JPH06212577A - Method for printing textile structure - Google Patents

Abstract

PURPOSE:To safely and efficiently furnish a textile structure with complicated printed pattern. CONSTITUTION:A textile structure comprising cellulosic fibers and/or protein fibers is printed with a treating liquid (pH7.5-12, or pH3-6.5)containing (A) a cationizing agent consisting of a quaternary ammonium salt bearing at least one kind of reactive group selected from vinyl, acryloyl and methacryloyl groups and (B) a polymerization initiation catalyst, followed by heat treatment and then printing the resultant textile structure with a second treating liquid containing an anionic dye.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to cellulosic fibers and / or
Alternatively, the present invention relates to a method for imparting a complicated printing pattern to a fiber structure composed of protein fibers.

[0002]

2. Description of the Related Art Conventionally, as a method for forming a pattern on a cloth such as a cellulosic fiber, a so-called textile printing has been known in which a printing paste containing a dye is printed by a screen printing machine, a roller printing machine or a rotary screen printing machine. There is. In this method, a pattern due to the hue difference can be provided, but there is a problem that the maximum number of colors according to the characteristics of the printing machine, for example, only 20 colors can be expressed by the screen printing machine.

Therefore, in order to double the maximum number of colors of the properties of the printing machine, a method of forming a resin film in a pattern and then coloring it (Japanese Patent Laid-Open No. 63-282375) or a cationizing agent is used. Coloring after forming into a shape (Japanese Patent Application Laid-Open No. Sho 6)
No. 3-85186).

[0004]

However, Japanese Unexamined Patent Application Publication No. Sho 6
Since the method described in JP-A-3-85186 uses a quaternary ammonium salt type chlorohydrin derivative as a cationizing agent, it is necessary to use a strong alkali such as caustic soda in combination, which poses a problem in terms of production work. . In addition, protein fibers have a problem of being brittle due to strong alkali, and the above method cannot be applied to animal hair fibers.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a method capable of safely and efficiently imparting a complicated printing pattern to a fiber structure.

[0006]

DISCLOSURE OF THE INVENTION The above object is to provide a fiber structure composed of cellulosic fibers and / or protein fibers with at least one reactive group selected from a vinyl group, an acroyl group and a metacroyl group. PH containing cationizing agent composed of primary ammonium salt and polymerization initiation catalyst
It is achieved by a method for printing a fiber structure, which comprises printing a treatment liquid having a pH of 7.5 to 12 or a pH of 3 to 6.5, and after heat treatment, printing a treatment liquid containing an anionic dye.

The present invention will be described in detail below.

In the present invention, the fiber structure means a woven fabric, a knitted fabric, a non-woven fabric, etc., and the cellulosic fiber is cotton,
Examples include hemp and rayon, and examples of protein fibers include animal hair fibers such as silk, wool, mohair, and alpaca. In the case of using animal hair fiber, it is better to use the one in which anion or cation or both are generated on the surface of animal hair fiber by oxidizing at least one of chlorine and oxygen from the viewpoint of the invention effect and utility value. preferable.

The cationizing agent used in the present invention is a quaternary ammonium salt having at least one reactive group selected from a vinyl group, an acroyl group and a methacroyl group, and is specifically shown below. Dimethylaminoethyl methacrylate quaternary compound, dimethyldiallylammonium chloride represented by the following, acrylamido-3-methylbutyltrimethylammonium chloride represented by the following, methacrylodiethyltrimethylammonium chloride represented by the following, 2-hydroxy- represented by the following 3-methacryloxypropyl trimethyl ammonium chloride etc. are mentioned.

[0010]

[Chemical 1]

The amount of the cationizing agent used is not particularly limited and may be about 1 to 40% by weight (the amount of the active ingredient), but considering stability and economy, it is about 3 to 20% by weight (the effective amount). It is preferable to use (amount of components).

The polymerization initiation catalyst used in the present invention includes
Peroxides such as ammonium persulfate, potassium persulfate and benzoyl peroxide; cerium salts such as ceric ammonium nitrate and ceric ammonium sulfate; 4,4'-
Azobis-4-cyanovaleric acid sodium salt, 4-4'-
Azobis-4-cyanovaleric acid ammonium salt, 2,2 '
Examples thereof include water-soluble azo compounds such as azobis (2-acidinopropane) hydrochloride. The amount used is 0.
It is 1 to 10% by weight, preferably 0.1 to 3% by weight.

A fibrous structure composed of cellulosic fibers and / or protein fibers is imprinted with a treatment liquid comprising the above cationizing agent and a polymerization initiating catalyst. The treatment liquid has a pH of 7.5 to 7.5.
It is important to adjust the pH to 12 or pH 3 to 6.5. Ammonium sulfate, ammonium acetate, sodium acetate, sodium carbonate, sodium hydrogen carbonate and the like can be used to make the pH of the treatment liquid weakly alkaline, while acetic acid, Oxalic acid, tartaric acid, boric acid, succinic acid, and apple acid can be used.

As a method of printing the treatment liquid, a screen printing machine, a roller printing machine, a rotary screen printing machine, an ink jet printing machine or the like can be used.
When a screen printing machine, a roller printing machine, or a rotary screen printing machine is used, the processing liquid contains a sizing agent. As the sizing agent component, sodium alginate, highly etherified locust bean gum, crystal gum, etc. can be used.

After printing the treatment liquid, 100 to 120 ° C.
For 1-3 minutes, and then heat-treated at a temperature of 120 to 210 ° C. with saturated steam, superheated steam, and dry heat. In the heat treatment, it is particularly preferable to perform atmospheric pressure steaming at 100 to 110 ° C. for 5 to 30 minutes. Then the temperature 40-90 ℃,
Wash for 10 seconds to 20 minutes and dry.

In the present invention, the cationized fiber structure is then printed with a treatment liquid containing an anionic dye.
Examples of the anionic dye include acid dyes, metal-containing dyes, reactive dyes, direct dyes and vat dyes. From the viewpoint of the effect of the invention, the use of reactive dyes is preferable. Further, as a method for printing a treatment liquid containing an anionic dye, a screen printing machine, a roller printing machine, a rotary screen printing machine, an ink jet printing machine or the like can be used. When a screen printing machine, a roller printing machine, or a rotary screen printing machine is used, the processing liquid containing the anionic dye contains a sizing agent. As the sizing agent component, sodium alginate, highly etherified locust bean gum, crystal gum, etc. can be used. Further, an auxiliary agent required for each dye is added to the treatment liquid, and after printing, it is dried and then fixed by a method according to the dye to fix the dye to the fiber.

[0017]

The cationizing agent composed of a quaternary ammonium salt having at least one reactive group selected from a vinyl group, an acroyl group and a metacroyl group is a hydroxyl group of the cellulosic fiber on the weak alkaline side or weak acidic side in the printing method. Alternatively, since it polymerizes with the functional groups of the protein fiber, there is no danger in the work and the protein fiber does not become brittle.

[0018]

EXAMPLES The present invention will be specifically described below with reference to examples.

The dyeing density and workability described in the examples were measured by the following methods. (1) Dyeing density Evaluation was made by comparing K / S values at the maximum absorption wavelength with a spectrophotometer (comparison when 100 without cationization treatment). (2) Workability ○: There is little danger in work △: There is some danger in work ×: There is danger in work

Example 1 Cotton flat fabric having a warp density of 120 yarns / inch and a weft yarn density of 60 yarns / inch consisting of 40 warps and 40 wefts (weight of 90 g / m 2)
² ) is desalted, scoured and bleached by a known method, and D
Q75 (Kyoeisha cationizing agent, dimethylaminoethyl methacrylate quaternary compound, active ingredient 75%) 10% by weight, Duck Algin NSPL (Kibun Food Co., Ltd. sodium alginate) 2% by weight, sodium carbonate 5% by weight, urea (moisturizing) Agent) 10% by weight, ammonium persulfate 1% by weight,
A treatment solution containing 82% by weight of water and having a pH of 11.5 was printed with a 150 mesh floral frame using an automatic screen printing machine. Then, after drying at 100 ° C. for 1 minute, 10
Steaming was performed at 5 ° C. for 8 minutes. Then 5 at 40 ℃
It was washed with water for a minute.

On the plain fabric thus treated with the cationizing agent, 10% by weight of Cibacron Red 30 (reactive dye manufactured by Ciba Geigy), 1% by weight of Duck Algin NSPL (sodium alginate manufactured by Kibun Foods), fine Gum H
EL (carboxymethyl cellulose manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5% by weight, baking soda 3% by weight, urea 10% by weight, M
A treatment liquid consisting of 0.5% by weight of S powder (reduction inhibitor manufactured by Meisei Chemical Co., Ltd.) and 85% by weight of water was subjected to full-screen printing with a 150-mesh solid frame using an automatic screen printing machine.
Then, after drying at 100 ° C. for 1 minute, steaming treatment was performed at 105 ° C. for 8 minutes, washing with hot water, washing with water and drying to obtain the product of Example 1.

Example 2 In Example 1, 5% by weight of acetic acid was used instead of sodium carbonate.
The same treatment as in Example 1 was performed except that (the pH of the treatment liquid was 4) was used to obtain a product of Example 2. Since the treatment liquid containing the cationizing agent used in Example 2 is separated in about 10 days, the treatment liquid thus prepared has a drawback that it cannot be stored.

Comparative Example 1 Caustic soda 5 was used in place of sodium carbonate in Example 1.
The same treatment as in Example 1 was performed except that the weight% (pH of the treatment liquid was 13) was used to obtain a product of Comparative Example 1.

Table 1 shows the dyeing density and the evaluation of workability of the products obtained in Examples 1 and 2 and Comparative Example 2.

[0025]

[Table 1]

As can be seen from Table 1, the products obtained in Examples 1 and 2 have different dyeing densities depending on whether they are treated with a cationizing agent or not, and form complicated printing patterns. I understand. Also, it can be seen that the workability is excellent.

Example 3 The same cotton flat fabric as in Example 1 was mixed with New Frontier C
-1615 (Daiichi Kogyo Co., Ltd. cationizing agent, dimethyldiallylammonium chloride, active ingredient 70%) 20
PH consisting of wt%, sodium acetate 5 wt%, urea 10 wt%, ammonium persulfate 1 wt%, water 82 wt%
11.5 processing liquid using automatic screen printing machine, 15
A floral pattern was imprinted with a 0 mesh floral frame. And 1
After drying at 00 ° C for 1 minute, steaming treatment was performed at 105 ° C for 8 minutes. Then, it was washed with water at 40 ° C. for 5 minutes.

The plain woven fabric thus treated with the cationizing agent was printed with a treatment liquid containing Remazole Red B in place of Cibacron Red 30 of Example 1, and treated in the same manner as in Example 1. 3 products were obtained.

Example 4 In Example 3, 5% by weight of acetic acid was used instead of sodium acetate.
The same treatment as in Example 3 was carried out except that (treatment liquid pH 4) was used to obtain a product of Example 4. Since the treatment liquid containing the cationizing agent used in Example 4 is separated in about 10 days, the treatment liquid thus prepared has a drawback that it cannot be stored.

Comparative Example 2 Caustic soda 5 was used in place of sodium acetate in Example 3.
The same process as in Example 3 was performed except that the weight% (pH of the treatment liquid was 13) was used to obtain a product of Comparative Example 2.

Table 2 shows the dyeing concentration and the evaluation of workability of the products obtained in Examples 3 to 4 and Comparative Example 2.

[0032]

[Table 2]

As can be seen from Table 2, the products obtained in Examples 3 and 4 have different dyeing densities depending on whether they are treated with a cationizing agent or not, and form complicated printing patterns. I understand. Also, it can be seen that the workability is excellent.

[0034]

As described in detail above, according to the method of the present invention, the polymerization reaction proceeds on the weakly alkaline side or the weakly acidic side so that there is little danger in working, and even when it is applied to protein fibers. It is very useful without embrittlement. In addition, since the obtained product is a deeply printed product that is very rich in variety, it can be used for casual purposes.

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[Procedure amendment]

[Submission date] April 1, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

[0010]

[Chemical 1]

Claims (1)

[Claims] 1. A cationizing agent comprising a quaternary ammonium salt having at least one reactive group selected from a vinyl group, an acroyl group and a methacroyl group in a fiber structure composed of cellulosic fibers and / or protein fibers. A method for printing a fibrous structure, which comprises printing a treatment liquid having a pH of 7.5 to 12 or a pH 3 to 6.5 containing a polymerization initiation catalyst, heating the treatment liquid, and then printing a treatment liquid containing an anionic dye.