JPH0791789B2 - Method for dyeing and printing cationized modified cellulose fiber material - Google Patents

Description

The present invention relates to a method for dyeing or printing a cationized modified cellulosic fiber with a reactive dye.

<Prior Art> Conventionally, for the purpose of diversifying design effects in dyeing, pre-dyed cotton or yarn and undyed cotton or yarn are spun and woven to make ovboro tone, cyan tone, different tone, dark and light tone. Have been dyed.

On the other hand, in order to obtain this kind of effect for woven cloth, the purpose is achieved by using a dye capable of dyeing one fiber with a mixed spun and mixed woven cloth of different fibers, but this effect is not obtained with a single fiber. It was supposed to depend on woven technology to seek.

Recently, for the purpose of speeding up the processing, cellulosic fibers are cation-modified with a cationizing agent, for example, a cationizing agent having a chlorohydrin group, in the state of cotton or yarn, and 15 to 50% ( (Weight) It is possible to achieve the purpose by preparing a mixed and woven fabric in advance and dyeing or printing it with a dye that can dye modified fibers. Attention has been paid.

<Problems to be Solved by the Invention> However, in general, the reactive dyes and acid dyes and metal complex salt type dyes that have been attempted in the past have poor wet fastness, and even after post-treatment with a fixing agent, the wet fastness is improved. However, it is pointed out that it is not possible to cope with the case where a high degree of fastness is required, because the degree of light fastness is decreased.

The present inventors have excellent build-up properties in addition to wet fastness, light fastness, such as water, sweat, and washing, which are important in dyeing and printing cationized modified cellulosic fibers,
In addition, as a result of intensive studies on industrially advantageous dyeing and printing methods, they have found that the object can be achieved by using a specific reactive dye, and have reached the present invention.

<Means for Solving Problems> The present invention relates to a method for dyeing and printing a cationized modified cellulosic fiber dye, wherein the following general formula (I): (In the formula, D is a residue of an organic dye having a sulfonic acid group, R ₁
And R ₂ are each independently a hydrogen atom or a C _{1 to} C ₂ alkyl group or hydroxy group, a cyano group, an alkoxy group,
Halogen, carboxy group, a carbamoyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a sulfo group, an optionally C ₁ -C ₄ alkyl group optionally substituted by a sulfamoyl group, A is a methyl group, an ethyl group, a methoxy group, chlorine, bromine Alternatively, phenylene optionally substituted by 1 or 2 substituents of sulfo group or naphthylene group optionally substituted by 1 sulfo group, X is a halogen atom, and Y is a group —SO ₂ CH═CH ₂ Or represents the group --SO ₂ CH ₂ CH ₂ Z,
Here, Z represents a group capable of leaving by the action of an alkali. The present invention provides a method for dyeing and printing a cationized modified cellulosic fiber material, characterized by using a reactive dye represented by

In the present invention, the cationized modified cellulose means cellulose modified by introducing a quaternary ammonium group into cellulose.

The cationized modified cellulosic fiber material used in the present invention can be produced by a known method.

As a cationizing agent used for cationization, chlorhydride
Quaternary ammonium compounds having a phosphorus group (for example, Cl
CH₂CH (OH) CH₂N (CH₃)₃Cl Etc.), epoxy group
Having a quaternary ammonium compound, having a trialkyl group
Quaternary ammonium compound, polycationic compound
Are exemplified.

The cationized modified cellulosic fiber material is, for example, cotton or thread-like cellulosic fiber as a cationizing agent, for example, thionone UK (a quaternary ammonium compound having a chlorohydrin group, on the other hand, a product of Fat & Oil Co., Ltd.) 100 g / caustic soda (flakes). Immersion treatment in a 15g / bath at 80 ° C for 60 minutes, washing with water, neutralization treatment (2-3ml / acetic acid), washing with water and drying, and then mixing modified fiber with a specified amount of unmodified cotton and spinning. It is manufactured by woven or woven the modified yarn in the warp or weft direction and the unmodified yarn in the weft or warp condition.

The blended amount of the modified cotton or yarn is arbitrarily adjusted depending on the design effect, but usually 15 to 50% (by weight) is used.

For the dyeing and printing, the reactive dye represented by the general formula (I) is used in a neutral state, and each method such as exhaust dyeing, cold pad batch dyeing, pad dyeing (steam or baking fixing) and printing (steam fixing) is performed. It can be carried out.

More specifically, the exhaust dyeing method can be carried out, for example, by immersing the fiber material in a dye solution, dyeing it at 60-80 ° C for 30-60 minutes, and then washing with water, soaping, washing with water and drying. Cold pad batch dyeing method, for example,
After impregnating the fiber material with the dye solution (pad solution), squeeze it with a pick-up 60-80%, and squeeze it as it is at room temperature for 10-24.
It can be carried out by leaving it for a time, then washing with water, soaping, washing with water and drying. The pad steam dyeing method includes, for example, impregnating a fiber material in a dye solution (pad solution), squeezing with a pickup of 60-80%, intermediate drying, and steaming at 100-120 ° C for 1-5 minutes or 12
It can be carried out by performing a baking treatment at 0 to 140 ° C. for 3 to 5 minutes, followed by washing with water, soaping, washing with water and drying.

The printing method includes, for example, printing a printing paste containing a dye on a textile material, intermediate drying, steaming at 100-120 ° C. for 3-5 minutes or baking at 120-140 ° C. for 3-5 minutes, and then, It can be carried out by washing with water, soaping, washing with water and drying.

In this case, a dark and light processed product can be obtained by using a small amount of alkali in combination with the dye solution or the printing paste.

If necessary, various agents for the dye pad liquid or the printing paste, for example, disodium salt of ethylenediaminetetraacetic acid as a sequestering agent, sodium metanitrobenzenesulfonate as a reduction inhibitor, migration inhibitor and paste for printing are used. , Sodium alginate, O / W type emulsion, locust bean gum, guar gum, etherified fibrin-derived paste alone or in a mixture, and urea or the like as a wetting / dissolving agent. However, it is desirable to keep the pH of the dye pad solution or the printing paste at 5-7 because of the effect of leaving the unmodified fiber white. On the other hand, in order to lightly dye a part of the unmodified fiber to obtain a deep and light tone, the purpose can be achieved by using an appropriate amount of an alkali agent such as an alkali metal hydroxide or carbonate.

In this way, the use of the reactive dye represented by the general formula (1) can greatly improve the wet fastness, which has hitherto been a problem, and is excellent in light fastness and build-up property. Can be obtained.

Next, the present invention will be specifically described with reference to examples. In the text, parts and% are parts by weight and% by weight, respectively.

Example 1 Cationonone UK (cationizing agent: a product manufactured by Yonesha Yushi Co., Ltd.) 100
1000 parts including 15 parts and 2 parts of caustic soda (flakes) and 2 parts of UDA-104K (cationizing agent leveling agent: Yatasha Yushi Co., Ltd. product)
1 part aqueous solution is prepared. Cotton cotton is dipped in this solution at a bath ratio of 1:20 and treated at 60 ° C. for 60 minutes. Then wash with water, acetic acid 0.3
After applying neutralization treatment at 40 ° C for 5 minutes with a liquid containing parts,
Wash with water and dry.

300 parts of the cotton thus obtained and 700 parts of the unmodified cotton are mixed and spun, and then woven into a warp and an untreated cotton as a weft. Separately a blue reactive dye having the following structure in the form of the free acid After dissolving 10 parts in 370 parts of boiling water and cooling, 5 parts of disodium salt of ethylenediaminetetraacetic acid, 10 parts of sodium metanitrobenzene sulfonate, duck algin NSPM (sodium alginate: product of Kibun Foods) 5% paste 600
Parts and 10 parts of sodium phosphate monobasic (pH adjuster) are added to prepare 1000 parts in total of uniform printing paste.

The printing paste is printed on the cotton cloth, then intermediate drying is performed, and then steaming is performed at 100 ° C. for 5 minutes under saturated steam.

Separately, 5 parts of 5MA-51 (anion-based masking agent: one-sided oil and fat company product), 350 parts of water, 600 parts of 5% paste of duck algin NSPM (sodium alginate: Kibun Food Co., Ltd. product) are added to make a uniform printing of 1000 parts. Prepare the glue.

This print paste is overprinted on the entire surface of the dye print, and 120
Perform intermediate drying at -130 ° C for 3 minutes. Then wash with water,
70 ° C ・ 5 in a soaping bath containing 8g / of bisnol RK (soaping agent for cationized modified cotton: Yatasha Yushi Co., Ltd. product)
After treatment for minutes, wash with water to finish.

By this method, a cyan blue-colored tough blue print was obtained. By the same method, CI Reactive Blue
19 (vinyl sulfone type reactive dye) and CI Reactive Blue 49 (monochlorotriazine type reactive dye) also showed chambray-like results, but they were in a state where they could not be put to practical use due to poor wet fastness to sweat and washing.

The comparative data of fastness are shown in the table.

Example 2 A cotton yarn is cationically modified in the same manner as in Example 1. Next, the modified yarn is woven into the warp yarn, the unmodified yarn is used into the weft yarn, and the interwoven cloth is woven. Separately a navy blue reactive dye having the following structure in the form of the free acid Dissolve 20 parts in 200 parts of boiling water and prepare a dye pad solution with a total of 1000 parts by volume with water. Apply this liquid to the cotton cloth at a liquid temperature of 20-30
Pad with 70% pickup at ℃, wind up and wrap the outer circumference with plastic film, and leave at room temperature 20-25 ℃ overnight.

Then, the product is washed with water, treated with a soaping bath containing 5 g / of bisnol RK (soaping agent for cationized cotton: a product of Yushisha Co., Ltd.) at 90 ° C. for 5 minutes, and washed with water to finish.

By this method a solid navy blue dyeing of ovolo tone is obtained. By the same method, CI Reactive Blue 147 (Vinyl sulfone type reactive dye) and CI Reactive Black 5 (Vinyl sulfone type reactive dye) also show an odor effect, but they have poor wet fastness such as perspiration and washing and are practically used. It was in a state where it could not be provided. The comparative data of fastness are shown in the table.

The test conditions and display are the same as in Example 1.

Example-3 A cationized cotton mixed spun woven fabric is prepared in the same manner as in Example 1.

Separately a red colored reactive dye having the following structure in the form of the free acid After dissolving 10 parts in 200 parts of boiling water and cooling, 50 parts of 2% Duck Algin NSPM (sodium alginate: Kibun Food Co., Ltd. product), 5 parts of primary sodium phosphate and the total amount of 1000 parts by volume of dye pad with water. Prepare the liquid.

Pad this liquid on the cotton cloth with 70% pickup and
Intermediate drying at ℃ for 3 minutes. Next, steaming is performed at 100 ° C for 3 minutes, then treated with a soaping bath containing 5 g / of bisnol RK (soaping agent for cationized cotton: a product manufactured by Yushi Fat & Oil Co., Ltd.) at 90 ° C for 5 minutes and washed with water. Finish.

This process gives a cyan red, fast red dyeing. By the same method, CI Reactable Red 114 (vinyl sulfone type reactive dye) and CI Reactable Red 24 (monochlorotriazine type reactive dye) also show the Schambray effect, but the wet fastness and light fastness of perspiration, washing, etc. It was inferior and could not be put to practical use. The comparative data of fastness are shown in the table. Reactibred 114 and Reactibred 24 are Danfix 505RE (fixing agent for cotton: Nitto Boseki Co., Ltd.) 15g /
After pad-drying, measure various fastnesses ()
As shown in the inside, there was no improvement in the wet fastness, and conversely the decrease in the light fastness was large.

The test method and display are the same as in Example 1.

Example 4 A cationized cotton-blended / woven fabric is prepared in the same manner as in Example 1.

Separately, a golden yellow reactive dye having the following structure in the form of a free acid Soak 10 g of the above cotton cloth (bath ratio 1:20) in a dye solution containing 0.2 g (2% o, w, f) and soda ash 2 g (5 g /) in a total amount of 400 ml, and exhaust dye for 40 minutes at 60 ° C. Do.

Then, the product is washed with water, treated with a soaping bath containing 5 g / of bisnol RK (soaping agent for cationized cotton: a product of Yushisha Co., Ltd.) at 90 ° C. for 5 minutes, and washed with water to finish.

By this method, a deep and light shade of fast yellow dyeing was obtained. By the same method, CI Reactive Yellow 76 (vinyl sulfone type reactive dye) and CI Reactive Orange 5 (monochlorotriazine type reactive dye) also show the same effect, but the wet fastness and light fastness to sweat and washing are poor. It was a thing. The comparative data of fastness are shown in the table.

The test method and display are the same as in Example 1.

Claims (1)

[Claims] 1. A method of dyeing and printing a cationized modified cellulosic fiber material, comprising: (In the formula, D is a residue of an organic dye having a sulfonic acid group, R ₁
And R ₂ are each independently a hydrogen atom or C _{1 to} C ₂ alkyl group or hydroxy group, cyano group, alkoxy group, halogen, carboxy group, carbamoyl group, alkoxycarbonyl group, alkylcarbonyloxy group, sulfo group,
C ₁ -C ₄ alkyl group optionally substituted by sulfamoyl group, A is a phenylene group optionally substituted by 1 or 2 substituents of methyl group, ethyl group, methoxy group, chlorine, bromine or sulfo group. Or a naphthylene group which may be substituted with one sulfo group, X represents a halogen atom, and Y represents a group —SO ₂ CH═CH ₂ or a group —SO ₂ CH ₂ CH ₂ Z, where Z is an alkali. Represents a group capable of leaving by the action of. ) A method for dyeing and printing a cationized modified cellulosic fiber material, which comprises using a reactive dye represented by