JP2006176935A - Method for coloring textile product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for coloring a textile product having a randomly decolored and natural washed-out appearance and applicable even to a thin to a thick cloths without damaging fibers. <P>SOLUTION: The method for coloring the textile product is to decolor the textile product to the washed-out appearance of various hues as follows. The textile product is dyed with two or more kinds of reactive dyes having different decoloring properties for a permanganate and the resultant textile product kept in a wet state is then brought into contact with a decoloring agent composed of a granular mixture of the permanganate and an inorganic salt in a dynamic state to perform decoloring operation. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for coloring a textile product by utilizing a difference in decolorization property of a reactive dye with respect to a permanganate, that is, a method for coloring a textile product having a natural wash-like appearance that is randomly bleached.

In general, textile products are usually made by coloring with dyes or pigments. In this case, it is an important index for determining the commercial value to dye evenly and uniformly. On the other hand, there are printing or discharging as a dyeing method different from uniform dyeing, and these methods are all continuous patterns by a printing machine such as a screen printing machine or a roller printing machine, and have an artificial appearance. It is a coloring method represented by.
However, in recent years, from the viewpoint of diversification of consumer needs and fashionability, artificial dyeing, which is different from uniform dyeing, printing or discharging, etc., and stone washing as seen in denim clothing The method of scraping off the dye on the fiber surface with pumice, and the method of decolorizing the surface of the denim product dyed with selenium dye with ozone gas, then scraping the surface with pumice etc. to expose the uncolored part (Patent Document) 1), and textile products that have a wash-like appearance treated with a chlorinated decoloring agent such as hypochlorite in a uniform fade tones are widely used as new products with high sensitivity. Is accepted.

  Also, the color of denim clothing was mostly indigo blue, but recently, after exhaustive dyeing of the pigment, it has a variety of special dyeing effects with a wash-out tone that uses the property of the pigment being easily removed. New textile products have also been developed and are highly regarded as highly marketable textile products. However, the method of scraping the dye on the surface of the fiber with pumice stone, or the method of treating with a chlorine-based decoloring agent such as hypochlorite in a uniform fade tone, both of which damage the fiber. It is limited and applied to denim clothing that is relatively thick. Also, in the method using pigments, the stain of the dyeing machine during exhaust dyeing is large, it is necessary to use a resin for fixing the final pigment, the process becomes complicated, and for example, if a resin is used However, in the dark color, the fastness to washing or the fastness to friction was poor, and there was a drawback that it was limited to light colors and intermediate colors.

Cellulosic fabrics are dyed with vinyl sulfone reactive dyes, biotreated with enzymes, decolorized with a reducing agent, and then dyed with reactive dyes again to change iridescent tone, light tones, different colors, core white tone, etc. Although a method of coloring (see Patent Document 2) is disclosed, it has the disadvantage that the process is complicated and the number of processes is large.
Japanese Patent Laid-Open No. 5-186973 JP-A-10-280276

The object of the present invention is to apply to a variety of textile products from light to heavy without the need for complicated processes, without damaging the fiber, excellent in fastness from light to dark, and also to create various hues and fashionability It is an object to provide a method for coloring a unique and natural washed-out fiber product excellent in color.
As a result of intensive studies to solve the above-mentioned problems, the present inventors have a wide range of hues and reactive dyes that are widely used mainly for the dyeing of cellulose fibers. It has been discovered that there are a wide range of products that exhibit high color to those that exhibit difficulty in decoloring, and these dyes are combined in an appropriate combination, and then decolorized with permanganate. The present invention was completed by finding that an appearance appears.

  The present invention is characterized in that a textile product is dyed with two or more reactive dyes having different decolorizing properties with respect to permanganate and then decolorized with a decolorizing agent comprising a granular mixture of permanganate and inorganic salt. This is a coloring method for textile products. The decolorizer uses a granular mixture of permanganate and inorganic salt containing 0.01 to 1.0% by weight of permanganate and diluted with inorganic salt based on the dry weight of the textile product. In the decolorization method, it is preferable that the fiber product is in a wet state, and the decoloring agent and the wet fiber product are brought into contact with each other in a dynamic state, and the wet state has a squeeze rate of 30% to 150%.

  The present invention blends reactive dyes having different decolorizing properties with respect to permanganate, and wets textile products that have been uniformly dyed, printed, or spotted with permanganate and its inorganic salt as a diluent. By bringing the granular mixture into contact in a dynamic state, a part of the dye on the surface of the textile product is decolorized, and by controlling the decolored area from white to an arbitrary hue, a natural washed fiber product having various hues is obtained. . Further, since the decolorization reaction proceeds in a semi-dry state in this coloring method, the damaged fiber remains only in the very shallow part of the fiber product surface, and the influence on the product strength can be minimized.

  The textile product referred to in the present invention is a woven fabric or knit and a sewn product obtained by sewing them. The material is not particularly limited as long as the dye of the dyed textile product interacts with the decoloring agent. Plant fibers such as cotton and hemp, animal fibers such as wool and silk, viscose rayon, copper Regenerated cellulose fibers such as ammonia rayon and solvent-spun cellulose fiber can be used. In addition, composite materials obtained by blending these materials and synthetic fibers such as polyester fibers, polyamide fibers, acrylic fibers, and the like can be used.

  The decoloring agent used in the present invention is preferably an oxidative decoloring agent among a reducing decoloring agent and an oxidative decoloring agent. Reductive decolorizers are not preferred because they produce aromatic amines as a result of the reduction reaction, and the aromatic amines may be detrimental and may reduce fastness such as light resistance. Examples of oxidative decoloring agents include dichromate, permanganate, hypochlorite, etc., but dichromate contains toxic heavy metals, and hypochlorite has a large decrease in fiber strength. Therefore, it is not preferred, and permanganate can be suitably used. Therefore, as the dye used in the present invention, a desired dye may be selected from a dye species exhibiting easy decolorization to hard decoloration with respect to permanganate. Examples of these dyes include direct dyes, sulfur dyes, acid dyes, and reactive dyes. Reactive dyes having various hues and widely used mainly for dyeing cellulose fibers can be preferably used.

  For example, reactive dyes that are easily decolorizable to permanganate among reactive dyes include, for example, Sumifix Brillant Orange 3R (manufactured by Sumitomo Chemical Co., Ltd.), Sumifix Red B (Sumifix Red B, manufactured by Sumitomo Chemical Co., Ltd.), Sumifix Brilliant Red BB (Sumifix Brillant Red BB, manufactured by Sumitomo Chemical Co., Ltd.), Cibacron Red FN-2BL (Cibacron Red FN-2BL, Ciba Specialty Chemicals Co., Ltd.), Sumifix Brilliant Blue R (Sumifix Brillannt Blue R, Sumitomo Chemical Co., Ltd.), Sumifix Supra Blue BRF (Sumifix Supra Blue BRF, Sumitomo Chemical Co., Ltd.) , Cibacron Brillant Blue FN-G (Cibacron Brillant Blue FN-G, Ciba Specialty) Chemicals Co., Ltd.), Cibacron Blue FN-R (Cibacron Blue FN-R, Ciba Specialty Chemicals Co., Ltd.), ReaNova Blue CA (Dastar Japan Co., Ltd.), etc. Can be mentioned.

  Examples of reactive dyes that exhibit difficulty in decolorization include Sumifix Yellow GR (Sumifix Yellow GR, manufactured by Sumitomo Chemical Co., Ltd.), Sumifix Supra Yellow 3RF (Sumifix Supra Yellow 3RF, manufactured by Sumitomo Chemical Co., Ltd.) , Cibacron Yellow FN-2R (Cibacron Yellow FN-2R, manufactured by Ciba Specialty Chemicals Co., Ltd.), Reanova Yellow CA (ReaNova Yellow CA, manufactured by Dystar Japan Co., Ltd.), Sumifix Supra Red 3BF (Sumifix Supra Red 3BF, manufactured by Sumitomo Chemical Co., Ltd.), Cibacron Red FN-R (Cibacron Red FN-R, manufactured by Ciba Specialty Chemicals), ReaNova Red CA (manufactured by ReaNova Red CA, manufactured by Dystar Japan) Sumifix Supra Blue E-XF (manufactured by Sumitomo Chemical Co., Ltd.) , Mention may be made of the Reanova Neivui CA (ReaNova Navy CA, manufactured by DyStar Japan Co., Ltd.), and the like.

As the permanganate used in the present invention, an alkali metal salt or an alkaline earth metal salt can be preferably used. Specific examples include lithium permanganate, potassium permanganate, sodium permanganate, magnesium permanganate, calcium permanganate and the like, with potassium permanganate being common. These permanganates are usually obtained as crystal lumps, but in the present invention, they are preferably granulated and used from the viewpoint of the effect.
The granular inorganic salt plays an important role in bringing the permanganate into contact with the fiber product in an appropriate and uniform manner as a diluent for the permanganate, including alkali metal or alkaline earth metal hydrochlorides, sulfates and Nitrate can be used. Specific examples include lithium chloride, potassium chloride, sodium chloride, magnesium chloride, calcium chloride, lithium sulfate, potassium sulfate, sodium sulfate, magnesium sulfate, calcium sulfate, lithium nitrate, potassium nitrate, sodium nitrate, magnesium nitrate, and calcium nitrate. However, sodium sulfate is commonly used as a dyeing aid for reactive dyes.

  In the present invention, these permanganate particulates and granular inorganic salts are added to the fiber product for treatment. However, when the permanganate is brought into contact with the fiber product in a high purity state, the fiber product has a remarkable strength. It is not preferable because it causes a decrease, and it is preferably used as a diluted permanganate granular material diluted with an inorganic salt. Further, since the sufficient amount of the permanganate used with respect to the dry weight of the textile product is 0.01 to 1.0% by weight, a sufficient effect can be obtained. It is preferable to use the manganate granular material because there are few measurement errors and mixing with the granular inorganic salt is facilitated. As such a diluted permanganate granular material, GS-KP (trade name, Sun Chemical Co., Ltd.) in which potassium permanganate was diluted with sodium sulfate and the content of potassium permanganate was 10% by weight. Made). GS-KP can be suitably used as the permanganate granular material of the present invention. In order to dilute the permanganate, a granular inorganic salt can be further added to the granular mixture of the permanganate and the inorganic salt. Further, the dry weight of the fiber product in the present invention is the weight of the fiber product in a standard state (temperature 20 ° C., relative humidity 65%).

  Next, a specific processing method will be described. First, a fiber product is dyed. The dyed fiber product in the present invention is a fiber product dyed uniformly by dip dyeing, a printed fiber product, or a spotted fiber product. Dyeing may be performed in a conventional manner by appropriately selecting from the two types of dyes described above according to the required hue. Decolorization is then performed. Decolorization is performed in a dynamic state in order to obtain an appropriate degree of homogeneity, but a stop for several seconds to several minutes may be repeated. The apparatus is not particularly limited as long as a dynamic state can be obtained, but a tumbler, a washer, or the like can be preferably used.

The dyed fiber product is put into these rotating devices and decolored in a wet state. The wet fiber product referred to in the present invention is a fiber product having a drawing rate of 30% to 150%, and preferably a drawing rate of 50. % To 100% textiles. In the decolorization method, a granular inorganic salt is prepared in a weight of 1 to 5 times the dry fiber product in advance, and the amount of permanganate used is 0.01 to 1.0% by weight based on the dry weight of the fiber product As described above, 0.1% by weight to 10% by weight of the above-described GS-KP (manufactured by Sun Chemical Co., Ltd.) is added to the rotating device together with the granular inorganic salt and stirred well, and then the wet fiber product is added thereto. Then, the decolorization operation is performed at room temperature for 5 minutes to 60 minutes, preferably 10 minutes to 40 minutes.
Water-insoluble manganese dioxide, which is a reaction product of permanganate and dyes or organic substances such as fibers, adheres to the decolored textiles. Wash them with water to remove unreacted permanganate and inorganic salts. After removal, if it is removed by treatment with a known method, that is, a reducing agent or the like, a natural wash-out appearance appears and a desired fiber product can be obtained. After removing manganese dioxide by treatment with a reducing agent, etc., it moves to steps such as soaping, resin processing, finishing oil treatment, etc., as necessary, but these steps are not particularly limited and are general methods Can be done.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to this range. In addition, the measurement of the dough strength and friction fastness in this example was performed based on the following method.
・ Fabric strength: JIS L 1018 8.17A method (Mulen method)
・ Friction fastness: JIS L 0849

[Example 1]
After scouring and bleaching a cotton No. 40 twin yarn knitted fabric by a conventional method and treating with a sewing oil, a T-shirt was produced. Sumifix Brilliant Red BB 150% (Sumifix Brillant Red BB, manufactured by Sumitomo Chemical Co., Ltd.), which is easily decolorized with respect to permanganate, is 4.0% by weight with respect to the T-shirt. Cibacron Yellow FN-2R (manufactured by Cibacron Yellow FN-2R, manufactured by Ciba Specialty Chemicals Co., Ltd.), which is difficult to decolorize against manganate, It dye | stained by the conventional method according to the dyeing | staining method of the reactive dye. Next, the obtained T-shirt was dehydrated so that the squeezing ratio was 80%, and then granular sodium sulfate 2.5 times the dry weight of the T-shirt and 2 times the dry weight of the T-shirt in advance. Put in a Shinzen-type washing machine (model: mini testing machine) manufactured by Jinmae Ironworks Co., Ltd. with 5% by weight of GS-KP (manufactured by Sun Chemical Co., Ltd.) and stir well. A dehydrated T-shirt was put in and decolorized for 30 minutes at room temperature. After taking out the decolorized T-shirt and washing it with water, it was treated at a bath ratio of 20, 60 ° C. for 15 minutes in a treatment bath containing 2.5 g / liter of a reducing agent (GS-N, manufactured by Sun Chemical Co., Ltd.). The manganese dioxide adhering to the T-shirt was washed with water to remove water.

Subsequently, the sample was soaped in a treatment bath containing 1 g / liter of a soaping agent (Tripon P-60, manufactured by Yushi Kogyo Co., Ltd.) at a bath ratio of 1:20 at 80 ° C. for 15 minutes and washed with water. Furthermore, after treating with an oil agent at a bath ratio of 1:20 and 50 ° C. for 10 minutes in a treatment bath containing 4 g / L of a finishing oil agent (FS-W-100), a portion of the surface dye is decolored by dehydration and drying. Got a T-shirt. The obtained T-shirt was decolorized in yellow because only the red dye that was easily decolored with respect to permanganate was decolored. Was also a natural wash-out tone. As a result of measurement of a fabric intensities before and after decolorization, before decolorization after decolorized whereas a 610kPa (kgf / cm ²⁾ was 530kPa (kgf / cm ^2). Although a slight decrease in fabric strength was observed, this level of decrease is not a problem in practice.
Table 1 shows the measurement results of the fastness to rubbing of the obtained washed-out T-shirt.
As can be seen from Table 1, even in wet friction, the T-shirt of the present invention exhibits excellent fastness despite being dark.

[Example 2]
As a sample, a plain fabric using a 50th single yarn of cotton fiber produced by the method of cationization modification to the spots disclosed by the applicant in Japanese Patent Publication No. 2004-162197 (War density: 132 yarns / 吋, Weft density: 80 yarns) Cibacron Blue FN-R (Cibacron Blue FN-R, manufactured by Ciba Specialty Chemicals Co., Ltd.), which is easy to decolorize to permanganate, is used for the sample. 0.5% by weight of Cibacron Red FN-R (Cibacron Red FN-R, manufactured by Ciba Specialty Chemicals Co., Ltd.) showing 1.5% by weight and hard decoloration to permanganate In the same manner as in Example 1, except that the above dye is blended and dyed by a conventional method, it is treated with granular sodium sulfate and GS-KP (manufactured by Sun Chemical Co., Ltd.) containing potassium permanganate. I got a thing. Since the red dye used is a dye that is difficult to decolorize with respect to permanganate, the color to be removed is reddish, and the contrast between the reddish blue of the uncolored area and the mottled dye is now It was a plain fabric with an unwashed appearance and excellent fashion.

  According to the method of the present invention, it can be applied to various textile products from thin to heavy without damaging the fibers, and it has excellent fastness from light to dark, and also creates various hues and fashion It is possible to obtain a unique and natural washed fiber product with excellent properties.

Claims (4)

  A textile product characterized by dyeing a textile product with two or more reactive dyes having different decolorizing properties for permanganate and then decolorizing with a decolorizing agent comprising a granular mixture of permanganate and an inorganic salt. Coloring method.   It is characterized by using a granular mixture of a permanganate and an inorganic salt diluted with an inorganic salt and containing 0.01 to 1.0% by weight of a permanganate based on the dry weight of the textile product. The method for coloring a textile product according to claim 1.   The textile product coloring method according to claim 1 or 2, wherein the textile product is in a wet state, and the decoloring agent and the wet textile product are brought into contact in a dynamic state.   The method for coloring a textile product according to claim 3, wherein the wet state of the textile product is a drawing rate of 30% to 150%.