ITMI971922A1 - DYEING AND DYEING-FINISHING PROCESS OF TEXTILE MATERIALS CONTAINING MODIFIED CELLULOSE REGENERATED FIBER - Google Patents

Description

DESCRIPTION

TECHNOLOGICAL BACKGROUND OF THE INVENTION

Sector of the invention:

The present invention relates to a dyeing and dyeing-finishing process of textile materials containing modified cellulose regenerated fiber to form the scattered pattern, the dungaree pattern, the cambri pattern, the squared pattern or the striped pattern, having a good shade, without cause staining of undyed parts, deformation, uneven dyeing and smudging. This procedure is suitably applied to fabrics.

Exposure of the prior art:

Cellulose fiber generally exhibits good dyeability for direct dyes and reactive dyes, but has poor dyeability for cationic dyes. There has long been a strong desire for the application of cationic dyes to cellulose fibers with a view to developing their bright color. Attempts have been made to introduce acidic groups into the cellulose fiber to make it dyeable with cationic dyes.

For example, Japanese patent publication No. 19207/1982 describes the introduction of aromatic acyl groups or aromatic sulfonic groups on the surface of the cellulose fiber by means of the aid of aromatic carboxylic acid or aromatic sulphonic acid. The cellulose fiber thus modified can be dyed with cationic dyes in the presence of an anionic surfactant having a sulphate ester group or a sulphonic acid group. However, the process requires complicated steps for the direct chemical modification of the cellulose molecules of the cellulose fiber. Additionally, the resulting modified cellulose fiber loses the feel and moisture absorption inherent in the cellulose fiber. Furthermore, in the case of dyeing with a dark color, the introduction of aromatic acyl groups or aromatic sulphonic groups on the surface of the cellulose fiber poses a problem in relation to color fastness, especially to light and washing.

Japanese Patent Publication No. 4474/1593 discloses modification of regenerated cellulose fiber. This modification is achieved by treating the regenerated cellulose fiber or textile material containing 0.1-20% by weight of sulfonated polystyrene having a molecular weight of 1,000-2,000,000, with an aqueous solution of tannic acid before or after dyeing with cationic dyes. The disadvantage of this process is that the dyed product is practically poor in color fastness since the tannic acid is simply attached to the surface of the fiber.

There is a strong demand in connection with dyeing an object that is capable of dyeing textile materials with a desired color design by single bath dyeing as the current dyeing process does not meet the requirements for a large variety of products in small batches and for rapid delivery. At present the shirts and trousers with the scattered design, the dungaree design, the cambri design, the squared design or the striped design, are produced by weaving or knitting of previously dyed yarns and bleached cotton yarns or regenerated cellulose fiber.

It is known that textile materials made of cotton or regenerated cellulose fiber are superior in the hand and in the absorption of humidity compared to those made of synthetic fiber but suffer from the disadvantage of being subject to creasing and shrinkage following washing.

It has been described (in Japanese patent published No. 158263/1996) that an insoluble polymer which is obtained by crosslinking a hydroxy-diphenylsulfone-sulfonate condensate with epoxy compounds having at least two epoxy groups in the molecule, is incorporated in the viscose of cellulose immediately before spinning. It is possible to obtain modified cellulose regenerated fiber which has practically sufficient resistance without any loss of the hand and moisture absorption inherent in the regenerated cellulose fiber and: - which has good dyeability for cationic dyes and good color fastness.

However, this discovery did not lead to the one-bath process for imparting the loose pattern, the rough cloth pattern, the cambri pattern, the checkered pattern or the striped pattern to textile materials containing modified regenerated cellulose fiber, and it did not lead to not even to a dyeing-finishing process to produce textile materials having good color fastness for cationic dyes, having good washing and use characteristics, having resistance to shrinkage upon washing and resistance to deterioration of strength, and having a good but no.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a dyeing process for textile materials containing modified cellulose regenerated fiber capable of being dyed with cationic dyes by single bath dyeing to form the scatter pattern, the dungaree pattern, the cambri pattern, the checkered pattern. or the striped design. It is another object of the present invention to provide a dyeing and dyeing-finishing process of textile materials to give them good color fastness, good washing and use characteristics, and good hand without deterioration of resistance and without shrinkage to washing and drying. ironing.

The first aspect of the present invention resides in a process for dyeing textile materials containing modified cellulose regenerated fiber capable of being dyed with cationic dyes, said process comprising the dyeing of textile materials with a dyeing solution containing only cationic dyes or containing cationic dyes and dyes other than cationic dyes through the single bath dyeing process to form the scattered design, the dungaree design, the cambri design, the squared design or the striped design. According to the second aspect of the present invention, the step of said dyeing process is followed by a sequential treatment with an aqueous solution of tannic acid, and after this with an aqueous solution of emetic tartar. aspect of the present invention, the steps of said dyeing-finishing process are followed by the further cross-linking treatment with resin, reactive towards cellulose. The modified cellulose regenerated fiber capable of being dyed with cationic dyes is obtained by incorporating, before spinning, into the spinning solution of polystyrene sulfonate or of an insoluble polymer which is obtained by crosslinking the hydroxy-diphenylsulfone-sulfonate condensate with compounds epoxies having at least two epoxy groups in the molecule.

DETAILED DESCRIPTION OF THE PREFERRED ACTUATIONS:

The present invention uses the expression "textile materials containing modified cellulose regenerated fiber" which embraces woven or knitted products formed by modified cellulose regenerated fiber capable of being dyed with cationic dyes and at least one type of fiber selected from the ordinary regenerated cellulose fiber, cotton and wool. They can be produced from previously prepared blended yarn or froté half wool yarn or they can be in the form of blended fabrics from single yarns. The modified cellulose regenerated fiber content in the textile material is not specifically limited, and it can be suitably established in accordance with the desired design and color.

The modified cellulose regenerated fiber used in the present invention can be produced by the viscose process (including polynosic) or the cuproammonia process. It can be incorporated with an inorganic pigment (such as titanium dioxide) for opacification.

The modified cellulose regenerated fiber can be made dyeable with cationic dyes by incorporating the solution of the cellulose viscose, etc., immediately before spinning, with sulfonated polystyrene or with a compound having anionic groups such as an insoluble polymer which is obtained by crosslinking of a dihydroxy-diphenylsulfone-sulfonate condensate with epoxy compounds having at least two epoxy groups in the molecule.

The sulfonated polystyrene should be one that has a molecular weight of 5,000 to 1,000,000, preferably 10,000 to 500,000. Its content should be 0.5 to 10% by weight, preferably 1.0 to 7% by weight, based on the weight of the cellulose.

The insoluble polymer which is obtained by crosslinking a dihydroxydiphenylsulfone-sulfonate condensate with epoxy compounds having at least two epoxy groups in the molecule, is obtained, in the form of an aqueous dispersion, by means of the process described by the present applicant in the Japanese patent published No.

158263/1996. This process consists of crosslinking a dihydroxydiphenyl-sulfone-sulfonate condensate (represented by formula 1) with one or more than one type of polyfunctional epoxy compounds in a slightly basic aqueous solution of pH 7.5-10 at 30-90% for 4-12 hours.

Formula 1

(Where M denotes a monovalent metal atom such as sodium and potassium, and n is an integer from 2 to 20).

Examples of polyfunctional epoxy compounds include polyglycidyl ether sorbitol, polyglycidyl ether pentaerythritol, polyglycidyl ether glycerol, diglycidyl ether resorcinol, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, and neopentyl glycol diglycidyl ether, etc.

Incidentally, the dihydroxydiphenylsulfone-sulfonate condensate and the epoxy compound as cross-linking agent should be used in a ratio of 1: 1 to 1: 3 in terms of hydroxy equivalents of the first and epoxy equivalents of the second. In the event that more than two epoxy compounds are used, the epoxy equivalent is in terms of the total value of their single epoxy equivalents. The amount of the insoluble polymer in the viscose solution should be 5-50% by weight, preferably 10-40% by weight on the weight of the cellulose. Its adequate quantity should be established in consideration of the color rendering of the cationic dye and the toughness of the fiber.

The cationic dyeable modified cellulose regenerated fiber can be prepared by incorporation with an insoluble polymer which is obtained by crosslinking a dihydroxydiphenylsulfone-sulfonate condensate with an epoxy compound having at least two epoxy groups in the molecule. It is preferable since it can be dyed, similarly to cellulose fiber, with direct dyes or reactive dyes.

The dyeing process and the dyeing-finishing process in accordance with the present invention consist in the dyeing of the textile material containing regenerated cellulose-modified fiber that can be dyed with cationic dyes alone or in combination with dyes other than cationic dyes by bath dyeing. unique. For dyes other than cationic dyes, direct dyes and reactive dyes are preferred. The dye is intended to form the scattered pattern, the dungaree pattern, the cambri pattern, the squared pattern or the striped pattern. Dyeing is followed by washing. In case it is desirable to dye the modified cellulose regenerated fiber and leave another fiber undyed, the dyeing can be carried out using cationic dyes alone. In case it is desirable to dye both the modified cellulose regenerated fiber and the other fiber, the dyeing can be accomplished using a dye solution containing the cationic dyes and the direct dyes or reactive dyes, and the dyeing is followed by washing.

The concentration of each dye varies depending on the desired color. An adequate amount of cationic dyes should be established based on the weight of the modified cellulose regenerated fiber, since the cationic dyes are received from the modified cellulose regenerated fiber. An adequate amount of direct dyes or reactive dyes should be established on the basis of the total weight of the textile material, since direct dyes and reactive dyes are received by all types of fibers.

The dyeing process according to the present invention is followed by the sequential treatment with an aqueous solution of tannic acid, and after that with an aqueous solution of emetic tartaric. This treatment is designed to improve color fastness. Therefore the specified order of treatment should be observed and the two aqueous solutions should be used in sequence; otherwise the dye will not be firmly attached to the fiber.

The aqueous solution of the tannic acid is usually adjusted to pH 3-6, preferably pH 4-5, with acetic acid. The concentration of the tannic acid to be received by the dyed fiber is usually 1.5-7% by weight, preferably 2-6% by weight, based on the weight of the dyed fiber. At a concentration of less than 1.5% by weight, the tannic acid does not produce the desired color fastness. With a concentration greater than 7% by weight, the tannic acid causes the cationic dyes to stain the undyed fiber. The treatment should be carried out at 30-90 ° C, preferably 50-70 ° C, for 10-60 minutes, preferably 20-40 minutes. The treatment with an aqueous solution of the tannic acid is followed by washing and then by the treatment with an aqueous solution of emetic tartar adjusted to pH 3-6, preferably pH 4-5, with acetic acid.

Treatment with an aqueous solution of emetic tartar is intended to cause the tannic acid to adhere firmly to the dyed fiber. The concentration of emetic tartar which is received by the dyed fiber should usually be 0.5-2.5% by weight, preferably 0.75-2% by weight, based on the weight of the dyed fiber. The treatment should be carried out at 30-90 ° C, preferably 50-70 ° C, for 10-60 minutes, preferably 20-40 minutes. The treatment with the aqueous solution of emetic tartar is followed by washing and then drying at 80-120 ° C.

After the aforementioned treatments, the fabric obtained is optionally subjected to cross-linking treatment with resins reactive towards cellulose to reduce shrinkage upon washing and pressing and to improve washing and use characteristics. This treatment causes crosslinking between the tannic acid and the cellulose molecule and between the cellulose molecules. Such resins include, for example, N-methylol compounds such as dimethylol ethylene urea, dimethylol dihydroxyethylene urea, dimethylol alkylcarbamate, dimethylol dimethoxyethylene urea methylated, etc., epoxy compounds such as polyalkylene glycol diglycidyl ether, glycerin diglycidylether, etc. diphenylmethane diisocyanate, etc., and vinylsulfone derivatives, exemplified by bis- {3-hydroxyethylsulfone. If necessary the resin can be used in combination with a hardener, softener, strength improver, hand regulator, etc.

Among these examples, the N-methylol compounds are preferable since the other compounds have their drawbacks as set forth below. Epoxy compounds are not as stable when stored as a solution containing a catalyst. Additionally they cause discoloration of the dyed product when they are used in combination with a metal borofluoride as a catalyst. Isocyanate compounds tend to cause discoloration over time and with heating. Additionally they are comparatively expensive and therefore not cheap. The vinylsulfone derivatives lower the resistance of the dyed product and require an alkaline catalyst and heat, which oxidize the cellulose to form polyoxycarboxylic acid derivatives. This makes it necessary to subject the dyed product with a light bright color to bleaching after finishing.

The quantity of the resin can be determined in accordance with the application of the textile materials to be dyed and finished. It is usually 2-6% by weight, preferably 2.5-4% by weight, on the weight of the textile material in consideration of the color fastness with the cationic dyes, washing shrinkage, tear resistance and burst resistance. The treatment is usually carried out by the dry curing method with filling in such a way that the resin is completely impregnated into the textile material. After treatment, the textile material is squeezed by rolling with a collection of 70-80% and then dried at 80-120 ° C and heated to dryness at 130-180 ° C.

The duration of the heat treatment is not specifically limited to the point where it is long enough for sufficient crosslinking to occur. It can be suitably established in accordance with the unit area weight of the textile material. Then the resin treated textile material is subjected to soaping, washing, drying and possibly oil treatment in the usual way. The treatment with resin will not cause the dye to escape from the fabric: dyed by virtue of the treatment with tannic acid and with: emetic tartar that precedes the treatment with the resin. In accordance with the present invention, it is possible to dye a textile material formed of regenerated cellulose fiber, modified and any type of regenerated cellulose fiber, cotton and wool, with cationic dyes alone or in combination with direct dyes or reactive dyes other than cationic dyes by the single bath dyeing method, thus forming the scattered pattern, the dungaree pattern, the cambri pattern, the squared pattern or the striped pattern. The modified cellulose regenerated fiber acquires dyeability with cationic dyes since it contains an insoluble polymer which is obtained by cross-linking a dihydroxydiphenylsulfone-sulfone condensate with epoxy compounds having at least two epoxy groups in the molecule.

Additionally, after dyeing with cationic dyes, the modified cellulose regenerated fiber firmly captures the tannic acid if it is sequentially treated with an aqueous solution of tannic acid and then treated with an aqueous solution of emetic tartar. Furthermore, after dyeing and treatment with the aqueous solution of tannic acid and the aqueous solution of emetic tartar, the textile material containing the regenerated modified cellulose fiber is improved in color fastness and in the washing and use characteristics if it is treated with a reactive resin with cellulose.

The present invention provides the dyeing and dyeing-finishing process of textile material containing modified cellulose regenerated fiber which is superior in color fastness for cationic dyes, washing and use characteristics, washability without shrinkage and without deterioration of strength, hand, color fixing, and colorability without deformation, staining of undyed parts, and smudging. The process of the present invention is suitable for the dyeing and dyeing-finishing of a large variety of products, each in small batches.

The invention will be described in greater detail with reference to the following examples, which are not intended to limit the scope of the invention. Using the test methods explained below, the samples were tested for color fastness, wash shrink, press shrink, wash and use characteristics, tear strength, burst strength, hand, color fastening and dyeability.

Color fastness:

Rubbing (dry / wet): JIS L-0849-1971

Light: JIS L-0842-1988 (20 hour exposure) Transudation (acidic, alkaline): JIS L-0848-1978, Method A

Washing: JIS L-0844-1986

Shrinkage on washing: JIS L-1042-1992,

Method F3 (centrifuge drying, drying) Shrinkage on pressing: JIS L-1042-1992, Method H-3 Washing characteristics and use: JIS L-1096-1979, 6.23,

Method A (Centrifuge Dry) Tear Strength: JIS L-1096-1979, 6.15.5, Method D Burst Strength: JIS M-1018-1990, Method A (Mullen Type)

Hand: sensory test by the five participants © (Good): all five participants agree

O (Fair): 4 or 3 participants agree

Λ (Poor): 2 or 1 participant agree

X (Bad): none of the five participants agrees. Color fixation: the color of the resin solution before treatment is compared to that after treatment through the sensory knowledge of five participants.

@ (Good): all participants recognize no color variation

0 (Fair): 4 or 3 participants recognize no color variation

/ \ (Poor): 2 or 1 participant recognize no color variation

X (Bad): All participants recognize the color variation.

Dyeability: sensory test by five participants in relation to staining, design deformation, uneven dyeing and smudging.

© (Good): All participants agree

O (Fair): 4 or 3 participants agree

/ \ (Poor): 2 or 1 participant agree

X (Bad): none of the participants agree.

Example 1

Dihydroxydiphenylsulfone sulfonate was prepared by adding sodium hydroxide to 400 parts by weight of an aqueous solution of dihydroxydiphenyl sulfonate condensate ("Nylox 1500"), 40% active ingredient, from Ipposha Yushi Kogyo Co., Ltd.). The dihydroxydiphenylsulfone-sulfonate was added to crosslink 55 parts by weight of diglycidyl ether resorcinol ("Denacol EX-201", having an epoxy equivalent of 118, from Nagase Kasei Co., Ltd.), and 65 parts by weight of neopentylglycol diglycidyl ether (" Denacol EX-211 ", having an epoxy equivalent of 140, from Nagase Kasei Co., Ltd.). The amount of the crosslinking agent is such that the hydroxy equivalents of the dihydroxydiphenylsulfone-sulfonate condensate couple with the total epoxy equivalents of the crosslinking agents.

After addition of water, the mixture of the dihydroxyphenylsulfone-sulfonate condensate and crosslinking agents was completely dispersed using a homogenizer, and the aqueous dispersion was adjusted to pH 8.0 with sodium hydroxide. The total amount of water and sodium hydroxide added was 479 parts by weight. The aqueous dispersion was stirred at 50 ° C for 6 hours to produce an aqueous dispersion of a crosslinked dihydroxydiphenylsulfone-sulfonate condensate polymer.

This aqueous solution was added to a polynosic viscose obtained in the usual manner immediately prior to spinning, so that it amounted to 40% by weight of the cellulose weight. After the usual spinning, a modified polynosic fiber, 1.25 denier, 38 mm was obtained.

The modified polynosic fiber was spun blended with polynosic fiber (1.25 denier, 38 mm) in a mix ratio of 30% to 70% to give a blended yarn (40 :). The blended yarn was woven into a plain weave fabric (110 warps / inch and 75 wefts / inch}. The plain weave fabric was carbonated, desizing, washing, bleaching, mercerizing, washing and drying in the usual manner.

Plain weave fabric was placed in a jet dye machine and dyed with a dye solution, as specified below, at 100 ° C for 40 minutes, with a fabric to dye solution ratio of 1:30 .

Composition of the dye solution:

. Cationic blue dye ("Astrazen Blue F2RL", from Hodogaya Kagaku Kogyo Co., Ltd.), 1.5% owf (for modified polynosic fiber)

. Cationic Orange Dye ("Cathilon Orange RH Liq", from Hodogaya Kagaku Kogyo Co., Ltd.), 1.3% owf (for modified polynosic fiber)

. Cationic yellow dye ("Cathilon Yellow 3GLH", from Hodogaya Kagaku Kogyo Co., Ltd.), 0.8 owf (for modified polynosic fiber)

Sodium lauryl sulfate, 1% owf (for modified polynosic fiber)

. Dispersing agent ("Daidesupaa X-45", from Ipposha Yushi Kogyo Co., Ltd.), 2% owf (for modified polynosic fiber) Acetic acid: 0.5 g / L

Sodium acetate: 0.25 g / L

pH 4.0

The dyeing was followed by washing and drying. In this way, a plain weave fabric with a scattered design was obtained with only the modified polynosic fiber dyed in black. It is called Sample No. 1

The modified polynosic fiber mentioned above was spun mixed with polynosic fiber and wool (Wool Bumtop (66 '), 38 mm) in a mix ratio of 45%, 25% and 30%, to give a blended yarn (v30' <s >). The yarn was knitted into a knitted fabric using a single tubular knitting machine (26 inch, 28 gauge, 2088 needles) manufactured by Fukuhara Seiki Co., Ltd.

The knitted fabric was placed in a jet dye machine and washed and bleached with a solution as specified above, at 95 ° C for 30 minutes, with a fabric to dye solution ratio of 1:30.

Composition of the solution:

. Hydrogen peroxide (35%): 4 g / L

. Stabilizer ("Haipaa" from Daito Yakuhin Co., Ltd.): 1 g / L

Sodium carbonate: 2 g / L

• Penetrating agent ("Daisaafu P-30" from Dai-ichi Kogyo Seiyaku Co., Ltd.): 0.5 g / L

The washing and bleaching step was followed by washing and drying.

Then the fabric obtained was dyed with a dye solution as specified below, at 100 ° C for 40 minutes, with a ratio of fabric to dye solution which was 1:30.

Composition of the dye solution:

. Red cationic dye ("Astra Phloxine FF conc", from Hodogaya Kagaku Kogyo Co., Ltd.), 0.25% owf (for modified polynosic fiber)

. Cationic yellow dye ("Cathilon Yellow 7GLH", from Hodogaya Kagaku Kogyo Co., Ltd.), 0.5% owf (for modified polynosic fiber)

. Sodium lauryl sulfate, 1% owf (for modified polynosic fiber)

. Dispersing agent ("Daidesupaa X-45", from Ipposha Yushi Kogyo Co., Ltd.), 2% owf (for modified polynosic fiber). Acetic acid: 0.5 g / L

Sodium acetate: 0.25 g / L

pH 4.0

The dyeing was followed by washing and drying. A knitted fabric with a scattered design was thus obtained with only the modified polynosic fiber dyed in red. It is called Sample No. 2.

The aforementioned modified polynosic fiber was extruded into a yarn (50 '<s>). The modified polynosic fiber yarn in combination with the polynosic fiber yarn (50 ') was woven into a plain weave fabric, with 144 warps and 82 wefts per inch. Ten yarns of each type were alternately arranged in both warps and wefts. The plain weave fabric was subjected to gassing, desizing, washing, bleaching, mercerizing, washing and drying in the usual manner.

The plain weave fabric was placed in a jet dye machine and dyed with a dye solution as specified below, at 100 ° C for 40 minutes, with the ratio of fabric to dye solution being 1:30.

Composition of the dye solution:

. Cationic blue dye ("Astrazen Blue F2RL" 200%, from Hodogaya Kagaku Kogyo Co., Ltd.) 1.2% owf (for modified polynosic yarn)

. Direct yellow dye ("Kayarus Supra Yellow GSL", from Nippon Kagaku Co., Ltd.), 0.2 owf

Sodium lauryl sulfate, 1% owf (for modified polynosic yarn)

. Dispersing agent ("Daidesupaa X-45", from Ipposha Yushi Kogyo Co., Ltd.), 2% owf (for modified polynosic yarn)

Acetic acid: 0.5 g / L

Sodium acetate: 0.25 g / L

Sodium sulphate: 10 g / L

pH 4.0

The dyeing was followed by washing and drying. Thus a plain weave fabric with a checkered design was obtained, with the modified polynosic yarn dyed in navy blue with the cationic dye and the direct dye and the polynosic yarn dyed in light yellow with the direct dye. It is called Campione li. 3.

The aforementioned yarn (50 ') of modified polynosic fiber in combination with a cotton yarn (50') was woven into a plain weave fabric, with 144 warps and 82 wefts per inch. Ten yarns of each type were arranged alternately in both warps and wefts. The plain weave fabric was subjected to gassing, desizing, washing, bleaching, mercerizing, washing and drying in the usual manner.

The plain weave fabric was dyed with a dye solution as specified below, at 100 ° C for 40 minutes, with the ratio of fabric to dye solution being 1:30.

Composition of the dye solution:

Cationic blue dye ("Cathilon Blue F2RL" 200%, from Hodogaya Kagaku Kogyo Co., Ltd.), 1.2% owf (for modified polynosic yarn)

Red reactive dye ("Kayaselon React Red CN-RB", from Nippon Kayaku Co., Ltd.), 0.2% owf

. Buffer ("Kayaku Buffer AC", from Nippon Kayaku Co., Ltd.), 1.5 g / L

Sodium lauryl sulfate, 1% owf (for modified polynosic yarn)

. Dispersing agent ("Daidesupaa X-45", from Ipposha Yushi Kogyo Co., Ltd.), 2% owf (for modified polynosic yarn)

. Acetic acid: 0.5 g / L

. Sodium acetate: 0.25 g / L

. Sodium sulphate: 20 g / L

pH 4.0

The dyeing was followed by washing and drying. Thus a plain weave fabric with a checkered design was obtained, with the modified polynosic yarn dyed in blue with the cationic dye and the reactive dye and the cotton yarn dyed in light pink with the reactive dye. It is called Sample No. 4. Samples No. 1 to 4 were tested for dyeability. The results are reported in Table 1.

Table 1

From Table 1 it is noted that the textile material containing the modified polynosic fiber or yarn is easily dyeable by the single-bath dyeing method without uneven dyeing, staining and smearing when dyed with a dye solution containing only one cationic dye or dye. cationic in combination with a direct dye or reactive dye other than cationic dyes. In other words, all samples are superior in dyeability and capable of cross-staining.

Example 2

Seven samples of sparse pattern woven materials were prepared for dyeing in the same manner as Sample No. 1 in Example 1. Each of them was treated with an aqueous solution containing tannic acid in different concentration as specified below, adjusted to pH 4 0 with acetic acid, at 70 ° C for 30 minutes, with a ratio of fabric to dye solution which was 1:30. This treatment was followed by washing. Concentration of tannic acid in the treatment solution: 1.0%, 1.5%, 2.0%, 5.0%, 6.0%, 7.0%, 8.0% owf for modified polynosic fiber . Each of the treated samples was further treated with an aqueous solution containing emetic tartar in different concentrations as specified below, adjusted to pH 4.0 with acetic acid, at 70 ° C for 30 minutes, with a ratio of tissue to dye solution. that was 1:30. This treatment was followed by washing and drying. Concentration of emetic tartar in the treatment solution: 0.3%, 0.5%, 0.75%, 1.5%, 2.0%, 2.5%, 3.0% owf for modified polynosic fiber.

Thus Samples Nos. 1-1 to 1-7 were obtained which carry tannic acid and emetic tartar. They were tested for color fastness and dyeability. The results are shown in Table 2.

Table 2

In Table 2 it is noted that the treatment with tannic acid and after this treatment with emetic tartar impart a good color fastness and dyeability to the modified polynosic fiber when the concentration of the tannic acid solution is 1.5-7% owf and of the emetic tartar solution is 0.5-2.5% owf, respectively, for the modified polynosic fiber.

Example 3

Six samples of woven materials with a pattern scattered by dyeing and subsequent processing were prepared

as for samples No. 1-4 in Example 2. The first of them was treated with a finishing solution as indicated below by filling, with the collection yield being 70%.

Composition of the finishing solution:

. Compound N-methylol ("Riken Resin RG-10E", 50% active ingredient, from Miki-Riken Kogyo Co., Ltd.): 80 g / L. Catalyst ("Riken Fixer MX-18", from Miki-Riken Kogyo Co., Ltd.): 25 g / L

. Silicone softening agent ("Raitosirikon A-544", from Kyoeisha Kagaku Co., Ltd.): 50 g / L

. Polyolefin softening agent ("Mabozoru PO", from Matsumoto Yushi Seiyaku Co., Ltd.): 20 g / L

This treatment was followed by drying at 120 ° C for 1 minute and heat treatment at 165 ° C for 1.5 minutes. Thus a finished plain weave fabric was obtained having a sparse pattern. It is called Sample N.

1-4-1.

The dyeing-finishing process mentioned above consists in the treatment with aqueous solution of tannic acid, treatment with aqueous solution of emetic tartar, and treatment with resin, which are carried out in sequence. For comparison purposes, five samples were prepared in the same manner as described above except that any one or two of the three treatments were omitted or the order of treatments was changed as follows. Sample No. 1-4-2: no treatment with heme tartar and resin.

Sample No. 1-4-3: no treatment with haemetic tartar.

Sample No. 1-4-4: with the order of treatments varied as follows: sequential treatments with emetic tartar -> tannic acid -> resin.

Sample No. 1-4-5: with the order of treatments varied as follows: simultaneous treatment with a mixed solution of tannic acid and emetic tartar and subsequent treatment with resin.

Sample No. 1-4-6: with the order of treatments varied as follows: sequential treatments with resin - * tannic acid - emetic tartar. ; Samples Nos. 1-4-1 through 1-4-6 were tested for color fastness, wash and press shrinkage, wash and use characteristics, tear resistance, hand, color fixation and dyeability. The results are shown in Table 3.; Table 3; ; From Table 3 we note the following. Sample No.; 1—4—2 is poor in color fastness, shrinkage when washing and pressing, washing and use characteristics, hand and dyeability due to the omission of treatments with emetic tartar and resin. Samples Nos. 1-4-3 through 1-4-5 are poor in color fastening, color fastness and dyeability. Sample No. 1-4-6 is very poor in color fixing and slightly poor in color fastness and dyeability. On the other hand, Sample No. 1-4-1 in accordance with the present invention is superior in color fixing given the sequential treatments with tannic acid and emetic tartar and is also superior in color fastness, shrinkage upon washing and pressing, characteristics of washing and use, tear resistance, burst resistance, hand, and dyeability given the treatment with the resin. ; Example 4; A knitted fabric of scattered design was prepared in the same manner as Sample No. 2 in Example 1. The knitted fabric was treated at 70 ° C for 30 minutes with an aqueous solution containing tannic acid, 5 % owf (for modified polynosic fiber), adjusted to pH 4.0 with acetic acid, with the ratio of fabric to tannic acid solution being 1:30. The treatment was followed by washing. The fabric was further treated at 70 ° C for 30 minutes with an aqueous solution of emetic tartar, 1.5% owf (for the modified polynosic fiber), adjusted to pH 4.0 with acetic acid, with the ratio of fabric to solution. of emetic tartar which was 1:30. The treatment was followed by washing and drying. The fabric was then treated with a finishing solution as specified below, by filling, with the collection being 80%. ; Finishing solution composition:; N-methylol compound ("Sumitex Resin NS-10", 45% active ingredient, from Sumitomo Chemical Industry Co., Ltd.): 100 g / L;. Magnesium chloride complex based catalyst ("Sumitex Accelerator X-80", from Sumitomo Chemical Industry Co., Ltd-J: 30 g / L; Aminosilicone softening agent ("Nikkasirikon AM-202", from Nikka Kagaku Co., Ltd .): 20 g / L; Polyethylene softening agent ("Yodozoru PE-400", from Kanebo NSC Co., Ltd.): 15 g / L; Formalin blocker ("Faidekkusu FCK", from Dainippon Ink & Chemicals, Ine. ): 5 g / L; This treatment was followed by drying at 120 ° C for 1 minute and heat treatment at 165 ° C for 1.5 minutes. After oiling a finished knitted fabric was obtained. It is called Sample No. 2-1 This sample was tested for color fastness, wash shrinkage, wash and use characteristics, tear resistance, hand, color fastening and dyeability The results are shown in Table 4.; Table 4; ; ;; From Table 4 it can be seen that Sample N. 2-1 is superior in color fixing given the sequential treatments with tannic acid and after this treatment with emetic tartar and is also superior in color fastness, shrinkage when washing, washing characteristics and use, tear resistance, hand and dyeability, given the treatment with resin. ; Example 5; Five spools of the same plain weave fabric as Sample No. 3 in Example 1 were treated at 70 ° C for 30 minutes with an aqueous solution containing tannic acid, 5% owf (for the modified polynosic yarn), adjusted pH 4.0 with acetic acid, with a ratio? between fabric and tannic acid solution which was 1:30. The treatment was followed by washing. The fabric was further treated at 70 ° C for 30 minutes with an aqueous solution of emetic tartar, 1.5% owf (for the modified polynosic yarn), adjusted to pH 4.0 with acetic acid, with a tissue to solution ratio of emetic tartar which was 1:30. The treatment was followed by washing and drying. Thus, five coils of plain weave fabric with a checkered pattern were obtained which were treated with tannic acid and emetic tartar after dyeing. Five types of resin treatment solutions were prepared in accordance with the following formulation. . Compound N-methylol ("(Sumitex Resin N-10", 45% active ingredient, from Sumitomo Chemical Industry Co., Ltd .: 63.5g / L, 80g / L, 90g / L, 127g / L , and 190 g / L;. Catalyst based on magnesium chloride complex ("Sumitex Accelerator X-80", from Sumitomo Chemical Industry Co-, Ltd.j: 30 g / L;. Aminosilicone softening agent ("Nikkasirikon AM-202 ", from Nikka Kagaku Co., Ltd.}: 20 g / L;. Polyethylene softening agent (" Yodozoru PE-400 ", from Kanebo NSC Co., Ltd.}: 15 g / L; Formalin blocker (" Faindekkusu FCK ", from Dainippon Ink & Chemicals, Inc.}: 5 g / L; Each coil of the aforementioned plain weave fabrics was treated with the aforementioned resin by filling, with a collection which was 703⁄4. This treatment was followed by the drying at 120 ° C for 1 minute and by heat treatment at 165 ° C for 1.5 minutes and by oiling. Thus samples of plain weave fabrics finished with a checkered pattern were obtained. They are called samples No. from 3- 1 a 3-5. ; These samples were tested for color fastness, wash and press shrinkage, wash and use characteristics, tear resistance, color fixation, hand and dyeability. The results are shown in Table 5.; Table 5; ;; From Table 5 it is noted that plain weave fabric composed of modified polynosic yarn and polynosic yarn as arranged in ten yarns each alternately in both warps and wefts, was capable of cross-dyeing with a cationic dye and a direct dye. Treatment with tannic acid (5% owf) and emetic tartar (1.5% owf) for the polynosic yarn improves color fixing. Furthermore, the treatment with a cellulose reactive resin (2-6% owf) improves the fabric in relation to color fastness, shrinkage when washed, washing and use characteristics, hand and dyeability. Sample N. 3-1 is slightly poor in relation to the washing and use characteristics since the quantity of resin fixed is slightly small. Sample No. 3-5 is slightly poor in tear strength and hand as the amount of resin fixed is slightly high. ; Example 6; Five spools of the same plain weave fabric as sample No. 4 in Example 1 were treated at 70 ° C for 30 minutes with an aqueous solution containing tannic acid, 5% owf (for the modified polynosic yarn) , adjusted to pH 4.0 with acetic acid, with the ratio of fabric to tannic acid solution being 1:30. The treatment was followed by washing. The fabric was further treated at 70 ° C for 30 minutes with an aqueous solution of emetic tartar, 1.5% owf (for the modified polynosic yarn), adjusted to pH 4.0 with acetic acid, with the ratio of fabric to solution of emetic tartar which was 1:30. The treatment was followed by washing and drying. Thus, five spools of plain weave fabric with a checkered pattern were obtained which were treated with tannic acid and emetic tartar after dyeing. Five types of resin treatment solutions were used, prepared in accordance with the following formulation. ;. Compound N-methylol ("Riken Resin RG-10E", 50% active ingredient, from Miki Riken Kogyo Co., Ltd.): 57 g / L, 72 g / L, 86 g / L, 114 g / L and 171 g / L;. Catalyst ("Riken Fixer MX-18", from Miki Riken Kogyo Co., Ltd.): 25 g / L; Silicone softening agent ("Raitosirikon A-544", from Kyoeisha Kagaku Co., Ltd.): 50 g / L ;. Polyolefin softening agent ("Mabozoru PO", from Matsumoto Yushi Seiyaku Co., Ltd.): 20 g / L; Each coil of the aforementioned plain weave fabrics was treated with the aforementioned resin solution by filling, with the collection which it was 70%. This treatment was followed by drying at 120 ° C for 1 minute and heat treatment at 165 ° C for 1.5 minutes and oiling. Thus samples of plain weave fabrics finished with a checkered pattern were obtained. They are called Champions No. 4-1 to 4-5. ; These samples were tested for color fastness, wash and press shrinkage, wash and use characteristics, tear resistance, color fixation, hand and dyeability. The results are shown in Table 6.; Table 6; ;; From Table 6 it is noted that plain weave fabric composed of the modified polynosic yarn and polynosic yarn as arranged in 10 yarns each alternately in both warps and wefts was capable of cross-dyeing with a cationic dye and a reactive dye. Treatment with tannic acid (5% owf) and emetic tartar (1.5% owf) for the modified polynosic yarn improves color fixation. Furthermore, the treatment with a reactive resin with cellulose (2-6% owf) improves the fabric in relation to color fastness, shrinkage when washed, washing and use characteristics, hand and dyeability. Sample No. 4-1 is slightly poor in washing and use characteristics since the quantity of resin fixed is slightly small. Sample No. 4-4 is slightly poor in tear strength and hand as the amount of resin fixed is slightly high. ; Example 7; The modified polynosic yarn (50 '<s>) obtained in the same manner as Example 1 and the polynosic yarn (50') were woven into a plain weave fabric, with 144 warps and 82 wefts per inch. The yarns of each type were arranged alternately in both warps and wefts. The plain weave fabric was subjected to gassing, desizing, cleaning, bleaching, mercerizing, washing and drying in the usual manner. ; Plain weave fabric was placed in a jet dye machine and dyed with a dye solution as shown below, at 100 ° C for 40 minutes, with the ratio of fabric to dye solution being 1:30 . ; Composition of the dye solution:;. Cationic blue dye ("Cathilon Blue 3GLH", from Hodogaya Kagaku Kogyo Co., Ltd.), 1.0% owf (for modified polynosic yarn); Sodium lauryl sulfate, 1% owf (for modified polynosic yarn);. Dispersing agent ("Daidesupaa X-45", from Ipposha Yushi Kogyo Co., Ltd.), 2% owf (for modified polynosic yarn); Acetic acid: 0.5 g / L; Sodium acetate: 0.25 g / L;. ph'4,0; Dyeing was followed by washing. Thus a plain weave fabric with a checkered design was obtained, with the modified polynosic yarn dyed in turquoise blue, and the polynosic yarn which remained undyed. ; The resulting fabric was treated at 70 ° C for 30 minutes with an aqueous solution containing tannic acid, 2% owf (for modified polynosic yarn), adjusted to pH 4.0 with acetic acid, with the ratio of fabric to solution of tannic acid which was 1:30. The treatment was followed by washing. The fabric was further treated at 70 ° C for 30 minutes with an aqueous solution of emetic tartar, 0.75% owf (for modified polynosic yarn), adjusted to pH 4.0 with acetic acid, with the ratio of fabric to solution of emetic tartar which was 1:30. The treatment was followed by washing and drying. ; The fabric was treated with a solution with the following formulation, by filling, with the collection being 80%. ; Compound N-methylol ("Riken Resin RG-10E", 50% active ingredient, from Miki Riken Kogyo Co., Ltd.): 10 g / L;. Catalyst ("Riken Fixer MX-18", from Miki Riken Kogyo Co. Ltd.): 25 g / L;. Silicone softening agent ("Raitosirikon A-544", from Kyoeisha Kagaku Co., Ltd.): 50 g / L;. Polyolefin softening agent ("Mabozoru PO", from Matsumoto Yushi Seiyaku Co., Ltd.): 20 g / L; Resin treatment was followed by drying at 120 ° C for 1 minute and heat treatment at 165 ° C for 1 , 5 minutes and from oiling. Sample No. 5 was thus obtained. This sample was tested for color fastness, washing and pressing shrinkage, washing and use characteristics, tear resistance, hand, color fastening and dyeability. The results are shown in Table 7.; Table 7 ;; ;; From Table 7 it is noted that the plain weave fabric composed of the modified polynosic yarn and the polynosic yarn was capable of cross-dyeing with a cationic dye which dyes only the former. Treatment with tannic acid (2% owf) and emetic tartar (0.75% owf) for modified polynosic fiber yarns improves color fixation. Furthermore, the treatment with a reactive resin with cellulose (4% owf) improves the fabric in relation to color fastness, shrinkage to washing, washing and use characteristics, tear resistance, hand and dyeability. ; Example 8; The modified polynosic fiber obtained in Example 1 was transformed into yarn (20 <'s>). This warp yarn and polynosic yarn (20 '<s>) for wefts were woven in a diagonally woven fabric, with 105 warps and 58 wefts per inch. The diagonally woven fabric was subjected to gassing, desizing, washing, bleaching, mercerizing, washing and drying in the usual manner. ; The diagonal weave fabric was placed in a jet dyeing machine and dyed with a dye solution under the same conditions as in Example 7. A diagonal fabric with a rough canvas design was thus obtained, with the modified polynosic yarn dyed in turquoise blue and the polynosic yarn that remained undyed. ; The diagonal fabric was treated with tannic acid and emetic tartar in the same manner as in Example 7, except that the tannic acid concentration ranged from 2% owf to 6% owf and the emetic tartar concentration ranged from 0.753⁄4 owf to 2% owf and the resin concentration ranged from 100 g / L to 50 g / L. Sample No. 6 was thus obtained, with only the modified polynosic yarn dyed in turquoise blue for the rough canvas design. This sample was tested for color fastness, wash and press shrinkage, wash and use characteristics, tear resistance, hand, color fixation and dyeability. The results are shown in Table 8.; Table 8 ;;; ;; : From Table 8 it can be seen that the diagonal fabric composed of modified polynosic yarns for the warps and polynosic fiber yarns for the wefts, and dyed in the raw canvas design is superior in color fixing, color fastness, shrinkage on washing and pressing , washing and use characteristics, tear resistance, hand and dyeability if the modified polynosic fiber is dyed with a cationic dye using a single bath dyeing method and the fabric is treated with tannic acid (6% owf) and emetic tartar ( 2% owf) for the modified polynosic fiber and further treated with a cellulose reactive resin (2% owf). *

Claims (6)

CLAIMS 1. Process for dyeing textile materials which contain modified cellulose regenerated fiber capable of dyeing with cationic dyes and "at least one type of fiber selected from ordinary regenerated cellulose fiber, cotton and wool, said process comprising the dyeing of said textile materials containing regenerated cellulose fiber modified with dyeing solution containing cationic dyes alone or containing cationic dyes and dyes other than cationic dyes, by single bath dyeing method, to form the scatter pattern, the dungaree pattern, the pattern of cambri, the squared design, or the striped design. 2. A process for dyeing textile materials according to claim 1, wherein said process comprises the dyeing of textile materials containing regenerated cellulose fiber modified with a dye solution containing cationic dyes alone or containing cationic dyes and different dyes. by cationic dyes, by the single-bath dyeing method, to form the scattered pattern, the dungaree pattern,. the design of cambri, the squared design, or the striped design, and the treatment of the textile material dyed in sequence with an aqueous solution of tannic acid, and after this an aqueous solution of emetic tartar. 3. A process for dyeing textile materials according to any one of claims 1 and 2, wherein said regenerated modified cellulose fiber is one which contains an insoluble polymer which is obtained by crosslinking a dihydroxyphenylsulfone-sulfonate condensate with epoxy compounds having at least two epoxy groups in the molecule. 4. Process for dyeing-finishing-of textile materials containing modified cellulose regenerated fiber capable of dyeing with cationic dyes and at least one type of fiber selected from ordinary cellulose regenerated fiber, cotton and wool, said process, including dyeing of textile materials containing, the regenerated cellulose fiber modified with a dyeing solution containing cationic dyes from, alone or containing cationic dyes and dyes other than cationic dyes, by the single bath dyeing method, to form the scattered drawing, dungaree drawing, 'drawing textiles according to claim 4, wherein the cellulose reactive resin is a cellulose reactive resin based on N-methylol. 6. A textile dyeing-finishing process according to any one of claims 4 and 5, wherein the regenerated modified cellulose fiber is one which contains an insoluble polymer which is obtained by crosslinking a dihydroxydiphenylsulfonesulfonated condensate with epoxy compounds having at least two groups epoxies in the molecule.