JPS6312783A - Method for dyeing and printing cationized modified cellulosic fiber material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention provides a cationized modified cellulose m
This relates to the dyeing or printing method of (a).

<Conventional technology> Conventionally, for the purpose of diversifying the design effects of dyeing, pre-dyed cotton or yarn and undyed cotton or yarn were spun and woven to create ovolo tones, chambray tones, different color tones, dark and light tones. We have obtained dyed products such as

On the other hand, in order to obtain this effect on woven fabrics, dyeing one fiber of a mixed or interwoven fabric with a high degree of heterogeneity and using a vine dye achieves the purpose, but this effect cannot be obtained with single RA fibers. In order to obtain the desired results, it was believed that weaving techniques were required.In order to speed up processing, cellulose fibers were treated with cationizing agents, such as chlorohydrin groups, in the form of cotton yarn. Prepare a woven fabric in advance by cationizing it with a cationizing agent and mixing it with unmodified cotton or thread by 15 to 50% (by weight), dyeing it in Kaiwmya style, and dyeing or printing it with a vine dye. This method is attracting attention as a method that can quickly meet the needs of today's small-volume, high-volume scales.

<Problems to be solved by the invention> However, the reactive dyes and acid dyes F metal complex dyes that have been tried in the past generally have poor wet fastness, and even after post-treatment with a fixing agent, wet fastness is poor. However, it is not suitable for cases where high fastness is required, as there is no improvement in light fastness.

The present inventors have discovered that cationized modified cellulose-based fibers have excellent build-up properties in addition to moisture fastness such as water, sweat, and washing fastness, which are important in dyeing and printing, and light fastness.
Furthermore, as a result of intensive studies on industrially advantageous dyeing and printing methods, it was discovered that the objective could be achieved by using a specific reactive dye, leading to the present invention. The invention relates to a method for dyeing and printing a cationized modified cellulose fiber material, which comprises the following general formula (I), (wherein D is a residue of an organic dye having a sulfonic acid group, R
1 and R2 are each independently a hydrogen atom or C1 to C
! an alkyl group or a human tetraxy group, a cyano group, an alkoxy group, a halogen, an epoxy group, a ybamoy/l/ group, an aycoquine carboxy group, a μ kylcarbony μ group, a sulfo group, a sulfamoyl group. C which may be substituted
1 to C4 A μ group, A is one phenylene or nurpho group which may be substituted with one or two substituents of methyl group, ethyl group, methoxy group, chlorine, bromine or sulfo group , X is a halogen atom, and Y is a group -8o, CH=C or a group -
8o, CH, C) I, Z, where 2 represents a group that is eliminated by the action of an alkali. ) A method for dyeing and printing a cationized modified cellulose fiber material is provided, which is characterized by using a reactive dye represented by the following.

In the present invention, cationized modified cellulose refers to cellulose modified by introducing a quaternary ammonium group into cellulose. The cationized modified cellulose fiber material used in the present invention is already known. ◇ As the cationizing agent used for cationization, Ria, U
Quaternary ammonium compounds having a hydrin group (e.g., C)cH, cH(oH)cH, $(cH, ), C7
0, etc.), quaternary ammonium compounds having an epoxy group, quaternary ammonium compounds having a trialkyl group, polycationic compounds, and the like.

The cationized modified cellulose-based fiber material is made by mixing cotton or thread-like cellulose fibers with a cationizing agent, such as Cationone UK (a quaternary ammonium compound having a chlorohydrin group, a product of Ipposha Yushi Co., Ltd.) 100f/j and caustic soda (flake). ) Immersed in a bath of 15j'/no at 80°C for 60 minutes, washed with water, and neutralized (acetic acid 2-8ml/))
After washing and drying, the modified IA fibers are mixed with a specified tray of unmodified fibers and spun and woven, or the modified IA fibers are made vertically or laminated.
Manufactured by weaving unmodified yarn horizontally or vertically.

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

Dyeing and printing are carried out using reactive dyes represented by the general formula (I) in a neutral state, such as exhaust dyeing, cold pad batch dyeing, pad dyeing (steam or baking fixation), and printing (X-team fixation). More specifically, the exhaust dyeing method can be carried out by each method, for example! The 0-cord batch dyeing method, which can be carried out by soaking textile materials in a dye solution and dyeing them at 60-80°C for 80-60 minutes, followed by washing, soaping, washing and drying, is, for example, a method for dyeing textile materials. This can be carried out by impregnating it with a dye solution (pad solution), squeezing it with a pick-up 60-804, rolling it up and leaving it at room temperature for 10-24 hours, then washing with water, soaping, rinsing with water, and drying. In addition, in the pad steam dyeing method, for example, the fiber material is impregnated with a dye liquid (pad liquid), squeezed with a pickup 60-804, and intermediately dried.
Steam for 1-5 minutes at ℃ or 120-140℃
This can be carried out by baking for 8-5 minutes at °C, followed by washing with water, soaping, washing with water, and drying.

The printing method involves, for example, printing a printing paste containing a dye on a textile material, drying it intermediately, and then steaming it at 100-120℃ for 8-5 minutes or baking at 120-140℃ for 8-5 minutes. 9! It is possible to give.

In this case, by using a small amount of 7μ potassium in the dye liquid or printing paste, it is possible to obtain processed products with dark and light tones.

For the dye pad solution or printing paste, various chemicals are added as necessary, such as disodium salt of sodium ethylenediaminetetophacetate as a metal ion sequestering agent, sodium metanitrobenzenesulfonate as a reduction inhibitor, migracilone, hMJ, and printing. As a sizing agent, sodium alginate, both types of emulsilon, low-strength nutbean gum, guar gum, etherified a-fiber-derived glue alone or in combination;
Urea, etc. can be used as a wetting/dissolving agent.@However, it is desirable to keep the pH of the dye pad solution or printing paste at 5-7 due to the white leaving effect of unmodified fibers. In order to dye a part lightly and obtain a dark or light tone, this purpose can be achieved by using an appropriate amount of an alkaline agent, such as an alkali metal hydroxide or carbonate.

In this way, by using the reactive dye represented by the general formula (1), it is possible to greatly improve the 3-moisture fastness, which has been considered an issue in the past, and the light fastness, H/L, = door lubricant. It is possible to obtain dyed products with excellent properties.

Next, the present invention will be specifically explained with reference to examples. In the following, parts are parts by weight.

Example 1 Cationone tJK (cationic and other agents manufactured by Yushisha Co., Ltd.)
100 parts and 15 parts of caustic soda (flake) and UDA-1
04K (Cationizing agent leveling agent Nikasha Yushisha product)
Prepare a total of 1000 parts of an aqueous solution containing 2 parts. Cotton cotton was immersed in this solution at a bath ratio of 1:20 and treated at 60°C for 60 minutes. Next, it was washed with water and heated at 40°C with a solution containing 0.8 part of acetic acid.
After neutralization treatment for 5 minutes, 800 parts of cotton cotton obtained as in 0 and 70 parts of unmodified cotton were washed with water and dried.
After mixing 0 parts and spinning, this is used as warp threads and untreated cotton threads are used as weft threads to make a fabric.10 parts of blue reactive dye having the following structure in free acid form are dissolved in 870 parts of boiling water and cooled. After that, 5 parts of disodium salt of ethylenediaminetetophacetic acid, 10 parts of sodium metanitrobenzenesulfonate, and duck algin NS were added.
PM (Sodium alginate: Kibun Food Co. product) 596
600 parts of Benito, monobasic sodium phosphate (pH adjuster) 10
to prepare a total of 1000 parts of uniform printing paste.

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

Separately, 50 parts of 5MA-51 (anionic masking agent manufactured by Jilt), 850 parts of water, 5 parts of Duck Algin NSPM (sodium alginate: Kibun Food Journal item)
% base) to prepare a total of 1000 parts of uniform printing paste. Overprint this printing paste on the entire surface of the dye printing, and
Perform intermediate drying for 8 minutes at 0-180°C. Then, it was washed with water, treated in a soaping bath containing 8 f/J of Bisnow/L/RK (soaping agent for cationized modified cotton, manufactured by Nichisha Yushisha Co., Ltd.) at 70°C for 5 minutes, and then washed with water. By this method, a solid blue print with a chambray tone was obtained. By similar method, 9, C, I.

Reactipub/7-19 (vinyl sulfone type reactive dye) and c, r, Reactipub/I/-49 (monochlorotriazine type reactive dye) exhibits moss Champagne tone effect, but poor wet fastness against perspiration and washing, making it difficult to put into practical use. It was in such a condition that it could not be used.

Comparative data on fastness is shown in the table 0 Sweat: JIS L-0848 (A-1 method) acidic, 7μ
Potassic washing: JIS L-0844 (A-4 method) Light resistance:
Grade judgment numerical value based on JIS L-0842 (carbon arc lamp) judgment Nigerley scale.

Example 2 Cotton yarn is cationically modified in the same manner as in Example 1. Then, a mixed woven fabric is woven with the modified yarn as the warp and the unmodified yarn as the weft. Separately, 20 parts of a navy blue reactive dye having the following structure in the form of a free acid was dissolved in 200 parts of boiling water and mixed with water for a total of 10 parts.
Prepare 00 parts by volume of dye pad solution. Pad the above cotton cloth with this solution at a solution temperature of 20-80°C and a pick-up of 70%, then roll it up, wrap the outer periphery with a glass film, and heat at room temperature of 20-25°C. Leave it overnight.

Next, wash with water in step A, process in a soaping bath containing Bisnow/L/RK (a soaping agent for cationic lines, manufactured by Nichisha Yushisha Co., Ltd.) for 5 minutes at 90°C, and finish by washing with water. By this method, a solid navy blue dyed product with an oboro tone was obtained. By the same method, C, L Reactippu/I/-147 (Vinice/L'7tt type reactive dye) and C, 1,! I Active Black 5 (Vini 7tz
7. μ-hon type j dye) also shows the oboro effect, but sweat and
It was in a state where it could not be put to practical use due to poor wet fastness when washed. Comparative data on fastness is shown in the table.

Test conditions and display are the same as in Example 1.

Example 8 A cationized cotton blend cloth is produced in the same manner as in Example 1.

Separately, 10 parts of a red color having the following structure in the form of a free acid was dissolved in 200 parts of boiling water, and after cooling, Duck Algin NS
PM (Sodium alginate: Kibun Food Co. product) 211
Prepare a dye pad solution with a total volume of 1000 parts by adding 60 parts of 1 paste, 5 parts of monobasic sodium phosphate, and the remaining amount of water.
Perform intermediate drying at 20°C for 8 minutes.
Treat at ℃ for 6 minutes and finish by washing with water.

By this method, a strong red dyeing with a chambray tone was obtained. fi, C, I in a similar manner.

Reactiple Red 114 (vinyl sulfone type reactive dye) and C,X, Reactiple Red 24 (monochlorotriazine type reactive detergent) also exhibit a chambray effect, but
The table shows comparative data for 0 fastness, which was in a state where wet fastness such as perspiration and washing and light fastness were so poor that it could not be put to practical use. In addition, Reactive Bread 114 and Reactive Bread 24 were replaced with Danfix 505RE (1/iS
Fixing agent: Nittobo Co., Ltd. product) After drying 15 fi1, various types of mold fastness were measured. However, there was no improvement in wet fastness, and on the contrary, there was a significant decrease in light fastness. The test method and display are the same as in Example 1. 〇Example 4 A cationic and other mesh blended fabric is produced in the same manner as in Example 1. Reactive dye 0.2f (2% o,,wSf) and soda ash 2P
Soak 10f of the cotton cloth (bath ratio 1:20) in a total amount of 4 Q Omj dye solution containing C5f/I) and perform exhaust dyeing at 60C for 40 minutes. Treat with a soaping bath containing 5 t/l of soaping agent Niiichisha Yushisha Co., Ltd. for 5 minutes at 90°C, and finish by washing with water.

By this method, a strong yellow dyed product with dark and light tones was obtained.C, 1, Reactive Ero-7
6 (vinylnurphone type reactive dye) and C,1, Reactive Red 5 (monochlorotriazine type reactive dye) showed similar effects, but their wet fastness against sweat and washing and light fastness were also inferior. Comparative data on fastness is shown in the table.

Claims (1)

[Claims] In the method of dyeing and printing cationized modified cellulose fiber materials, there are the following general formulas, ▲mathematical formulas, chemical formulas, tables, etc.▼ (wherein, D is an organic dye having a sulfonic acid group). residue, R
_1 and R_2 are each independently a hydrogen atom or C_
1-C_2 alkyl group or hydroxy group, cyano group,
C_1 to C_4 alkyl group which may be substituted with alkoxy group, halogen, carboxy group, carbamoyl group, alkoxycarbonyl group, alkylcarbonyloxy group, sulfo group, sulfamoyl group, A is methyl group, ethyl group,
A methoxy group, a phenylene group optionally substituted with one or two substituents of chlorine, bromine, or a sulfo group, or a naphthylene group optionally substituted with one sulfo group, X is a halogen atom, and Y is Group -SO_2CH=C
H_2 or the group -SO_2CH_2CH_2Z, where Z represents a group which is eliminated by the action of an alkali. ) A method for dyeing and printing a cationized modified cellulose fiber material, characterized by using a reactive dye represented by: