond that contributes to the S—S exchange reaction with the thiol group of the polymer layer is preferably one that is in a position where it is less likely to cause a decrease in enzyme activity or a structural change in the higher-order structure, for example, a terminal disulfide bond.

However, due to the nature of the disulfide bond, cystine is extremely rarely located at the end of the amino acid sequence, and the amino acid sequence usually contains cystine in addition to the end. Therefore, for a peroxidase having no terminal disulfide bond, it is necessary to introduce a disulfide bond at the terminal. The terminal disulfide bond is
It is formed by reacting a compound having a functional group capable of binding to an amino group or a carboxyl group at the end of an amino acid sequence and a disulfide bond with peroxidase. The compound used here is N-succinimidyl-3- (2) capable of reacting with an enzyme at room temperature and a pH around neutral.
-Pyridyldithio) propionate (SPDP) is preferred. SPDP reacts with the terminal amino group of peroxidase to form an amide bond, introducing a non-bridged disulfide bond into peroxidase.

The S--S exchange reaction between the non-crosslinking disulfide bond on the peroxidase side and the thiol group of the polymer layer coated on the fiber is carried out by placing the polymer-coated fiber in the peroxidase solution containing the non-crosslinking disulfide bond. It is achieved by reacting at room temperature. At this time, S
The -S exchange reaction proceeds at room temperature, and a new disulfide bond is formed between the sulfur atom of the thiol group and the sulfur atom that achieves the disulfide bond, which is bonded to the enzyme side. This allows the peroxidase to bind to the fiber.

Next, the dyeing process of the above fiber will be described. In the dyeing step, the above fibers are immersed in an aqueous solution of a hydrogen peroxide and a reduced product of a dye which is insolubilized by oxidation. Here, a general vat dye is used as a reductant of a dye which is insolubilized by oxidation. Further, a color change indicator such as 4-chloro-1-naphthol which is used when measuring the activity of peroxidase can also be used. It is not necessary to adjust the concentration of the aqueous solution of the hydrogen peroxide and the reductant of the dye which becomes insoluble by such oxidation. However,
It is necessary that the reduced form of the dye and hydrogen peroxide are always contained in a large excess with respect to the fiber.

The fibers after the immersion treatment are thoroughly washed with water and then dried. In the dyeing process described above, it is important to control the temperature and pH of the aqueous solution. The temperature needs to be adjusted within a temperature range in which the peroxidase immobilized on the fiber is not inactivated. Therefore, it is preferable to set the aqueous solution to a room temperature near room temperature. On the other hand, the pH also needs to be set in a region where the enzyme is not inactivated, but it is usually preferable to set the pH to around neutral.

In the above-mentioned dyeing step, the reduced form of the dye moves in the aqueous solution on a molecular order and permeates into the fiber gaps, fiber bundle gaps and fiber constituent molecule gaps. Then, the reduced form of the dye that has penetrated between the fibers is oxidized and insolubilized, and adheres to the fibers. This dyes the fibers. In such a dyeing mechanism, peroxidase decomposes hydrogen peroxide in the presence of a reduced form of the dye that acts as an electron-donating compound, and the decomposition product oxidizes the reduced form of the dye. For this reason,
Since the reductant of the dye is oxidized in the immediate vicinity of the fiber, the aqueous solution itself is not easily oxidized unless the peroxidase is eliminated from the fiber.

The dyeing density can be adjusted by the time of immersing the fiber in the aqueous solution. That is, when the immersion time is set to be long, the dyeing density is increased, and when the immersion time is shortened, the dyeing density is decreased. This is because the amount of the dye reductant insolubilized and fixed to the fiber is proportional to the immersion time. Therefore, the staining density can be set by adjusting the amount of peroxidase immobilized on the fiber.

After the dyeing step is completed, it is preferable to remove the peroxidase immobilized on the fiber. here,
When the peroxidase is immobilized on the fiber by a disulfide bond, the peroxidase can be easily removed.
Here, when the dyed fiber is treated with a reducing agent such as DTT at room temperature, the disulfide bond connecting the peroxidase and the fiber is reduced and the peroxidase is removed.

[0023]

Example 1 6 mm square polyester ultrafine fiber woven fabric (single yarn fineness 0.0
7d) keratin solution extracted from wool (100 μg /
The keratin was physically adsorbed on the surface of the polyester ultrafine fiber fabric by immersing in 1 ml of borate buffer solution, pH 8.0) for 1 hour.

This polyester ultrafine fiber woven fabric is
Dithiothreitol (DTT) borate buffer solution 4ml
After dipping it in the solution for 30 minutes to reduce the disulfide bond of keratin, it was washed 5 times with borate buffer. on the other hand,
Peroxidase manufactured by Toyobo Co., Ltd. (derived from horseradish, molecular weight 40000, enzyme activity 260 U / mg)
100 μl of solution and 0.1 M phosphate buffer (pH 7.
4) A mixed solution with 350 μl was prepared, and 50 μl of 10 mM N-succinimidyl-3- (2-pyridyldithio) propionate (SPDP) was added thereto, and the mixture was stirred at room temperature for 30 minutes.
Let react for minutes. As a result, an enzyme solution having a terminal disulfide bond in which 1.8 2-pyridyl disulfide groups were bonded per molecule of peroxidase was obtained.

The above polyester ultrafine fiber woven fabric in which the disulfide bond was reduced was dipped in this enzyme solution for 2 hours, and peroxidase was immobilized on the polyester ultrafine fiber woven fabric by the SS exchange reaction. The amount of peroxidase bound was 20 ng /
cm ² . Next, 20 ml of dye solution (1 m
1 of 0.2% 4-chloro-1-naphthol in ethanol, 19 ml of phosphate buffer (pH 6.86) and 0.02 ml of 30% hydrogen peroxide solution) at room temperature for 1 to 10 minutes. It was immersed. As a result, a fabric in which light blue gray to deep blue gray was continuously discolored was obtained. Example 2 5 mg of 6 mm square wool fiber fabric was immersed in 4 ml of 1 mM dithiothreitol (DTT) borate buffer solution for 30 minutes. , Reduced the disulfide bond of keratin, a component of wool. The fabric was then washed 5 times with borate buffer solution.

The thus treated wool fiber cloth was dipped in the same enzyme solution as in Example 1 for 2 hours, and peroxidase was immobilized on the wool fiber cloth by the SS exchange reaction. The amount of peroxidase bound was 330 ng / cm ² , as measured by enzyme activity. Next, the peroxidase-fixed wool fiber cloth was dipped in the same dye solution as in Example 1 at room temperature for 10 seconds to 3 minutes. As a result, a fiber fabric was obtained in which the color changed from light blue gray to dark blue gray continuously. Example 3 A 0.2% solution of 4-chloro-1-naphthol in ethanol was dissolved in 0.1% of a soluble vat dye (Mikethlen Blue B).
C: manufactured by Mitsui Toatsu Chemicals, Inc.) A dye solution similar to that of Example 1 was prepared except that the solution was changed to an aqueous solution. In this dye solution,
The same wool fiber fabric used in Example 2 with immobilized peroxidase was soaked at room temperature for 1 to 5 minutes. As a result, a fiber fabric was obtained in which the color changed from light blue to dark blue continuously. Comparative Example 1 A 6 mm square wool fiber cloth without peroxidase immobilized was immersed in a dye solution similar to that used in Example 1 at room temperature for 1 day, but the wool fiber cloth was not dyed at all. Comparative Example 2 The same wool fiber fabric used in Example 2 with immobilized peroxidase was immersed in a dye solution similar to that used in Example 1 for 1 day at room temperature except that it did not contain hydrogen peroxide. However, the wool fiber fabric was not dyed at all. Comparative Example 3 A 6 mm square wool fiber cloth on which peroxidase was not immobilized was immersed for 1 day at room temperature in the same dye solution as in Example 1 except that 4-chloro-1-naphthol was previously insolubilized with peroxidase. The wool fiber fabric was discolored when washed with water and was not dyed at all.

[0027]

EFFECTS OF THE INVENTION According to the fiber dyeing method of the present invention, since fibers on which peroxidase is immobilized are immersed in an aqueous solution of a reductant of a dye which insolubilizes by oxidation and hydrogen peroxide, dyeing can be carried out at room temperature. Further, the shade of dyeing can be easily adjusted.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Yutaka Takagaki 1-369 Nakamichi, Higashinari-ku, Osaka

Claims (2)

[Claims] 1. A method for dyeing a fiber, which comprises the steps of preparing a fiber on which a peroxidase is immobilized, and immersing the fiber in an aqueous solution of a reductant of a dye insolubilized by oxidation and hydrogen peroxide. 2. The fiber dyeing method according to claim 1, wherein the peroxidase is immobilized on the fiber by a disulfide bond.