KR101069620B1 - Spun yarn for melange fabrics and dying method of textile products - Google Patents

Abstract

The present invention is to provide a spun yarn for melange fabric, a spun yarn for melange fabric, and a method for dyeing other textile products obtained by melange fabric satisfying soft texture and excellent hygroscopicity and moisture resistance by the same material as cellulose fiber. Specific mixtures of modified regenerated cellulose fibers containing a pretreatment agent, cationized denatured cotton fibers and / or cationized denatured regenerated cellulose fibers, and refined and bleached cotton fibers or refined and bleached cotton fibers and regenerated cellulose fibers By blending and blending in proportions, the melange fabric can be represented by a melange exhibiting a frosty appearance with a wide range of colors and colors. Get

Melange, Spinning Yarn, Multicolored Dyeing, Cellulose, Naphthol Dye

Description

Dyeing method for yarn and textile products for melange fabrics {SPUN YARN FOR MELANGE FABRICS AND DYING METHOD OF TEXTILE PRODUCTS}

The present invention relates to a dyeable fiber comprising a modified regenerated cellulose fiber containing a pretreatment agent of a naphthol dye and a cationized modified cotton fiber and / or a cationized modified regenerated cellulose-based fiber, and a scouring / bleached cotton fiber or a scouring / bleaching agent. After mixing one cotton fiber and an undyed fiber composed of regenerated cellulose fibers, a yarn was produced, and the knitted fabric using the yarn was dyed with a naphthol dye developer and a specific anion dye, thereby producing multicolored melange. The present invention relates to a dyeing method of textile products including a spinning yarn for melange and a spinning yarn for melange that can express the effects of melange (also called uphill) in a wide range of colors and colors.

In order to create a high value-added textile product, the examination of the production system which implements a multicolored pattern on a textile product has been performed conventionally.

Even now, the production method of expressing multicolored patterns using the same material is a method of so-called "dymitis" in which yarns are dyed in a desired color and then interwoven by combining a plurality of dyed yarns. It is becoming mainstream. This method is mainly applied to cellulose-based textile products, but it takes a long time from design and color determination to the completion of textile products, and increases the risk of long-term inventory of raw materials, which are dyed spun yarn. It has long been called for improvement. In order to solve this problem, a so-called "post dyeing" method is proposed in which different kinds of textile products interwoven with a combination of different materials are added and dyed in a sequential or the same bath using different dyeability of materials. It is becoming.

Specifically, it is composed of a combination of other materials such as cotton fiber and polyester fiber, regenerated cellulose fiber and acrylic fiber, cotton fiber and polyester fiber and nylon fiber. However, as a cellulose-based fiber product, the natural and flexible feel, which is a characteristic of cellulose materials, has a drawback that characteristics of the material cannot be realized by combination with heterogeneous materials such as synthetic fibers. In view of this, it is possible to express the melange and the grandrelle tone effect by different dyeing treatment of knitted products using cationized and uncationized cotton or their yarns with a combination of cellulose fibers alone. It is disclosed (for example, refer nonpatent literature 1). However, these cellulose-based materials are characterized by emphasizing the difference in dyeability to anionic dyes, and it is impossible to express two or more colors using a single material. In order to be able to express more than two colors in a single material, the dyeing apparatus needs to be changed again, and a combination of new cellulose-based fibers having excellent color fastness with dyeing is required. Therefore, the present applicant has conceived of naphthol dyeable denatured regenerated cellulose fibers having the same cellulose-based material and being denatured and having different dyeability (see Patent Document 1).

On the other hand, the present applicant is a method of dyeing a fiber structure comprising a modified cellulose regenerated fiber having a cationic dye dyeing ability in a single bath with a melangetone or the like with a dye solution consisting of a cationic dye alone or a dye other than a cationic dye and a cationic dye Was invented (see Patent Document 2). However, this dyeing method required complex countermeasures such as treatment with an aqueous tannic acid solution after dyeing, an aqueous tinite solution, followed by crosslinking treatment with a fibrin-reactive resin in order to improve dyeing fastness.

[Non-Patent Document 1] Viewline and Its Development (Shinichi Fukuoka Textile Processing Handbook, 24, VOL.38, 1986, pages 32-37)

Patent Document 1-Japanese Patent Laid-Open Publication No. 2003-3322 (2nd page, 2nd stage)

Patent Document 2-Japanese Patent Laid-Open No. 10-121384

The present invention relates to a modified regenerated cellulose fiber containing a naphthol dye pretreatment agent, a cationized modified cotton fiber and / or a cationized modified regenerated cellulose fiber, a refined bleached cotton fiber or a refined bleached cotton fiber and a regenerated cotton fiber By blending cellulose fibers in a specific mixing ratio, it is easy to carry out, and the appearance having a wide range of colors and colors can be represented by a melange showing a frosty state, and also satisfies the soft texture, excellent hygroscopicity and moisture resistance. It is an object to provide a spun yarn for melange from which a fiber product is obtained.

Another object of the present invention is to use a combination of a dichroic material and the same material called cellulose-based fibers, thereby enabling the tricolor and more multi-color expression to the fiber products that have been difficult to date by dyeing, not by the dyeing. It is intended to contribute greatly to the development of the field of garment materials by providing a dyeing method.

In addition to cationized modified cellulose, it is necessary to develop a third new cellulose-based fiber having excellent dyeing fastness in addition to cation-modified cellulose in order to enable the same cellulose-based material and multi-color expression of three or more colors from a single color. In view of this, the Applicant can pay attention to the pretreatment of naphthol dyes, and dye any specific pretreatment by dissolving in thermal alkali in the presence of a dissolution aid and mixing and spinning in viscose immediately before spinning, thereby dyeing with the developer of naphthol dyes only. It was invented and filed to obtain modified modified cellulose fibers (Japanese Patent Laid-Open No. 2003-3322). In addition, the present invention has been completed by discovering that this modified regenerated cellulose fiber can be effectively used for achieving the object of the present invention as a third cellulose material.

In addition, the present inventors have diligently studied, and the appropriate mixing ratio of the naphthol salt-modified regenerated cellulose fibers constituting the dyed yarn for melange and the cationized modified cellulose-based fibers can express a wide range of colors and colors with melange. The present invention has been completed by focusing on satisfying soft texture and excellent hygroscopicity and moisture resistance.

That is, the first feature of the present invention is a dyeable fibrous group consisting of modified regenerated cellulose fibers containing a pretreatment agent of naphthol dyes, cationized modified cotton fibers and / or cationized modified regenerated cellulose fibers, and refined and bleached. A spun yarn for melange comprising a mixture of undyed fiber groups consisting of cotton fibers or refined / bleached cotton fibers and regenerated cellulose fibers.

The second aspect of the present invention is that the mixing ratio of the whole yarn of the dyeable fiber group is 10 to 50% by weight, the mixing ratio of the non-dyed fiber group is 90 to 50% by weight, and in the total fibers constituting the yarn. It is a spun yarn for melange whose mixing ratio of regenerated cellulose fibers is 10 to 30 wt% and cotton fibers is 90 to 70 wt%.

The third aspect of the present invention is that the mixing ratio of the whole yarn of the dyeable fiber group is 30 to 50% by weight and the mixing ratio of the cationized modified cotton fiber and / or the cationized modified regenerated cellulose fiber in the dyeable fiber group. It is a spun yarn for melange in the range of 20-40 weight%.

A fourth and fifth aspect of the present invention is a modified regenerated cellulose fiber containing a pretreatment agent of naphthol dyes, a cationized modified cotton fiber and / or a cationized modified regenerated cellulose fiber, a refined, bleached cotton fiber or refined Spinning yarn for melange, wherein the mixing ratio of the mixture of bleached cotton fibers and regenerated cellulose fibers is 1: 1: 8 or 2: 2: 6.

The dyeing method of the cellulose-based fiber product according to the present invention comprises a naphthol dye comprising a fiber product composed of three different fibers, a modified regenerated cellulose fiber containing a pretreatment agent of a naphthol dye, a cationized modified cellulose fiber and an ordinary cellulose fiber. It is a dyeing method of cellulose-based fiber products which are dyed with a color developer and then dyed with an anionic dye, and anionic dyes include acid dyes or reactive dyes having low affinity with cellulose fibers. In addition, another dyeing method is a cellulose-based fiber product which dyes a fiber product consisting of the three different fibers using a naphthol dye developer, and then dyes directly with a reactive dye having a high affinity with a dye or cellulose fiber. It is a dyeing method, and another invention is that a textile product consisting of three different fibers is dyed with a naphthol dye developer, followed by dyeing with an acid dye or a reactive dye having low affinity with cellulose fibers, followed by direct dye or cellulose fibers. It is a dyeing method of cellulose fiber products which are dyed with reactive dyes having high affinity.

(Embodiments)

The modified regenerated cellulose fiber containing the naphthol dye pretreatment agent is the modified regenerated cellulose fiber described in Japanese Patent Laid-Open No. 2003-3322, which is a pretreatment agent for naphthol dye, which is higher than moderate to cellulose fiber. A pretreatment having a degree of affinity is used at 0.5-3.0% by weight based on regenerated cellulose fibers, and dissolved in the pretreatment agent with a thermal alkali solution such as sodium hydroxide in the presence of a dissolution aid such as lot oil or ethanol. It is obtained by mixing and spinning the cellulose dissolving stock solution by the viscose method or the copper ammonia method immediately before. Moreover, the modified regeneration cellulose fiber containing the pretreatment agent of the naphthol dye obtained by other methods can also be used, For example, a solvent spinning regeneration cellulose fiber etc. are mentioned. In this case, when the pretreatment is dissolved or finely dispersed in a solvent which dissolves cellulose, solvent spinning regenerated cellulose fibers containing the pretreatment can be produced.

The cationized modified regenerated cellulose fiber according to the present invention is a quaternary ammonium group-containing compound having a chlorohydrin group after saponifying or hardening a regenerated cellulose fiber selected from viscose rayon, copper ammonia rayon, and solvent spinning regenerated cellulose fiber. After treatment with cation to denature the cation, it can be used to emulsion treatment. The cationic denatured cotton fiber is not particularly limited to the production area, and can be used by treating the common cotton using a quaternary ammonium group-containing compound having a chlorohydrin group or the like, followed by cationic modification and then emulsion treatment. . As a quaternary ammonium group containing compound which has a chlorohydrin group etc., for example, Nagase (Westex N-50 (brand name) manufactured by Chemical Industry Co., Ltd.) Cationone UK (brand name) manufactured by Ippsha Oil Holding Co., Ltd.) Etc. can be mentioned.

The refined and bleached cotton fibers referred to in the present invention are not particularly limited to those produced in the region, and those obtained by emulsifying ordinary cotton fibers with refined and bleached cotton fibers by a conventional method can be used. The regenerated cellulose fibers are regenerated cellulose fibers selected from viscose rayon, copper ammonia rayon, and solvent spun cellulose fibers, and are preferably used after pretreatment of saponification or hardening before dyeing.

Dyed yarn for melange of the present invention is a dyeable fiber comprising a modified regenerated cellulose fiber containing a pretreatment agent of naphthol dye, a cationized modified cotton fiber and / or a cationized modified regenerated cellulose fiber, and a refined and bleached cotton After mixing the fibers or undyed fibers composed of refined and bleached cotton fibers with regenerated cellulose fibers, the yarns are spun yarns. However, the method of mixing and spinning the fibers can be carried out using conventional methods.

The mixing ratio of regenerated cellulose fibers and cotton fibers in the spun yarn for melange of the present invention is configured so that the regenerated cellulose fibers are 10 to 30% and the cotton fibers are 90 to 70% in the whole yarn. In the case of the yarns in which recycled cellulose fibers and cotton fibers are mixed, this increases the mixing ratio of regenerated cellulose fibers, resulting in a decrease in tension and elasticity, softening the texture, but decreasing the strength. In consideration of the balance of strength and strength, the mixing ratio of regenerated cellulose fibers is limited to 10 to 30%, and the moisture content of cotton fiber that can be set at a standard state of 20 ° C and 65% relative humidity is 7%. Since the regenerated cellulose fibers are 12 to 14%, the spun yarn mixed with them increases the moisture content than that of the single cotton fibers, and the hygroscopicity and the moisture resistance are good. In consideration of these properties, a preferable range of the mixing ratio of each fiber was selected and specified.

The fiber part which can be dyed for the melange spun yarn of this invention was 10-50 weight% of the whole spun yarn. Melange's effect can be expressed in the range of 6 to 80% by the concentration or amount of color to be dyed, but by 10 to 50%, the effect of melange showing the appearance of a frosty state is clear. Can be determined. The group of dyeable fibers of the yarn for melange yarns of the present invention includes a modified regenerated cellulose fiber containing a pretreatment agent of naphthol dye, a cationized modified cotton fiber, or a cationized modified regenerated cellulose fiber, or a cationized modified cotton fiber It is a mixture of cationized and modified regenerated cellulose fibers, and can be dyed with an acidic dye or a reactive dye, which is a developer of a naphthol dye and a specific anionic dye, respectively.

In order to further utilize the melange effect of the spun yarn of the melange spun yarn of the present invention, the dyeing concentration in the expression of the same color melange and the expression of the dichroic melange is utilized by utilizing the excellent characteristics of the naphthol dye, the acid dye, or the reactive dye to be used. It is preferable to dye the dark part with a good color fastness of naphthol, and to obtain a wide range of colors and colors, increase the amount of cationized modified cotton fibers or cationized modified cellulose fibers to dye them with acid dyes or reactive dyes. It is desirable to. As an example, in order to compensate for the drawback of not being able to express the color of turquoise blue as a naphthol dye, it is first dyed blue with a naphthol dye, and then dyed with a color of turquoise blue that is brighter than an anionic dye. It is possible to express the effect of melange which is excellent in cow / shading.

Moreover, in the yarn for dyeing melange, the expression of the same color melange is mainly an acid dye or a reactive dye, which is a specific anion dye that can cover a wide range of colors and colors, and is a cationized modified group which is a group of fibers to be dyed. It is preferable to increase the amount of the cotton fiber or the cationized modified regenerated cellulose fiber or the mixture of the cationized modified cotton fiber and the cationized modified regenerated cellulose fiber, and the modified regenerated cellulose containing the pretreatment agent of the naphthol dye is preferred. When the mixing ratio of the fiber is in the range of 10 to 20% by weight, the cationized modified cotton fiber, or the cationized modified regenerated cellulose fiber, or the mixture of the cationized modified cotton fiber and the cationized modified regenerated cellulose fiber The mixing ratio is 20 to 40% by weight, and the sum of the mixing ratios of both is 30 to 5 of the whole fiber. It is preferable to set it as the range of 0 weight%.

The expression of the dichroic melange using the yarn for melange according to the present invention may be a combination of general gray and any color, or a combination of any two colors. The mixing ratio of the modified regenerated cellulose fiber containing the pretreatment agent of the naphthol dye and the cationized modified cotton fiber or the cationized modified regenerated cellulose fiber is preferably equivalent in proportion to the balance of the fibers to be dyed. If the sum of the mixing ratios of both is in the range of 10 to 50% by weight of the entire fiber as in the foregoing, the sum of the mixing ratios of both is 20% by weight and 40% by weight, so that the selective combination becomes easy. By adjusting the dyeing density, the effect of melange can be expressed in the former in light color and the latter in dark color. If the sum of the mixing ratios is less than 10%, the concentration of the color to be dyed is limited, and if it exceeds 50%, the expression of the effect of melange is limited by the concentration and the amount of the color to be dyed.

The method for dyeing the yarn for melange of the present invention firstly dyes the modified regenerated cellulose fibers containing the pretreatment agent of the naphthol dye. This is because the pretreatment agent of the naphthol dye increases the molecular weight of the dye by coupling reaction with the developer and is fixed to the modified regenerated cellulose fiber.

The colorant of the naphthol dye to be used may be selected as appropriate, even if an aromatic amine is used, even if a salt in which a diazotized and stabilizer or the like is used is used. Moreover, you may use it, adding surfactant which is a wetting agent, etc. to these dyeing liquids. The dyeing conditions are easily proceeded even at room temperature when the coupling reaction between the pretreatment and the developer is carried out, so that the ratio is adjusted to the optimum pH of the developer used at a bath ratio of 1:10 to 1:50 and at a temperature of 20 to 40 ° C for 10 to 30 minutes. By dyeing, only modified regenerated cellulose fibers containing a naphthol dye pretreatment agent can be dyed without contaminating the cationized modified cellulose fibers or the refined / bleached cotton fibers. In addition, by combining modified regenerated cellulose fibers with different pretreatments of naphthol dyes, dyeing with a developer will have the effect of obtaining two or more dyes.

Subsequently, the cationized modified cotton fibers, or cationized modified cotton cellulose fibers, or a mixture of cationized modified cotton fibers and cationized modified regenerated cellulose fibers, are dyed with anionic dyes, but anionic dyes are reactive dyes or acidic. Dye can be used suitably. As the reactive dyes used in the present invention, for example, the dye name of the product may include reactive dyes of Procion P, Kayacion P, Cibaclone P, Mikacion, Kayacion E, Procion M, or Levafix E. From these, it can select suitably. As the dyeing conditions, only a strong base catalyst such as sodium hydroxide may be used as a dyeing aid, and a method of dyeing for 20 to 60 minutes at a temperature of 50 to 100 ° C. and a bath ratio of 1: 10 to 1:50 is employed.

Moreover, it is preferable to satisfy dye fastness required for a product as an acid dye used by this invention, For example, the half milling type, milling type, and metal complex salt type acid dye are mentioned. As the half milling type, the dye name of the product may be acid dyes such as sminolfast, kayanol, and sand run MF, and the milling type dye name of the product may be sminol milling, kayanol milling, or sand run N. And the like. Examples of the metal complex salt type include dyestuffs such as Ranyl W, Kayalax, and Isolen S, which can be appropriately selected from these. What is necessary is just to employ | adopt the method of dyeing for 20 to 40 minutes at the temperature of 80-100 degreeC and bath ratio 1: 10-1: 50 using only an acid dye as dyeing conditions. In addition, in order to block the dyed seat remaining in the cationized modified cellulose-based fiber, a blocking agent under static charge can be appropriately used, and a fixation agent can be used depending on the required color fastness.

The dyeing product after the dyeing step is transferred to a process such as saponification, resin processing, finishing emulsion treatment, etc., but these steps are not particularly limited and can be carried out by a commonly used method.

In addition, the dyeing method of the cellulose-based fiber product according to the present invention, after dyeing a fiber product consisting of three different fibers using a developer of naphthol dyes, the reactivity with a high affinity to the dye or cellulose fibers directly Dyeing method of dyeing, dyeing textile products consisting of three different fibers with a naphthol dye developer, followed by dyeing with a reactive dye having low affinity with acid dyes or cellulose fibers, followed by direct affinity with dyes or cellulose fibers There is a dyeing method of a cellulose fiber product dyed with this highly reactive dye, and these dyeing methods will be described.

Reactive dyes having low affinity with cellulose fibers used in the present invention are reactive dyes having low adsorption to cellulose fibers and are dyes having a monochlorotriazine-based reactor, dyes having a trichlorotriazine-based reactor, and the like. For example, the dye name of the trade name may be Proceon P, Kayacion P, Cibaclon, Drimarene or reactive dyes of the reactone, and the like. Moreover, the reactive dye which has high affinity with the cellulose fiber used by this invention is a reactive dye with high adsorption to a cellulose fiber, and is a dye which has a reactor of a dichloro triazine, a dye which has a reactor of a dichloroquinoxaline system, etc. For example, the dye name of a brand name can mention the reactive dye of mica, procion M, kayacion E, or levafix E, etc., and can select from these suitably.

In the first method, since the modified regenerated cellulose fibers containing the pretreatment agent of the naphthol dye are dyed, only the cationized modified cellulose fibers are dyed without dyeing the usual cellulose fibers, and thus have low affinity with acid dyes or cellulose fibers. Reactive dyes are used. These dyes may be appropriately selected and used according to the desired color, but for example, acidic dyes have a low affinity for modified regenerated cellulose fibers containing a pretreatment agent of naphthol dyes and ordinary cellulose fibers. Reactive dyes having a characteristic of selectively dyeing modified modified cellulose fibers and having low affinity with cellulose fibers can be cationic modified modified cellulose fibers by using only a strong base catalyst such as caustic soda (sodium hydroxide) as a dyeing aid. Only the dye can be selectively dyed. As dyeing conditions, acid dyes may be used, or only reactive dyes and strong base catalysts may be used as dyeing aids, and dyeing may be performed at a temperature of 50 to 100 ° C. for 20 to 60 minutes. In addition, in order to block the dyed seat in which the cationized modified cellulose fiber remains, an electrostatic charge blocking agent can be suitably used. In the first invention, since normal cellulose fibers are not dyed, they exhibit an effect as a white phase.

As a second method, after dyeing a modified regenerated cellulose fiber containing a pretreatment agent of naphthol dye, three materials of modified regenerated cellulose fiber, a cationized modified cellulose fiber and ordinary cellulose fiber containing a pretreatment agent of naphthol dye Is a method of dyeing at the same time, using a direct dye or a reactive dye having a high affinity with the cellulose fibers by the conventional method. For example, in the case of using a reactive dye having high affinity with cellulose fibers, a neutral catalyst such as manganese (sodium sulfate) or salt (sodium chloride) and a basic catalyst such as soda ash (sodium carbonate) are used as a dyeing aid, and the temperature is 50 to 100 ° C. The dye may be used for 20 to 60 minutes, and when using a direct dye, the neutral salt may be dyed for 40 to 60 minutes at a temperature of 80 to 100 ° C. using a neutral salt. Moreover, according to the required dyeing fastness, a fixation agent can be used.

In the third method, since the modified regenerated cellulose fibers containing the pretreatment agent of the naphthol dye are dyed, only the cationic modified cellulose fibers are dyed without dyeing other cellulose fibers, and according to the first invention, the acid dyes or cellulose fibers are Use reactive dyes with low affinity. In addition, a second dye using a reactive dye having a high affinity with direct dyes or cellulose fibers is dyed at the same time by dyeing three kinds of materials such as modified regenerated cellulose fibers, cationized modified cellulose fibers and cellulose fibers containing a pretreatment agent of naphthol dyes. It is a method of dyeing by the method of the invention.

The color of the cellulose fiber dyed twice by the second and third methods is that the respective colors overlap, so that the desired color can be appropriately obtained by the dye used. For example, in the case of modified regenerated cellulose fibers containing a pretreatment agent of naphthol dyes, they are dyed dark brown with a developer, and then dyed pale yellow with direct dyes, resulting in a dark brown color. Is dyed dark blue with reactive dye, and then dyed pale yellow with direct dye to dark green. In addition, by using a plurality of modified regenerated cellulose fibers having different kinds of pretreatment agents of naphthol dyes, the number of colors obtained can be increased, and a fiber product of a desired color can be appropriately obtained by a combination of dyes to be used.

The dyeings which have been dyed are transferred to processes such as saponification and finishing emulsion treatment, but these steps are not particularly limited and can be carried out by a method which can be generally used.

As a fourth method, a fiber product in which three spun yarns of three kinds of cellulose-based materials such as modified regenerated cellulose fibers containing a pretreatment agent of naphthol dye, cationized modified cellulose fibers and ordinary cellulose fibers are interlaced, or three kinds of cellulose-based materials Use a knitted textile product using a blended yarn. As a fiber product in which spun yarns using three kinds of cellulose-based materials are interwoven, the proportion of each cellulose-based fiber may be arbitrarily determined according to the desired dichroic effect. In order to produce melange yarns using a spun yarn obtained by blending three kinds of cellulose-based fiber, the ratio (weight%) of each fiber material is determined by (modified regenerated cellulose fiber + cationized denatured containing a pretreatment agent of naphthol dye). Cellulose fiber): When expressed as a normal cellulose fiber (modified regenerated cellulose fiber + cationized modified cellulose fiber containing a pretreatment agent of naphthol dye): normal cellulose fiber = (3 + 3): 94 to [(3 to 77 ) + (77-3)]: It is not preferable because the melange effect is not expressed unless it is within the range of 20. In addition, since the melange effect is expressed by the balance of the color and quantity of the normal cellulose fiber of the white phase in the uncolored two kinds of cellulose-based materials and undyed, and the presence of the white phase is important, Dyeing method is adopted.

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to this range. In addition, the determination method of the effect of the melange in this Example was measured in accordance with the following method.

Method of judging the effect of melange

The dyed sample was judged by the following criteria by the sensory test by five test | inspectors.

5 power supply good: ◎, 3-4 good: ○, 1 to 2 good: △, 5 power supply poor: ×

EXAMPLE 1

Each sample was obtained by the method of following (1)-(8).

(1) CIACC10 (trade name: Kako Grounder), a pretreatment agent for naphthol dyes by CIACC (Co1our Index Azoic Coupling Component) described in COLOR lNDEX (SECOND EDITION 1956) VOLUME 3 AZOIC SECTION published by Chorlcy & Pickersgil Ltd. E, Sowa Chemical Co., Ltd.], 350 g of ethanol, 175 g of lot oil and 350 g of pure water were kneaded, and then the dough was added to 350 g of 48% aqueous sodium hydroxide solution and 995 g of pure water was heated to 60 ° C. In addition, it melt | dissolved stirring. Then C.I.A.C.C. About 2500 g of pure water was further added so that the concentration of 10 might be 7.0%, and 5000 g of the dissolved stock solution of C.I.A.C.C.10 having a concentration of 7.0% was adjusted.

The pretreatment dissolution stock solution of the adjusted naphthol dye of 7.0% of the adjusted concentration was added to and mixed with the polynostic viscose so that the pretreatment agent of the naphthol dye was 1.5% based on the cellulose content of the polynosic viscose. A porous nozzle was used to spin in a spinning bath in which 22.0 g / l sulfuric acid, 65.0 g / l sodium sulfate, and 0.5 g / l zinc sulfate were dissolved at a spinning speed of 30 m / min, followed by sulfuric acid at a temperature of 25 ° C. Stretched twice in a bath containing 2.0 g / l and 0.05 g / l of zinc sulfate, cut to 38 mm, and then relaxed in a bath in which 1.0 g / l of sodium carbonate and 2.0 g / l of sodium sulfate at a temperature of 60 ° C. were dissolved. . Thereafter, the resultant was further treated in a bath in which 5.0 g / l of sulfuric acid at a temperature of 65 ° C. was dissolved, followed by washing with water and emulsifying and modifying regenerated cellulose fibers (A) containing a pretreatment agent of naphthol dye of about 1.4 O dtex, About 1000g was produced so that a thread might not break. The content of the pretreatment agent of the naphthol dye contained in the obtained modified regenerated cellulose fiber (A) was 1.4% as a result of the measurement. After degrading the modified regenerated cellulose fiber (A) containing the pretreatment agent of the obtained naphthol dye, a spun yarn of 14.76tex was produced using a quick spin system (type: QSS-R20, manufactured by SDL International LTD.). This was made into tester A.

(2) 35% hydrogen peroxide aqueous solution 5g / L, stabilizer of hydrogen peroxide [trade name: IP chelate D-40, Ippsha Oil Holding Co., Ltd.] 2g / L, 48% sodium hydroxide aqueous solution 4g / L, refinement Permeating agent (trade name: Epitol BSconc, manufactured by Sun Chemical Co., Ltd.), with a treatment solution containing 0.5 g / l, rinsing and bleaching at a bath ratio of 1:15 at a temperature of 95 ° C. for 40 minutes, followed by washing with water and acetic acid. Acetic anhydride and Kanto Chemical Co., Ltd.] 1 g / L, a neutralizing bath at a bath ratio of 1:15 and a temperature of 50 ° C. for 15 minutes, followed by washing with a cationic agent (trade name: Cationone UK, Ipposha) Oil and fat industry]] 70 g / L, reaction catalyst [brand name: reagent sodium hydroxide, Kanto Chemical Co., Ltd.] 10 g / L, wet penetrant [brand name: Cline N-15, Itosha Yuji Co., Ltd.] ] After a reaction bath containing 2 g / L at a bath ratio of 1:15 and a temperature of 60 ° C. for 60 minutes, the mixture is washed with water sufficiently to give acetic acid. Acetic anhydride and Kanto Chemical Co., Ltd.] 1 g / L, a neutralizing bath at a bath ratio of 1:15 and a temperature of 50 ° C. for 15 minutes, followed by washing with water, followed by a flexible smoothing finishing agent [trade name: John's TA- 460-15, Matsumoto Yuji Pharmaceutical Co., Ltd.] 8 g / L, spinning emulsion [Trade name: Telon LE, Matsumoto Yuji Pharmaceutical Co., Ltd.] 2 g / L The treatment bath containing a bath ratio 1: 15, temperature After processing at 50 ° C. for 20 minutes, centrifugal dehydration was performed, followed by drying with warm air at 80 ° C., to prepare about 100 g of a refined and bleached cationized modified cotton fiber (Bl).

After refining and bleaching the obtained cotton fiber (B1) denatured, a spun yarn of 14.76 tex was produced using a quick spin system, which was defined as test yarn B1.

(3) After washing and bleaching cotton fibers in the US under the same conditions as in (2) above, washing them with water, neutralizing them, washing them with water, followed by casting, centrifugal dehydration, warm air drying, and washing and bleaching cotton. Approximately 100 g of fiber (C) was prepared.

(4) 1.40 dtex and 38 mm length of regenerated cellulose fiber (D) (trade name: Junron, After Fat Co., Ltd.) were prepared.

Four kinds of modified regenerated cellulose fibers (A) containing a pretreatment agent of naphthol dye, refined and bleached and then cationic denatured cotton fibers (Bl), refined bleached cotton fibers (C) and regenerated cellulose fibers (D) After mixing at the mixing ratio shown in Table 1, the spin yarn of 14.76 tex was manufactured using the quick spin system, and these were set as test yarns 1-4.

These were used to knit a sock fabric having a length of about 30 cm using a sock knitting machine, and each was made into woven fabrics 1-4.

TABLE 1

Examiner 1 Examiner 2 Examiner 3 Examiner 4 A 10% 20% 5% 3% B1 10% 20% 5% 3% C 60% 50% 65% 67% D 20% 10% 25% 27% A + B1 20% 40% 10% 6% A + D 30% 30% 30% 30% Fabric Name Fabric 1 Fabric 2 Fabric 3 Fabric 4

(5) Wet penetrant [brand name: Cline N-15, Ipposha Oil Industry Co., Ltd.] 1 g / L, acetic acid [brand name: reagent anhydrous acetic acid] , Kanto Chemical Co., Ltd.] 0.5 g / L, and after washing for 15 minutes at a bath ratio of 1:20 and a temperature of 60 ° C., washed with water. Subsequently, C.I.A.D.C. (Co1or Index Azoic Diazo Component) 20 of a color index, which is a color developer, was used. Kako Blue BB Sa1t, manufactured by Kawasaki Kogyo Co., Ltd.] was 2.5% owf, C.I.A.D.C. 44, based on modified regenerated cellulose fibers (A) containing a pretreatment agent of naphthol dyes. Kako Yellow GC Sa1t, manufactured by Kawasaki Kogyo Co., Ltd.], 2.5% owf to a modified regenerated cellulose fiber (A) containing a pretreatment agent of naphthol dyes, a nonionic surfactant [trade name: Cline N-15, Ipposha Yuji INDUSTRIAL CO., LTD] treatment in a dyeing solution containing 2.0 g / L for 5 minutes under the conditions of bath ratio 1:20 and a temperature of 40 degreeC, the dyeing solution was prepared at pH 7.0 with 0.4% sodium hydroxide aqueous solution, and 30 minutes. The modified regenerated cellulose fibers containing the pretreatment agent of the naphthol dye were dyed and washed with water. As a result, Test Yarn A, a modified regenerated cellulose fiber, was dyed black. Next, bath ratio 1: 20 in a dyeing solution containing 2.0% owf with respect to the cotton fiber (Bl) refine | purified and bleached the red reactive dye [Kayacion Red P-4BN, the Nippon Kayaku Co., Ltd. product]. After 20 minutes of treatment in a fixed solution containing 4 g / l of a basic reaction catalyst (trade name: Espolo A-609, manufactured by Ipposha Oil Industry Co., Ltd.), treatment was performed at a bath ratio of 1:20 at a temperature of 70 ° C. for 20 minutes. Then, the scouring and bleached cationized modified cotton fibers were dyed. As a result, Test B1 was dyed dark red. Subsequently, after saponification at a bath ratio of 1:20 and a temperature of 80 ° C. for 15 minutes in a treatment solution containing a surfactant (trade name: Bisol RK, manufactured by Ippossha Oil Industry Co., Ltd.) 3.0 g / L, the product was washed with water and then, It dried with the warm air of 120 degreeC, and obtained sample No. 1 dyed from the cloth 1.

The observation result of the external appearance color of obtained sample No. 1, and the effect of a melange were determined, and the result is shown in following Table 2.

(6) Three kinds of the fabric 2, the test yarn A 1g, and the test yarn B1 1g were treated as described in (5) above to obtain sample No. 2, test yarn A, and test yarn B1 stained with the cloth 2. As a result, Test Yarn A, a modified regenerated cellulose fiber containing a pretreatment agent of naphthol dye, was dyed black, and Test Yarn B1, a cationic modified cotton fiber, was dyed red.

The observation result of the external appearance color of obtained sample No. 2, and the effect of a melange were determined, and the result is shown in following Table 2.

(7) Three kinds of the fabric 3, 1 g of test yarn A and 1 g of test yarn B1 were treated with a developer and a nonionic surfactant as described in the above (5), and then prepared at pH7.0 to contain a pretreatment agent of naphthol dye. Denatured regenerated cellulose fibers were dyed and washed with water. As a result, Test Yarn A, a modified regenerated cellulose fiber containing a pretreatment agent of naphthol dye, was dyed black. Subsequently, in the dyeing solution containing 3% owf with respect to the cotton fiber (Bl) refined and bleached with a dark blue acid dye (trade name: Suminol Fast Navy Blue R, manufactured by Sumitomogagaku Kogyo Co., Ltd.) 1:20 After dyeing at a temperature of 80 ° C. for 30 minutes, saponifying in a treatment solution containing the same surfactant as in the above (5), washing with water, centrifugal dehydration, drying with warm air, and dyeing with fabric 3 And tester B1 were obtained. As a result, Test Yarn B1, a cationic denatured cotton fiber, was dyed dark blue.

The observation result of the external appearance color of obtained sample No. 3, and the effect of a melange were determined, and the result is shown in following Table 2.

(8) Three kinds of the woven fabric 4, 1 g of test yarn A and 1 g of test yarn B1 were treated with a developer and a nonionic surfactant as described in the above (5), and then prepared at a pH of 7.0 to contain a modified agent containing a naphthol dye pretreatment agent. The washed cellulose fibers were dyed and washed with water. As a result, Test Yarn A, a modified regenerated cellulose fiber containing a pretreatment agent of naphthol dye, was dyed black. Subsequently, in the dyeing liquid containing 0.2% owf with respect to the cotton fiber (B1) refine | purified and bleached the red acid dye [Brand name: Sandolan Red MFTNS, the product made by Clariant Japan Co., Ltd.] Dye for 30 minutes at and washed with water. As a result, Test Yarn B1, a cationic denatured cotton fiber, was dyed pink. Subsequently, after saponifying in the process liquid containing surfactant similar to above-mentioned (4), it washed with water, and after centrifugal dehydration, it warmed and air-dried and the comparative sample No. 1 dyed with the cloth 4 was obtained.

The observation result of the external appearance color of obtained comparative sample No. 1, and the effect of a melange were determined, and the result is shown in Table 2.

TABLE 2

Sample No. One Sample No. 2 Sample No. 3 Comparative Sample No. One A (color: mix ratio) Black: 10% Black: 20% Black: 5% Black: 3% B1 (Color: Mixing Ratio) Dark red: 10% Dark red: 20% Navy blue: 5% Pink: 3% Dyeing part (mixed ratio) 20% 40% 10% 6% Regenerated cellulose portion (mixed ratio) 30% 30% 30% 30% Melange effect ◎ ◎ ◎ △ Color of appearance Melange image of gray + red system Melange image of gray + red system Gray Melange Award Melange image of gray + pink

As Table 2 shows, Samples No. 1 to No. 2 show that the modified regenerated cellulose fibers containing a pretreatment agent of naphthol dye are black, and the cationized modified cotton fibers are dyed dark red. The sample No. 1 exhibits the appearance of two colors of melange of light gray and red color, and the sample No. 2 shows the appearance of two colors of melange of dark gray and red color, and the fabric of excellent quality is obtained. lost. Sample No. 3 is a modified regenerated cellulose fiber containing a pretreatment agent of naphthol dye in black, and the cationized modified cotton fibers are dyed in navy blue, and the appearance is bluish grey, and an excellent melange-like fabric was obtained. . Comparative sample No. 1 is a modified regenerated cellulose fiber containing a pretreatment agent of naphthol dye is black, the cationized denatured cotton fibers are dyed pink, but the appearance is very hazy red gray melange, but the effect of melange The rating was low.

EXAMPLE 2

Each sample was obtained by the method of following (9)-(13).

(9) The same wet penetrant as described in Example 2 (2) and 2 g / l of soda ash were used, using 40dtex and 38 mm length of regenerated cellulose fibers (trade name: Junron, after-fat Co., Ltd.). In a treatment bath to be treated, the mixture was rinsed at a bath ratio of 1:15 at a temperature of 80 ° C. for 20 minutes, and then washed with water sufficiently. After reacting for 60 minutes at a bath ratio of 1:15 and a temperature of 60 ° C. in a treatment bath containing 1 L, it is sufficiently washed with water and neutralized for 15 minutes at a bath ratio of 1: 15 and a temperature of 50 ° C. in a treatment bath containing 1 g / L of acetic acid. After that, it was washed with water, and then treated in a treatment bath containing 8 g / l of a flexible smoothing finisher and 2 g / l of a spinning oil emulsion similar to that described in (2) of Example 1, at a bath ratio of 1:15 at a temperature of 50 ° C. for 20 minutes. After centrifugation, the resultant was dehydrated and dried by warm air at 80 ° C. to prepare about 50 kg of cationic modified regenerated cellulose fiber (B2). .

After refining and bleaching the obtained cellulose-modified regenerated cellulose fiber (B2), a spun yarn of 14.76 tex was produced using a quick spin system, which was defined as test yarn B2.

Modified regenerated cellulose fiber (A) containing the pretreatment agent of naphthol dye of (1) of Example 1, cotton fiber (Bl) modified and cationicly modified after refining and bleaching of (1) of Example 1, above Regenerated cellulose fiber (B2) subjected to cationization and denatured after bleaching, bleaching, refined bleached cotton fiber (C) based on (1) of Example 1, and regenerated cellulose fiber (D) based on (1) of Example 1 After mixing the four selected from the mixing ratio shown in Table 3, using a quick spin system to produce a spun yarn of 14.76 tex, these were set to test yarns 5-7.

Using a yarn 5-7, a socks fabric of about 30 cm in length was knitted using a sock knitting machine, and each was made into 5-7 fabrics.

[Table 3]

Examiner 5 Examiner 6 Examiner 7 Examiner 8 A 10% 10% 10% 20% B1 0% 15% 40% 30% B2 20% 20% 0% 0% C 70% 55% 30% 40% D 0% 0% 20% 10% A + (B1 + B2) 30% 45% 50% 50% A + (B2 or D) 30% 30% 30% 30% Fabric Name Fabric 5 Fabric 6 Fabric 7 Fabric 8

(10) After refining three kinds of the fabric 5 and the test yarn A 1g of (1) substrate of Example 1 and the tester B 2 1g of the above-mentioned (9) substrate, in the same manner as in the procedure of (5) of Example 1 A washing agent, CIADC13 (trade name: Kako Scarlet RC Base, manufactured by Showa Chemical Co., Ltd.), which was diazotized by a conventional method, was then applied to a modified regenerated cellulose fiber containing a pretreatment agent of naphthol dye. In a dyeing solution of 0.5% owf and a 0.5% owf permeant for 5 minutes at a bath ratio of 1:20 and a temperature of 30 ° C., after which sodium acetate was added to the dyeing solution and adjusted to pH 5.6, containing a pretreatment agent of naphthol dye. The modified regenerated cellulose fibers were dyed for 20 minutes and washed with water. As a result, the modified regenerated cellulose fibers containing the pretreatment agent of the naphthol dye were dyed dark red. Subsequently, the red acid dye (trade name: Sandolan Red MFTNS, manufactured by Clariant Japan Co., Ltd.) was refined and bleached, and then cationicly denatured regenerated cellulose fibers in a dye solution containing 1.0% owf in a bath ratio of 1:20, It washed with water, after dyeing at 80 degreeC for 30 minutes. As a result, test yarns B1 and B2 were dyed red. Subsequently, after saponifying in the processing liquid containing the same surfactant as the base material of Example 1 (4), it washed with water, and centrifugal dehydration, it dried warmly, and sample No. 4 which was dyed with the cloth 5 was obtained.

The observation result of the external appearance color of obtained sample No. 4, and the effect of a melange were determined, and the result is shown in following Table 4.

(11) Four kinds of fabric 6, 1 g of test yarn A of (1) substrate of Example 1, 1 g of test yarn B1 of (1) substrate of Example 1, and 1 g of test yarn B2 of (9) substrate described above were carried out. After scouring as in (5) of Example 1 and washing with water, the developer CIADC20 was then 2.0% owf to the modified regenerated cellulose fiber (A) containing the pretreatment agent of the naphthol dye, 2.0 g / l. After treating for 5 minutes in a dyeing solution containing a bath ratio of 1:20 and a temperature of 40 ℃, the dyeing solution was adjusted to 7.0 in a 0.4% sodium hydroxide aqueous solution to 7.0, and washed with water after dyeing for 30 minutes. As a result, Tester A was dyed very dark navy blue. Subsequently, the turquoise reaction dye (trade name: Kayacion Turquoise P-NGF, manufactured by Nihon Kayaku Co., Ltd.) was refined and bleached, followed by cationic denatured cotton fiber (Bl), followed by refining and bleached regenerated cellulose. The resultant was dyed for 30 minutes at a bath ratio of 1:20 at a temperature of 80 ° C. in a dyeing solution containing 2.5% owf to the sum of the weights of the fibers (B2) and washed with water. As a result, tester B1 and tester B2 were dyed with dark turquoise blue of approximately the same color. Subsequently, after saponifying in the processing liquid containing surfactant like Example 5 (5), it washed with water, centrifugal dehydration, and warm air drying, and sample No. 5 dyed with the fabric 6 was obtained.

The observation result of the external appearance color of obtained sample No. 5, and the effect of a melange were determined, and the result is shown in following Table 4.

(12) After pretreatment of three kinds of fabric 7 and test yarn A 1g of (1) base material of Example 1 and test thread B1 1g of base material (1) of Example 1 in the same manner as in Example (5) Colorant CIADC20 3.5% owf to modified regenerated cellulose fibers (A) containing a naphthol dye pretreatment agent, CIADC44 1.5% owf to modified regenerated cellulose fibers (A) containing a pretreatment agent of naphthol dyes Except for making into (5) the same as in Example 1, the modified regenerated cellulose fibers containing the naphthol dye pretreatment agent were dyed and washed with water. As a result, Test Yarn A, a modified regenerated cellulose fiber containing a pretreatment agent of naphthol dye, was dyed brown. Next, 2.0% owf of blue reactive dye [Brand name: Kayacion Orange PG, manufactured by Nihon Kayaku Co., Ltd.] was refined and bleached, followed by cationic denatured cotton fiber (Bl). Kayacion Blue P-3R, manufactured by Nihon Kayaku Co., Ltd.], was dyed and treated as in Example 1 (5), except that 0.3% owf of the cationic denatured cotton fiber (Bl) was used. , Sample No. 6 on which the cloth 7 was dyed, and test yarn B1 were obtained. As a result, Test B1 was dyed dark brown.

The observation result of the external appearance color of obtained sample No. 6, and the effect of a melange were determined, and the result is shown in following Table 4.

(13) After pretreatment of three kinds of woven fabric 8 and 1 g of test yarn A of (1) base material of Example 1 and 1 g of test yarn B1 of (1) base material of Example 1, The modified regenerated cellulose fiber containing the naphthol dye pretreatment agent in the same manner as in Example 1 (5), except that the developer CIADC44 was 1.8% owf to the modified regenerated cellulose fiber containing the naphthol dye pretreatment agent (A). Dyeing and washing with water. As a result, Test Yarn A, a modified regenerated cellulose fiber containing a pretreatment agent of naphthol dyes, was dyed in dark orange. Subsequently, 1.0% owf of brown acid dye [Brand name: Kayanol Milling Orange G, Nihon Kayaku Co., Ltd.] was refined and bleached, and then cationicly denatured cotton fiber (Bl). Kayanol Milling Brown 4GW, manufactured by Nihon Kayaku Co., Ltd.], was then dyed and treated as in Example 7 (7) except that 0.5% owf of the cationic denatured cotton fiber (Bl) was used. Sample No. 7 and test yarn B1 obtained by dying woven fabric 8 were obtained. As a result, Test B1 was dyed dark orange.

The observation result of the external appearance color of obtained sample No. 7, and the effect of a melange were determined, and the result is shown in Table 4.

[Table 4]

Sample No. 4 Sample No. 5 Sample No. 6 Sample No. 7 A (color: mixture ratio) Dark Red: 10% Dark Ultramarine Blue: 10% Brown: 10% Dark orange: 20% B1 and B2
(Color: mixture ratio) Red: 20% Turquoise: 20% Dark brown: 40% Dark orange color: 30% Dyeing part (mixed ratio) 30% 30% 50% 50% Color cellulose (mixed ratio) 30% 30% 30% 30% Melange effect ◎ ◎ ◎ ◎ Exterior color Red Melange Blue system melange Brown Melange Orange color melange award

As clearly shown in Table 4, Sample Nos. 4 to 7 stained regenerated cellulose fibers containing a pretreatment agent of naphthol dye and cationized modified cellulose fibers with the same color. Because of their different colors, high-quality fabrics were obtained on melanges with excellent cow / shading.

Next, examples of the dyeing method according to the present invention are shown. In addition, content and dyeing density | concentration of the pretreatment agent of the naphthol dye in the following Examples were measured in accordance with the following method.

Measurement method of content of pretreatment agent of naphthol dye

A sample of a modified regenerated cellulose fiber containing a pretreatment agent of naphthol dye was accurately weighed, 100 ml of 0.1 N sodium hydroxide was added and treated at 50 ° C. under slow stirring for 1 hour, and the pretreatment was extracted to give a test solution. Using a spectrophotometer (model: DU640, manufactured by Beckman Co., Ltd.), the absorbance at the maximum absorption wavelength of the test solution was measured, and the concentration of the pretreatment agent was determined using a calibration curve prepared in advance. Content of the pretreatment agent of the naphthol dye in a fiber was calculated | required.                     

[Equation 1]

How to measure the dye concentration

The stained samples were measured using a spectrophotometer (model: SICOMUC-20, manufactured by Sumika Analysis Center), and the dye concentration value (K / S value) at the maximum absorption wavelength was measured by Kubelka-Munk. Obtained from Kubelka-Munk's equation.

[Equation 2]

Where K is the absorption coefficient, S is the scattering coefficient, and R is the reflectance at the maximum absorption wavelength.

EXAMPLE 3

Each test company and the sample were obtained by the method of following (1)-(8).

(1) Color Index Azoic described in COLOUR INDEX (SECOND EDITION 1956) VOLUME 3 AZOIC SECTION published by Chorlcy & Pickersgil Ltd in the same manner as that described in Japanese Patent Laid-Open No. 2003-3322. CIACC pretreatment agent for naphthol dye, a coupling component (hereinafter abbreviated as CIACC) 10 [brand name: Kako Grounder E, Showa Chemical Co., Ltd.] 350 g of ethanol, 175 g of lot oil and 350 g of pure water were kneaded, and then the dough was added to 350 g of 48% sodium hydroxide aqueous solution and 995 g of pure water was added to 60 g. Hot sodium hydroxide heated to ° C was added to dissolve and stirred. Subsequently, about 2500 g of pure water was added so that the concentration of C.I.A.C.C.10 might be 7.0%, and 5000 g of a dissolution stock solution of C.I.A.C.C.10 at a concentration of 7.0% was prepared.

A pretreatment dissolution stock solution of the prepared naphthol dye of 7.0% of concentration was added to and mixed with the polynostic viscose so that the pretreatment agent of the naphthol dye was 1.5% with respect to the cellulose powder of polynosic viscose. The nozzle was spun in a spinning bath in which 22.0 g / l sulfuric acid, 65.0 g / l sodium sulfate, and 0.5 g / l zinc sulfate were dissolved at a temperature of 35 ° C. at a spinning speed of 30 m / min, followed by sulfuric acid at a temperature of 25 ° C. Stretched twice in a bath containing 2.0 g / l and 0.05 g / l zinc sulfate, cut to 38 mm, and then relaxed in a bath in which 1.0 g / l sodium carbonate and 2.0 g / l sodium sulfate at a temperature of 60 ° C. were dissolved. . Thereafter, after further treatment in a bath in which 5.0 g / l of sulfuric acid at a temperature of 65 ° C. was dissolved, water washing and emulsion treatment were performed, and about 100 g of a modified regenerated cellulose fiber of about 1.40 dtex was produced so that the yarn did not break.

The content of the pretreatment agent of the naphthol dye contained in the obtained modified regenerated cellulose fiber was 1.4% as a result of the measurement.

Using the modified regenerated cellulose fiber containing the pretreatment agent of the obtained naphthol dye, the yarn of 19.68 tex was manufactured by the method of Example 1, and this is referred to as test yarn P-1.

(2) In the same manner as in Example 1, 19.68 tex spun yarn was made of American cotton, which was then tested yarn Q-1.                     

(3) 2 g / l of the same wet penetrant and 2 g / l of soda ash, which were used to prepare Test Company Q-1, using 1.4 dtex and 38 mm of regenerated cellulose fibers (trade name: Junron, After Fat Co., Ltd.). In a treatment bath comprising a, a ratio of 1: 15, 20 minutes at a temperature of 80 ℃ and then rinsed sufficiently with water, a treatment bath containing the same cationic agent 40g / L, reaction catalyst 5g / L, wet penetrant 2g / L, Bath ratio 1: 15, after 60 minutes of reaction at a temperature of 60 ° C., washed with water sufficiently, neutralized with a treatment bath containing 1 g / L acetic acid for 15 minutes at bath ratio 1: 15, temperature 50 ° C., and then washed with water. A treatment bath containing 8 g / l of a flexible smoothing finisher and 2 g / l of a spinning emulsion. After treatment at a bath ratio of 1:15 and a temperature of 50 ° C. for 20 minutes, centrifugal dehydration, drying with a warm air at 80 ° C., and cationic modification Approximately 100 g of regenerated cellulose fibers were prepared.

Using the obtained cationized modified regenerated cellulose fibers, a spun yarn of 19.68 tex was produced using a quick spin system as in (1), and this was referred to as test yarn Q-2.

(4) A cationized modified solvent spinning cellulose fiber was treated under the same conditions as Test Q-2 of (3) above using a 1.7 dtex, 38 mm long solvent spinning regenerated cellulose fiber (trade name: manufactured by Tencel, Ltd.). About 100Og was prepared.

Using the obtained cationized modified solvent spinning regenerated cellulose fiber, a spun yarn of 19.68 tex was produced using a quick spin system as in (1), and this was referred to as test yarn Q-3.

(5) After washing and bleaching the American cotton under the same conditions as the above (2), washing with water, neutralizing and washing with water, followed by casting treatment, centrifugal dehydration, warm air drying, and washing the washed and bleached cotton. About 100Og was prepared.

Using the obtained refined bleached cotton, the spun yarn of 19.68 tex was manufactured using the quick spin system like (1), and it is set as test yarn R-1.

(6) Using the tester P-1, the tester Q-1, and the tester R-1, using a sock knitting machine, the yarns were alternately supplied at intervals of about 3 cm. Equivalent sock fabrics are knitted, and this is referred to as sample No. 11.

(7) Using the hosiery knitting machine in the same manner as the tester P-1, the tester Q-2, and the tester R-1, a sock fabric is knitted as in (6) above, and this is referred to as Sample No. 12. .

(8) A tester P-1, a tester Q-3, and a tester R-1 are similarly knitted using a hosiery knitting machine, and the hosiery fabric is knitted as in (6) above, and this is referred to as sample No. 13. .

Obtained Sample No. 11 to Sample No. 13 were wet penetrants (trade name: Cline N-15, manufactured by Ipposha Oil Industry Co., Ltd.) 1 g / L, acetic acid [brand name: Reagent acetic anhydride, Kanto Chemical Co., Ltd.] In the treatment liquid bath containing 0.5 g / L, after washing | cleaning process for 15 minutes at the bath ratio 1:20 and the temperature of 60 degreeC, it washed with water. Subsequently, the Co index index Azoic Diazo Component based on the color index, which is a developer, is abbreviated as CIADC) 22 (brand name: Kako Blue VR Salt, manufactured by Wawa Kogyo Co., Ltd.) 1.0% owf, nonionic surfactant -15, manufactured by Ipposha Oil Industries Co., Ltd.], 2.0 g / l, for 5 minutes under a bath ratio of 1:20 at 40 ° C, and then the dyeing solution was diluted with a 0.4% aqueous sodium hydroxide solution to pH 8.5. It was prepared and then washed with water after dying the modified regenerated cellulose fibers containing the pretreatment agent of naphthol dye for 30 minutes. As a result, the part using tester A-1 was dyed by dark blue. Subsequently, after treatment for 20 minutes at a bath ratio of 1:20 and a temperature of 70 ° C in a dye solution containing a reactive dye [Kayacion Red P-4BN, manufactured by Nihon Kayaku Co., Ltd.] 1.0% owf having low affinity with cellulose fibers, Basic reaction catalyst [Brand name: Espolon A-609, manufactured by Ipposha Oil Industry Co., Ltd.] Treated for 20 minutes at a bath ratio of 1:20 and a temperature of 70 ° C. in a fixation treatment solution containing 4 g / l, and cationic modified cellulose fibers. Dyed. As a result, portions using test yarns B-1 to B-3 were dyed to a deep red color. Subsequently, after saponification at a bath ratio of 1:20 and a temperature of 80 ° C. for 15 minutes in a treatment solution containing a surfactant (trade name: Bisol RK, manufactured by Ippossha Oil Industry Co., Ltd.) 3.0 g / L, the product was washed with water and then, It dried with the warm air of 120 degreeC, and obtained the sample No. 11 '-No. 13' which were dyed.

Samples corresponding to the test company P-1, the test company Q-1, and the test company R-1 in the obtained sample No. 11 'were taken as P-1-1, test company Q-1-1, and test company R-1-1. Table 5 shows the results of observing each color and measuring the dyeing density value (K / S value).

The sample corresponding to the test company P-1, the test company Q-2, and the test company R-1 in the sample No. 12 'obtained similarly is P-1-2, the test company Q-2-1, and the test company R-1. Table 2 shows the results of color observation and dye concentration (K / S value) measured at -2.

The sample corresponding to the test company P-1, the test company Q-3, and the test company R-1 in the sample No. 13 'obtained similarly is P-1-3, the test company Q-3-1, and the test company R-1. Table 3 shows the results of observing each color and measuring the dyeing density value (K / S value) as -3.

TABLE 5

Sample Name color K / S value Sample Name color K / S value Sample Name color K / S value Sample No. 11 ' Tester P-1-1 Dark blue 23.2 Examiner Q-1-1 Dark red 18.6 Tester R-1-1 light ash color 0.2 Sample No. 12 ' Tester P-1-2 Dark blue 22.7 Examiner Q-2-1 Dark red 19.2 Tester R-1-2 light ash color 0.2 Sample No. 13 ' Tester P-1-3 Dark blue 23.8 Examiner Q-3-1 Dark red 18.5 Tester R-1-3 light ash color 0.2

According to the results, the test yarns P-1-1 to P-1-3, which are the dyes of the modified regenerated cellulose fibers containing the naphthol dye lowering agent, had a dye concentration value (K) under the condition of the developer concentration of .0% owf. / S value) was 22.7-23.8, dyed in two uniform dark blues, and contamination by reactive dyes having low affinity with cellulose fibers was not recognized. Tester Q-1-1, Tester R-2-1, Tester Q-3-1, which are the dyes of the cationized modified cellulose fiber, were tested under the conditions of 1.0% owf of reactive dye concentration having low affinity with cellulose fiber. The / S values of 18.5 to 19.2 were all dyed to uniform dark reddish brown, and no contamination by the developer of the naphthol dye was recognized. Testers R-1-1 to R-1-3, which are ordinary dyeings of refined and bleached cotton, were stained with a slight K / S value of 0.2, but remained grayish white. The dyed hosiery fabric consisting of three kinds of materials is composed of dark dyed parts and white parts left in gray white, all of which have high quality without any problem in appearance, and have a clear tricolor of dark blue, dark red brown and gray white. The fiber product which consists of was obtained.

EXAMPLE 4

Testers R-2 to R-4 and Sample Nos. 14 to 16 were obtained by the following methods (1) to (6).                     

(1) US cotton is spun in a conventional manner to prepare a spun yarn of 19.68 tex, which is referred to as test yarn R-2.

(2) 1.4 dtex and 38 mm long regenerated cellulose fibers (trade name: Junron Co., Ltd.) were spun in a conventional manner to prepare a spun yarn of 19.68 tex, which is referred to as test yarn R-3.

(3) A 1.7 dtex, 38 mm long solvent spinning regenerated cellulose fiber (trade name: manufactured by Tencel, a rental company) was spun in a conventional manner to prepare a spun yarn of 19.68 tex, which is referred to as test yarn R-4.

(4) Using a tester P-1 of Example 1, tester Q-1, and tester R-2 of (1), using a sock knitting machine, the yarns were alternately supplied at intervals of about 3 cm. To prepare a sock fabric having approximately the same ratio of three species of about 1 m in length.

(5) Using the hosiery knitting machine in the same manner using the test yarn P-1 and the test yarn Q-1 described in Example 5 and the test yarn R-3 described in the above (2), A sock fabric is knitted and this is set as sample No. 15.

(6) Using the hosiery knitting machine in the same manner using the test yarn P-1 and the test yarn Q-1 of Example 5 and the test yarn R-4 of the above (3), A sock fabric is knitted and made into sample No. 16.

The obtained sample No. 14 was rinsed under the same conditions as in Example 5 and washed with water, and then the developer C.I.A.D.C. The same tester P-1 was stained and washed with 22. As a result, the part using test company P-1 was dyed dark blue. Subsequently, the same treatment as in Example 5 (2) was used, and the treatment contained 4 g / l of 35% aqueous hydrogen peroxide solution, 19 / l of stabilizer of hydrogen peroxide, 2 g / l of 48% sodium hydroxide aqueous solution, and 0.5 g / l of refining penetrant. After washing and bleaching for 1 minute at bath ratio 1:15 and temperature 90 degreeC with liquid for 30 minutes, it washed with water. Subsequently, test dye Q-1 was dyed and washed with the same dyes and conditions as in Example 5 using a reactive dye having a low affinity with cellulose fibers and a basic reaction catalyst. As a result, the part using test company Q-1 was dyed dark red. Subsequently, saponification, water washing, centrifugal dehydration, and warm air drying were performed to obtain Sample No. 14 ', which was dyed.

The obtained samples No. 15 and No. 16 were rinsed in the same manner as in Example 5 and washed with water. Then, the test yarn P-1 was dyed using the same developer as in Example 5, followed by washing with water. As a result, the part using test company P-1 was dyed dark blue. Subsequently, the test yarn Q-1 was dyed and washed with water under the same conditions as in Example 5 using a reactive dye having a low affinity with cellulose fibers and a basic reaction catalyst. As a result, the part using tester Q-1 was dyed dark red. Subsequently, saponification, washing with water, centrifugal dehydration, and warming and drying the samples No. 15 'and No. 16' were obtained.

The sample corresponding to the test company P-1, the test company Q-1, and the test company R-2 in obtained sample No. 14 'was tested by test company P-1-4, test company Q-1-2, and test company R-2. Table 1 shows the results of measuring the color and dyeing density values (K / S values) at -1.

The samples corresponding to the test company P-1, the test company Q-1, and the test company R-3 in the same sample No. 15 'obtained were tested company P-1-5, test company Q-1-3, test company The result of measuring each color and dyeing density value (K / S value) as R-3-1 is shown in Table 6.

The tester P-1, the tester Q-1, and the tester R-4 of the sample No. 16 'obtained similarly were made into the tester P-1-6, the test company Q-1-4, and the test company R-. Table 6 shows the results of observing each color and measuring the dyeing density value (K / S value) as 4-1.

TABLE 6

Sample Name color K / S value Sample Name color K / S value Sample Name color K / S value Sample No. 14 ' Tester P-1-4 Dark blue 21.1 Tester Q-1-2 Dark red 15.3 Tester R-2-1 light ash color 0.2 Sample No. 15 ' Tester P-1-5 Dark blue 24.2 Tester Q-1-3 Dark red 19.0 Tester R-3-1 light ash color 0.3 Sample No. 16 ' Tester P-1-6 Dark blue 24.5 Tester Q-1-4 Dark red 19.8 Tester R-4-1 light ash color 0.2

According to the results, test yarns P-1-4 to P-1-6, which are dyes of modified regenerated cellulose fibers containing a pretreatment agent of naphthol dye, had K / S values of 21.1 under the condition of 1.0% owf of the developer. All of -24.5 were dyed to uniform dark blue, and contamination of the reactive dyes having low affinity with cellulose fibers was not recognized. Testers Q-1-2 to Q-1-4, which are dyes of cationized modified cellulose fibers, have a uniform K / S value of 15.3 to 19.8 under the condition of 1.0% owf of reactive dye concentration having low affinity with cellulose fibers. Stained with dark red, no contamination with the developer of naphthol dye was recognized. Test yarn R-2-1, which is a dyeing material of US cotton, test yarn C-3-1 of regenerated cellulose fiber, and test yarn R-4-1 of solvent spinning regenerated cellulose fiber, had a K / S value of 0.2-0.3 Contamination was noticed but white remained in off-white. The test yarn P-1-4, which is a dye, and the test company P-1-1, which is a dye, of Example 1 showed a difference of 2.0 in the K / S value, but there was a slight difference in concentration in appearance, and there was no difference in quality. . In addition, the test company Q-1-2, which is a dye, and the test company Q-1-1, which is a dye, of Example 1 had a K / S value of 3.3, but there was a slight difference in appearance, and a difference in quality. Was not. The dyed sock fabric consisting of three kinds of materials had a slight difference in appearance concentration even after the refining and bleaching process was added after dyeing with a developer. Each part dyed with dark color and the part with white residue in grayish white had no problem in appearance and had high quality, and a textile product consisting of three colors of dark blue, dark red and grayish white was obtained.

[Example 5]

Using a test yarn P-1 described in Example 3, a test company Q-2 and a test company R-4 described in Example 2, each of the yarns was alternately supplied at intervals of about 3 cm using a sock knitting machine, and the length was about 1 m. Sock fabrics of approximately equal proportion to three types are knitted, and sample No. 18 is used.

The obtained sample No. 18 was rinsed after scouring under the same conditions as in Example 3, followed by developing a colorant CIADC44 (trade name: Kako Yellow GC Salt, manufactured by Wako Chemical Co., Ltd.) 1.2% owf, CIADC20 0.3 After treatment for 5 minutes in a dyeing solution containing% owf, 2.0 g / l of nonionic surfactant at a bath ratio of 1:20 and a temperature of 40 ° C, the dyeing solution was treated with 0.4% aqueous sodium hydroxide solution to 7.0. In the same manner, the test yarn P-1 was dyed for 30 minutes and washed with water. As a result, the part using test yarn A-1 was dyed by dark brown of a dark density. Subsequently, direct dyeing [brand name: Kayarus Supra Scarlet BNL, Nihon Kayaku Co., Ltd.] 1.0% owf, dyeing solution containing 10 g / L of forget-me-not with a bath ratio 1: 20, the test company P-1 for 40 minutes at the temperature 90 degreeC. It washed with water after dying tester Q-2 and tester R-4. As a result, the part using test yarn P-1 was dyed to a dark reddish brown color, and the part using test yarn Q-2 was dyed yellow to medium red, and the part using test yarn R-4 to yellow red. Subsequently, in a treatment solution containing 1.0 g / l of a fixation agent (trade name: Kayafix M, manufactured by Nihon Kayaku Co., Ltd.), the solution was treated at a bath ratio of 1:20 at a temperature of 60 ° C. for 15 minutes, followed by washing with water, followed by centrifugal dehydration. , The warm air was dried to obtain a dyed sock fabric sample No. 18 '.

The sample corresponding to the test company P-1, the test company Q-2, and the test company R-4 of obtained sample No. 8 'was tested by the test company P-1-7, the test company Q-2-3, and the test company R-4. Table 2 shows the results of observing each color and measuring the dye concentration (K / S value) as -2.

TABLE 7

Sample Name color K / S value Sample Name color K / S value Sample Name color K / S value Sample No. 18 ' Sample company P-1-7 Dark reddish brown 25.1 Sample company Q-2-3 Medium yellow red 15.4 Tester R-4-2 Yellow red 6.3

According to the results, the test company P-1-7, which is a dyeing product of modified regenerated cellulose fibers containing a pretreatment agent of naphthol dye, was dyed dark brown under the condition of 1.5% owf of developer, and then directly dye concentration. Since they were dyed yellow-red under the condition of 1.0% owf, the two colors overlapped, and the K / S value was dyed to a uniform dark reddish brown of 25.1. Test company Q-2-3, which is a dye of cationized modified regenerated cellulose fibers, was dyed uniformly to reddish yellow at a concentration of about 15.4 of K / S value under the condition of direct dye concentration of 1.0% owf. Test yarn R-4-2, which is a dye of the solvent-spun cellulose conventional yarn, was dyed uniformly yellowish red with a K / S value of 6.3 under the condition of a direct dye concentration of 1.0% owf.

Dyed hosiery fabric consisting of three kinds of materials is a cellulose fiber of the same material and a combination of two dyeing methods is used to obtain a textile product which is not conventionally obtained three-color dyeings, i.e., dark reddish brown, medium yellow red and yellow red. Could get And they have a high grade without a problem in appearance.

The spun yarn for melange of the present invention can express a wide range of colors and colors with melange by the posterior dye in the mixing ratio of several species, and also is a characteristic for blended yarns of regenerated cellulose fibers and cotton fibers, that is, the texture is soft and excellent hygroscopicity and In addition to moisture resistance, and considering the mixing ratio of cotton fibers and regenerated cellulose fibers, and also excellent in strength, hygroscopicity and moisture resistance, it is optimal as a material of practical garment material, and can contribute greatly to the fashion industry.

In addition, the method of the present invention is a method of dyeing a fiber product consisting of a modified regenerated cellulose fiber containing a pretreatment agent of naphthol dye, a cationized modified cellulose fiber and a normal cellulose fiber with a naphthol dye, followed by dyeing with an anionic dye In addition, by appropriately combining a dye or a high-activity dye affinity with a direct dye or cellulose fibers, etc., by simultaneously dyeing the three materials of cellulose fibers, cationized modified cellulose fibers and ordinary cellulose fibers at the same time It is a method of dyeing multicolored textile products. By interweaving three kinds of cellulose fibers and appropriately selecting the dyes and dyeing methods to be used, the yarns were expressed in melange, or the same cellulose fibers could be dyed in harmony with the dyes caused by dyes. If a non-dyed fiber product made of the above fibers is prepared, the fiber product of the desired color can be dyed as early as desired by the post-dye, and a melange tone can be expressed when a mixed room is used. It can be effective.

Claims (9)

Dyeable consisting of a modified regenerated cellulose fiber containing a pretreatment agent of a naphthol dye, a cationized modified cotton fiber, a cationized modified regenerated cellulose fiber, or a mixture of a cationized modified cotton fiber and a cationized modified regenerated cellulose fiber A yarn for melange fabric comprising a mixture of fibers and undyed fibers consisting of refined and bleached cotton fibers or refined and bleached cotton fibers and regenerated cellulose fibers. The method of claim 1, The blending ratio of the dyeable fibers to the whole yarn is 10 to 50% by weight, the blending ratio of the non-dyed fibers is 90 to 50% by weight, and the mixing ratio of the regenerated cellulose fibers in the total fibers constituting the yarn is 10. Spinning yarn for melange fabrics having a mixing ratio of -30 wt% and cotton fibers of 90-70 wt%. The method according to claim 1 or 2, The blending ratio of the dyeable fibers to the whole yarn is 30-50% by weight, the blending ratio of the undyed fibers is 70-50% by weight, and the cationized modified cotton fibers and cationized modified regenerated cellulose in the dyeable fibers. A spun yarn for melange fabrics in which the mixing ratio of fibers or a mixture of cationized modified cotton fibers and cationized modified cellulose fibers is in the range of 20 to 40% by weight. The method according to claim 1 or 2, (i) modified regenerated cellulose fibers containing a pretreatment agent of naphthol dyes, and (ii) cationized modified cotton fibers, cationized modified regenerated cellulose fibers, or cationized modified cotton fibers and cationized modified regenerated cellulose fibers And (iii) a spun yarn for melange fabrics in which the mixing ratio of refined and bleached cotton fibers or a mixture of refined and bleached cotton fibers and regenerated cellulose fibers is 1: 1: 8 by weight. The method according to claim 1 or 2, (i) modified regenerated cellulose fibers containing a pretreatment agent of naphthol dyes, and (ii) cationized modified cotton fibers, cationized modified regenerated cellulose fibers, or cationized modified cotton fibers and cationized modified regenerated cellulose fibers And (iii) a spun yarn for melange fabrics in which the mixing ratio of refined and bleached cotton fibers or a mixture of refined and bleached cotton fibers and regenerated cellulose fibers is 2: 2: 6 by weight. Dyeable consisting of a modified regenerated cellulose fiber containing a pretreatment agent of a naphthol dye, a cationized modified cotton fiber, a cationized modified regenerated cellulose fiber, or a mixture of a cationized modified cotton fiber and a cationized modified regenerated cellulose fiber Of a cellulose based fiber product comprising the steps of mixing the fibers with fibers of refined and bleached cotton fibers or refined and bleached cotton fibers and regenerated cellulose fibers, dyeing them with a naphthol dye developer, and then dyeing them with anionic dyes. Dyeing method. The method of claim 6, A method of dyeing a cellulose based fiber product, wherein the anionic dye is a reactive dye having low adsorption to cellulose fibers having an acidic dye or a monochlorotriazine-based reactor or a trichlorotriazine-based reactor. Dyeable consisting of a modified regenerated cellulose fiber containing a pretreatment agent of a naphthol dye, a cationized modified cotton fiber, a cationized modified regenerated cellulose fiber, or a mixture of a cationized modified cotton fiber and a cationized modified regenerated cellulose fiber The fiber product obtained by mixing the fibers with the fibers consisting of refined and bleached cotton fibers or refined and bleached cotton fibers and regenerated cellulose fibers is dyed with a naphthol dye developer, and then dyed with anionic dyes, followed by direct dyeing. Or dyeing with a reactive dye having high adsorption to cellulose fibers having a dichlorotriazine-based reactor or a dichloroquinoxaline-based reactor. Modified regenerated cellulose fibers containing a pretreatment agent of naphthol dyes, cationized modified cellulose fibers, and fiber products knitted from ordinary cellulose fibers are dyed with a naphthol dye developer, followed by direct dyeing or dichlorotriazine-based reactors. Or dyeing with a reactive dye having high adsorption to cellulose fibers having a dichloroquinoxaline-based reactor.