JP2010047866A - Silver-dyeing method for animal fiber, method of silver-dyeing control using aqueous solution of 2-mercaptoethanesulfonic acid salt, and animal fiber applied with these methods - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a simple method for dyeing animal fiber, free from any problem involving environmental pollution, and intended for obtaining well-designed textile products. <P>SOLUTION: The method for dyeing animal fiber includes (1) a step of depositing silver onto animal fiber such as wool or silk and (2) a step of steaming the resultant animal fiber. Alternatively, the method includes, in addition to the steps (1) and (2), a step of treating the animal fiber with an aqueous solution of 2-mercaptoethanesulfonic acid salt following the step (1). The animal fiber obtained by the method is also provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for dyeing silver in animal fibers, a method for controlling silver staining using a 2-mercaptoethanesulfonate aqueous solution, and animal fibers to which these methods are applied.

In order to color animal fibers such as silk and wool, a dyeing method using a dye has been conventionally employed. Silk and wool, which are animal fibers, are dyed using an acid dye or the like, and are usually colored and commercialized by dyeing or printing using a dye.
In such a dyeing method using an organic compound, a pH adjusting agent or leveling agent is added together with the dye, and the fiber is heated and reacted. For this reason, since the composition of the solution largely changes with respect to the waste water after dyeing, it cannot be reused normally. In addition, dyeing wastewater may become an environmental pollution problem.

In recent years, with the growing interest in environmental sanitation, many textile products such as clothing and towels that have been antibacterial treated have been distributed. As one of the antibacterial treatments, a method of antibacterial treatment using silver has been conventionally used.
On the other hand, it is known that silver is colored under certain conditions, such as being used as a photosensitizer. Several silver dyeing methods for fibers have also existed in the past, specifically, a method of coloring silk using silver nitrate and a reducing agent (Patent Document 1), and after treating a solid surface such as fibers with an aqueous noble metal salt solution, A method of performing heat treatment is known (Patent Document 2).

Japanese Patent Publication No. 5-88672 Japanese Unexamined Patent Publication No. 2-154063

  In the method for coloring the silk described in Patent Document 1 using silver nitrate and a reducing agent as described above, it is necessary to adjust and use many chemical solutions in the work process, so that the work is complicated or satisfied. I couldn't get a good color. Patent Document 2 discloses a method of dyeing filter paper or cotton using silver nitrate, but there is no specific description of a method using animal fibers.

  Furthermore, textile products such as clothes using animal fibers are required to have high design properties, and it is necessary to provide products with various designs. A coloring method capable of forming a certain pattern by silver staining method is disclosed in Patent Document 2, but silver is attached to only a part of the product, and it is not sufficient as a textile product from the viewpoint of antibacterial properties. There wasn't.

As a result of intensive studies based on the above situation, the present inventors have found a method of dyeing animal fibers by a silver dyeing method and capable of imparting sufficient antibacterial properties to animal fibers.
Specifically, the present invention
(1) A process of attaching silver to animal fibers,
(2) heating the animal fiber with water vapor;
A method for dyeing animal fibers with silver.

Furthermore, the present inventors have found that the silver staining can be controlled with an aqueous 2-mercaptoethanesulfonate solution, and as a result, animal fibers dyed in various patterns can be obtained.
In particular,
(1) A process of attaching silver to animal fibers,
(2) a step of further treating the animal fiber with an aqueous 2-mercaptoethanesulfonate salt;
(3) a step of heating the animal fiber with water vapor;
A method for controlling silver staining of animal fibers.

In the dyeing method of the present invention, the used silver solution can be reused, and there is no problem of waste liquid treatment unlike the method of dyeing using an organic compound. Moreover, the fiber obtained by the dyeing | staining method of this invention exhibits the refined brown color, and can obtain the textile product of refined texture. Furthermore, the part which controlled the color development with the 2-mercaptoethanesulfonate aqueous solution also shows antibacterial properties. By combining these methods, dyeing can be controlled and a pattern can be applied to the fiber itself.
In addition, it is also possible to obtain a fiber product with high design having artificially various hues by changing the method of contacting water vapor with animal fibers. For example, when it is spread and steamed, it is uniform, and when it is twisted and steamed, multiple colors such as yellow and gray are displayed in addition to brown.

The present invention is characterized by dyeing animal fibers.
The animal fiber used in the present invention is a fiber obtained from animal hair and is a protein fiber containing keratin and the like. As shown in the following examples, chemical fibers such as nylon and polyester and cellulosic fibers such as cotton are not sufficiently dyed by the dyeing method according to the present invention. That is, the dyeing method according to the present invention is characterized by dyeing animal fibers in particular.
The animal fiber used in the present invention is not particularly limited, and specific examples include silk and wool, animal hair alpaca, Angola, cashmere, and mohair. Among these, wool and silk are preferable. Wool is easy to attach a lot of silver, and silk can express patterns of various hues by one heating operation with water vapor.

In the first step of the present invention, silver is deposited on the animal fibers. The method for attaching silver is not particularly limited as long as silver adheres to the fiber surface. Specifically, a method of immersing a fiber in an aqueous silver salt solution, a method of spraying an aqueous silver salt solution onto animal fibers, and the like can be mentioned. From the viewpoint that silver can easily and uniformly adhere to the fiber and the solution can be reused, it is preferable to immerse the animal fiber in the aqueous silver salt solution. The time for immersing the animal fiber in the silver salt aqueous solution is usually 5 minutes to 1 hour, but the fiber can be immersed and stored in a state of being immersed for 24 hours or more. The temperature of the silver salt aqueous solution at the time of immersion does not require heat energy at room temperature, and the mass of the silver salt aqueous solution required at the time of immersion is preferably about 20 to 200 times the dry weight of the animal fiber to be immersed. The bath ratio is not limited as long as animal fibers are completely immersed in the silver salt aqueous solution.
Specifically, the concentration of the aqueous silver salt solution is usually 0.5% by mass to 20% by mass, for example, when an aqueous silver nitrate solution is used.
Further, the pH of the silver solution is preferably in the neutral range. If an acidic solution is used, the dyeing may not be sufficient. If an alkaline solution is used, there may be a problem in safety in terms of work. Specifically, the pH of the silver solution is preferably 6 to 7, and more preferably 7.
In addition to silver nitrate, a silver solution such as silver acetate or silver chloride can also be used.

After the animal fibers are dehydrated as necessary, the animal fibers to which silver has adhered are heated with water vapor to cause color development.
As a specific heating method using water vapor, a decompression device such as a vacuum pump is used. A method is preferred in which the inside of the heating apparatus is depressurized to atmospheric pressure or lower, and saturated steam at 100 ° C. or lower generated by depressurizing saturated steam at 100 ° C. or higher with a control valve, that is, the heat of vacuum steam is transferred to the fiber. In this heating method, since the heat transfer method to the fibers is latent heat transfer, uniform and very quick heating can be performed.
In addition, as a simple method, a method using a steam generator, a combination of a steam generator and a heat treatment device such as a tenter, which is used in a conventional finishing method for textile products, may be used. Here, the method for generating water vapor is not limited to vacuum steam, and it is also possible to use a device capable of high temperature and pressure using a device capable of applying a high frequency and a pressure vessel. In addition, as a simple method, a method of spraying boiled warm water vapor onto animal fibers in a container made of stainless steel or the like is also possible.

The heating temperature is preferably as high as or lower than the heat-resistant temperature of animal fibers in terms of obtaining a highly colored fiber or a colored fiber having a strong color contrast. Specifically, the heating temperature is in the range of 50 to 120 ° C., and the heating time is 30 to 60 minutes.
In addition, by masking a part of the same animal fiber and changing the degree of contact with the heated water vapor, the degree of color development changes, and it is possible to dye various colors with the same fiber, making it more designable It is also possible to provide a product having a high color density, and it is possible to dye the same fiber with a light and shade depending on the intensity of heating by steam.

In the present invention, after silver is adhered to animal fibers, when 2-mercaptoethanesulfonic acid salt is applied thereto, the color development by silver is controlled even if the applied portion is heated with water vapor. It becomes milky white, and it is possible to obtain animal fibers dyed in brown and silvery colors with silver. As a result, a wide variety of design properties can be imparted to the fiber product using the animal fibers obtained as a result. And even if it is the part by which the color development by silver was suppressed, the antimicrobial property was shown, and the animal fiber processed with the dyeing | staining method of this invention shows a high antimicrobial property.
Examples of 2-mercaptoethanesulfonate include sodium 2-mercaptoethanesulfonate, potassium 2-mercaptoethanesulfonate, and magnesium 2-mercaptoethanesulfonate.
Among them, sodium 2-mercaptoethanesulfonate is known as a urinary agent and is a compound having a mercapto (sulfur) reactive group that easily binds to silver and a sulfonate group that binds to a fiber.
As 2-mercaptoethane sulfonate, sodium 2-mercaptoethane sulfonate is mainly used, and this aqueous solution is used when used. At this time, the concentration of the aqueous 2-mercaptoethane sodium sulfonate solution is usually 0.01 to 20 g / L.

A sodium 2-mercaptoethanesulfonate aqueous solution prepared at the above concentration is applied to animal fibers to which silver has been adhered and dehydrated. As a method of application, a part of animal fiber is immersed in an aqueous solution of sodium 2-mercaptoethanesulfonate, or is applied to a part of animal fiber by using a spray or a brush.
The animal fiber thus treated with the 2-mercaptoethanesulfonate aqueous solution is heated with water vapor in the same manner as described above.

Animal fibers obtained by dyeing according to the present invention include tie, cushion, muffler, stall, interior, ladies' clothing, nightwear, clothing lining, sleeve lining, umbrella fabric, Japanese clothing, and other textile materials. Etc. (FIG. 1).
In addition, when the whole animal fiber is treated with 2-mercaptoethanesulfonate to obtain a white fiber, it has antibacterial properties and can be used as a textile product for medical care. is there.

Example 1
Each 1 kg of skein 21/4 silk thread and 1 kg of 21 silk thread / 21 silk were each immersed in 30 L of 3 wt% silver nitrate solution for 12 hours at room temperature. After pulling it up, washing and dewatering, steam heating at 100 ° C for 40 minutes with a steam heating vacuum dryer (manufactured by Yasushima Can Co., Ltd., vacuum setting machine), washing with water and drying to make silver gray A variety of hues of silk with a tea-based color and a partial gold color were obtained. In the same aqueous silver nitrate solution after use, 1 kg of untreated skein of 4 skein-like silk yarns under 21 conditions were dipped and dried under the same conditions to obtain a similarly colored silk yarn. Further, after the treatment with the aqueous silver nitrate solution, the dehydrated yarn was heated with water vapor without washing with water, and a dark silk yarn was obtained. Furthermore, this silver nitrate aqueous solution was diluted and the same operation was performed to obtain a light-colored silk thread. When heated with steam, when the skein was spread, it colored in a uniform tea system, and when the skein was twisted, it partially colored with a metallic luster other than that of the brown system, and was colored unevenly. These silk yarns are classified into four types, including dark, intermediate and light colors, as well as uncolored white, and the warp yarns are warped into random multi-stripe shapes with 4 colors with a total of 2880 warps. Weaving using 21/2 silk thread heated and colored with steam, one thread itself is patchyly colored and has a variety of hues, and stripes lined with yarn are the key A high-quality stall with an unprecedented design that was arranged in multiple colors with four color depths was obtained (Fig. 2).

(Example 2)
21/3 silk threads were immersed in 30 L of 15% aqueous silver nitrate solution at room temperature for 12 hours. This was pulled up and dehydrated, then immersed in an aqueous solution of sodium 2-mercaptoethanesulfonate having a concentration of 2 g / L for 10 minutes, and then a steam-heated vacuum dryer (Yasushima Can Co., Ltd. And was heated with water vapor at 100 ° C. for 40 minutes. These silk threads had a metallic luster color in addition to the colored and milky parts of the tea line (FIG. 3).
In addition, in FIG. 3, the silk thread (Example 1, Example 2) colored in the patchy tone obtained by this invention is shown. Spread the skein-like animal fiber on the left side and heat it with water vapor, and the animal fiber colored in a uniform tea system. -Animal fibers that are suppressed from coloring by silver with sodium mercaptoethanesulfonate.

(Test Example 1)
Polywoven fabric in which 8 types of fibers are woven including animal fibers such as silk and wool, synthetic fibers such as polyester, nylon, acrylic and semi-synthetic fibers acetate, rayon as regenerated fibers, and cotton as plant fibers. The silver nitrate concentration was changed to 0.5, 1.5, and 7.5% by mass at pH 7, and heated to 100 ° C. in the solution, and the coloring degree of the fiber was examined for each concentration. The results are shown in the table below. As can be seen from the following results, animal fibers such as wool or silk are significantly more colored than non-animal fibers such as cotton.

(Test Example 2)
Attached white cloth conforming to JIS L 0803 of silk, wool, polyester and nylon was simultaneously immersed in a silver nitrate solution having a concentration of 1.2% by mass for 12 hours. Four types of attached white cloth are heated at 100 ° C for 1 hour in the same steam-heated vacuum dryer, and the degree of coloring after each attached white cloth is dehydrated using a computer color matching system (AUCOLOR-10A Kurabo Industries Co., Ltd.). Calculated as the total K / S value (light absorption coefficient / scattering coefficient in the dyed product) Polyester is not colored enough due to water vapor heating, but the wool is dark brown, silk is brown, nylon From the total K / S, wool was 7.4 times higher than nylon and 58 times higher than polyester, and silk was 3 times higher than nylon and 24 times higher than polyester.

(Test Example 3)
The antibacterial effect of the product of the present invention is shown below.
When animal fibers colored by heating in an aqueous silver nitrate solution were examined for the antibacterial effect of colored wool with different silver adhesion amounts, the strength of the antibacterial effect proportional to the amount of silver adhesion to the wool was observed (FIG. 4). ). When the antibacterial effect was evaluated, it was based on JIS L1902 “Method for testing antibacterial properties of textile products”. At this time, the number of E. coli was about 4.1 × 10 ⁶ cfu / ml.
In addition, silk (skein-like yarn) having a coloration degree next to wool was immersed in an aqueous silver nitrate solution, and then heated with water vapor at a temperature of 100 ° C. for 1 hour to color the silk yarn. The silk was cut out into a cocoon shape having a length of about 6 cm from a randomly selected portion of the colored silk. This was then donated to the antibacterial test. At this time, the number of E. coli was about 2.3 × 10 ⁶ cfu / ml. As a result, it was confirmed that an antibacterial region (antibacterial region) called a halo of about 1 mm appeared in the colored portion (FIG. 5).

(Test Example 4)
Subsequently, the antibacterial effect of the portion whose color is controlled with sodium 2-mercaptoethanesulfonate is shown. Part of 80g of silk thread immersed in 15% silver nitrate aqueous solution (21 in 3) is soaked in 2g / L sodium mercaptoethane sulfonate aqueous solution and heated with water vapor (100 ° C x 50 minutes). The result was a patchy skein-like thread with a mixture of uncolored and colored parts. When the value indicating the color density of the uncolored portion and the colored portion of the patchy yarn was calculated using a computer color matching system (AUCOLOR-10A Kurabo Industries Co., Ltd.), the uncolored portion was 3 and the colored portion was 100. Yes, the color density value was controlled to about 1/33. The animal fiber was cut into a cage shape of about 6 cm in length from 7 randomly selected animal fibers that had been color-controlled, and provided to the antibacterial test in the same manner as described above. The antibacterial test method is the same as Test Example 3. As a result, it was confirmed that an antibacterial region (antibacterial region) called a halo of about 1 mm appeared in the uncolored portion where the coloring was controlled (FIG. 6). The same antibacterial effect was confirmed for any of the seven animal fiber test pieces in the uncolored part.

Next, the amount of silver attached to the portion where the color development was controlled was examined. For the silk yarn heated with water vapor, animal fibers were cut out from 6 randomly selected locations into a cage shape having a length of about 6 cm, and the mass of the animal fibers was measured. Next, about 20 mg of each animal fiber was wet-ashed with concentrated nitric acid, and an aqueous solution diluted with distilled water was diluted with an inductively coupled plasma mass spectrometer (ICP-MS, manufactured by Agilent Technologies) and The silver concentration was measured using an inductively coupled plasma emission spectrometer (ICP-AES, HORIBA Co., Ltd.) to obtain a silver adhesion amount value per 1 g of fiber. In the measurement by ICP-MS, mass numbers 107 and 109 were used, and the detection wavelength by ICP-AES was quantified using 328 nm. The ICP measurement was an average of three times. The measurement locations were three uncolored sites by treatment with sodium 2-mercaptoethanesulfonate and three color sites of normal treatment (FIGS. 7 and 8).
The measurement of the adhesion amount of silver in Test Examples 3 and 4 was performed by the same test method.

It is the figure which showed the example of the textiles using the animal fiber of this invention. It is the figure which showed the textile product of Example 1. FIG. The silk thread (Example 1 and Example 2) colored to the tone obtained by this invention is shown. It is a figure which shows the adhesion amount of the silver of the animal fiber colored with silver. It is a figure which shows the antibacterial effect of the animal fiber colored with silver by this invention. It is a figure which shows the antibacterial effect of the animal fiber which suppressed coloring by silver with 2-mercaptoethanesulfonic acid sodium by this invention. Fig. 2 shows the amount of silver deposited on the colored part of animal fibers dyed according to the present invention and the uncolored part of which the coloring is controlled by sodium 2-mercaptoethanesulfonate. According to the present invention, an animal fiber having a colored portion and an uncolored portion in which coloring is controlled is shown. The left side is an uncolored portion in which coloring is suppressed, and the right side is a colored portion. The amount of silver in the uncolored portion and the colored portion corresponds to the result shown in FIG.

Claims (7)

(1) A process of attaching silver to animal fibers,
(2) heating the animal fiber with water vapor;
A method for silver staining of animal fibers, comprising: (1) A process of attaching silver to animal fibers,
(2) a step of further treating the animal fiber with an aqueous 2-mercaptoethanesulfonate salt;
(3) a step of heating the animal fiber with water vapor;
A method for controlling silver staining of animal fibers, comprising:   The method according to claim 1 or 2, wherein the silver of (1) is derived from an aqueous silver nitrate solution.   The method according to any one of claims 1 to 3, wherein animal fibers are immersed in an aqueous silver nitrate solution to deposit silver.   The method according to any one of claims 1 to 4, wherein the animal fiber is selected from any of silk, wool, alpaca, Angola, cashmere or mohair.   Animal fiber to which the method according to any one of claims 1 to 5 is applied.   A textile product using the animal fiber according to claim 6.

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