JPS6056838B2 - Anti-discharge printing method for polyester fibers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a discharge-proof printing method for polyester fibers. Specifically, the present invention relates to a method for discharge-proof printing polyester fibers. Specifically, the present invention uses a dicyanoimidazole-based monozo dye as a dye when carrying out discharge-proof printing on polyester fiber fabrics, and uses a discharge-proof printing agent as a dye. The purpose of this method is to use an inorganic or organic base as a base, and to obtain a variety of clear and robust printing patterns with little damage to the fibers and good whiteness in the discharge-proof printing area.

That is, in forming various printing patterns on polyester fiber fabrics, the present invention uses a dye of the following general formula (wherein R1 represents a substituted or unsubstituted alkyl group or alkenyl group, and R2 and R3 each represent a hydrogen atom). , represents a substituted or unsubstituted alkyl group, alkenyl group or cyclohexyl group, and R4 is a hydrogen atom, a chlorine atom,
It represents a bromine atom, an alkyl group, a substituted or unsubstituted alkoxy group or an alkenyl group, and R5 represents a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group, an alkoxy group, a hydroxyl group or an acylamino group.

) is used, and at least one base selected from alkali metal and alkaline earth metal hydroxides, organic weak acid salts, inorganic weak acid salts, ammonia, and aliphatic amines is used as a discharge printing agent. This is achieved by doing. In the general formula [1], R1 is an alkyl group such as a methyl group, an ethyl group, a linear or branched propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group; a methoxyethyl group ,
Lower alkoxyalkyl groups such as ethoxyethyl group and butoxyethyl group; Lower alkoxyalkoxyalkyl groups such as methoxyethoxyethyl group and ethoxyethoxyethyl group; Lower alkoxyalkoxyalkoxyalkyl groups such as methoxyethoxyethoxyethyl group and ethoxyethoxyethoxyethyl group ; optionally substituted phenoxyalkyl groups such as phenoxyethyl group, nitrophenoxyethyl group, chlorophenoxyethyl group; aralkyloxyalkyl groups such as benzyloxyethyl group, phenethyloxyethyl group, chlorobenzyloxyethyl group; Cyano lower alkyl groups such as cyanomethyl group, cyanoethyl group, cyanopropyl group; Hydroxy lower alkyl groups such as hydroxyethyl group, hydroxypropyl group, hydroxybutyl group; Acetyloxyethyl group, chloroacetyloxyethyl group, chloropropionyloxyethyl group base,
Acyloxy lower alkyl groups such as benzoyloxyethyl group, methoxycarbonyloxyethyl group, methoxyethoxycarcobonyloxyethyl group; carbamoyl lower alkyl groups such as carbamoylmethyl group, carbamoylethyl group; ethylaminocarbonylethyl group, diethylaminocarbonylethyl group, Mono- and dialkylaminocarbonyl lower alkyl groups such as 2-ethylhexylaminocarbonylethyl group; methoxycarbonylmethyl group,
Alkoxycarbonyl lower alkyl groups such as ethoxycarbonylmethyl group, methoxyethoxycarbonylmethyl group, ethoxycarbonylethyl group, benzyloxycarbonylmethyl group; aralkyl groups such as benzyl group, phenethyl group, chlorobenzyl group, nitrobenzyl group; allyloxyethyl Allyloxy lower alkyl groups such as groups; Allyloxycarbonyl lower alkyl groups such as allyloxycarbonylethyl groups and allyloxycarbonylmethyl groups;
Examples include acetylmethyl group; benzoylmethyl group; mono- and diallylaminocarbonyl lower alkyl groups such as allylaminocarbonylmethyl group and diallylaminocarbonylethyl group; alkenyl groups such as allyl group, methallyl group and crotyl group. In the general formula [1] shown above, R
2 and R3 are hydrogen atoms: methyl group, ethyl group, linear or branched propyl group, butyl group,
Alkyl groups such as pentyl group, hexyl group, heptyl group, octyl group; Lower alkoxyalkyl groups such as methoxyethyl group, ethoxyethyl group, butoxyethyl group; Lower alkoxyalkoxyalkoxyalkyl groups such as methoxyethoxyethyl group, ethoxyethoxyethyl group Groups: Lower alkoxyalkoxyalkoxyalkyl groups such as methoxyethoxyethoxyethyl groups and ethoxyethoxyethyl groups; Phenoxyalkyl groups that may be substituted such as phenoxyethyl groups, nitrophenoxyethyl groups, and chlorophenoxyethyl groups; Benzyloxyethyl groups , phenethyloxyethyl group, chlorobenzyloxyethyl group, etc.; cyano lower alkyl group such as cyanomethyl group, cyanoethyl group, cyanopropyl group; hydroxy lower alkyl group such as hydroxyethyl group, hydroxypropyl group, hydroxybutyl group Group; Acyloxy lower alkyl group such as acetyloxyethyl group, chloroacetyloxyethyl group, chloropropionyloxyethyl group, benzoyloxydiethyl group, methoxycarbonyloxyethyl group, methoxyethoxycarbonyloxyethyl group; Carbamoylmethyl group, carbamoylethyl group carbamoyl lower alkyl groups such as; mono- and dialkylaminocarbonyl lower alkyl groups such as ethylaminocarbonylethyl group, diethylaminocarbonylethyl group, 2-ethylhexylaminocarbonylethyl group;
Alkoxycarbonyl lower alkyl groups such as methoxycarbonylmethyl group, ethoxycarbonylmethyl group, methoxyethoxycarbonylmethyl group, ethoxycarbonylethyl group, benzyloxycarbonylmethyl group, aralkyl group such as benzyl group, phenethyl group, chlorobenzyl group, nitrobenzyl group, etc. Group; Allyloxy lower alkyl group such as allyloxyethyl group; Allyloxycarbonyl lower alkyl group such as allyloxycarbonylethyl group, allyloxycarbonylmethyl group; Acetylmethyl group; Benzoylmethyl group: Allylaminocarbonylmethyl group, diallylaminocarbonyl Mono- and diallylaminocarbonyl lower alkyl groups such as ethyl groups; tetrahydrofurfuryl groups; succinimide lower alkyl groups such as succinimidoethyl groups; cyanoalkoxy lower alkyl groups such as cyanoethoxyethyl and cyanomethoxyethyl groups; allyl groups , alkenyl groups such as methallyl group and crotyl group; cyclohexyl group and the like.

In the general formula [1] shown above, R4 is a hydrogen atom; a chlorine atom; a bromine atom; a methyl group, an ethyl group, a linear or branched propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, Alkyl groups such as octyl groups; alkoxy groups such as methoxy groups and ethoxy groups; lower alkoxyalkoxy groups such as methoxyethoxy groups and ethoxyethoxy groups; lower alkoxyalkoxyalkoxy groups such as methoxyethoxyethoxy groups and ethoxyethoxyethoxy groups;
Examples include halogeno lower alkoxy groups such as chloroethoxy group and bromoethoxy group; cyano lower alkoxy groups such as cyanoethoxy group; alkenyl groups such as allyl group, methallyl group and crotyl group.

In the general formula [1] shown above, R5 is a hydrogen atom; a chlorine atom; a bromine atom; a methyl group, an ethyl group, a linear or branched propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, Alkyl groups such as octyl groups; alkoxy groups such as methoxy and ethoxy groups; hydroxyl groups;
Acetylamino group, chloroacetylamino group, bromoacetylamino group, methoxycarbonylamino group, ethoxycarbonylamino group, benzoylamino group, methoxyethoxycarbonylamino group, methoxybenzoylamino group, methylsulfonylamino group, benzenesulfonylamino group, ethyl Examples include acylamino groups such as amino 1 carbonylamino group and bromopropionylamino group.

On the other hand, inorganic or organic bases used as discharge-proofing agents in discharge-proof printing pastes include alkali metal and metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; alkaline earth metals such as calcium hydroxide. Hydroxide: Alkali metal phosphates such as disodium hydrogen phosphate, sodium dihydrogen phosphate, trisodium phosphate, monopotassium hydrogen phosphate; Alkali metal carbonates such as potassium carbonate, sodium carbonate, lithium carbonate ; Alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; Alkali metal trialkyl phosphates such as sodium trimethyl phosphate and potassium toluethyl phosphate; Alkali metal borates such as sodium borate and potassium borate; ammonia aliphatic amines such as triethylamine, tripropylamine, tributylamine, ethanolamine, dimethylethanolamine, diethylethanolamine, diethanolamine, methyldiethanolamine, ethyldiethanolamine, propyldiethanolamine, and triethanolamine;

Various methods are known as anti-discharge printing methods for polyester fibers, but the first method is to dye polyester fiber fabrics in a dispersion containing a monoazo dye represented by the general formula [1] and various auxiliary agents. The dyed fabric obtained by padding and drying at a temperature of 80°C to 15°C is printed with a discharge-proof printing paste containing the base and various auxiliaries described above as a discharge-proofing agent, and then dried at a temperature of 100°C to 230°C. Examples include a method in which the monoazo dye represented by the general formula [1] shown above is decomposed in the area where the fixed and anti-discharge printing paste is printed by heat treatment at high temperature, and then post-treatment is carried out by a conventional method. .

In the second method, first, a polyester fiber fabric is printed with a discharge-proof printing paste, and then dried at a temperature of 80°C to -150°C, or continued as it is, and then printed with a dye represented by the general formula [1] shown above. The above-mentioned general formula [1] is printed with a printing paste containing a monoiso dye and various auxiliary agents, and then heat-treated at a temperature of 100°C to 230°C to print with a fixing and discharge-proof printing paste. An example of this method is to decompose the monoazo dye represented by the formula and then post-process it using a conventional method. In a third method, first, a polyester fiber fabric is printed with a printing paste containing a monoazo dye represented by the general formula [1] and various auxiliary agents; The monoazo dye represented by the general formula [1] shown above is fixed by drying, then printing with an anti-discharge dyeing paste, and then heat-treating at a temperature of 100°C to 230°C. An example of this method is to perform post-treatment using a conventional method after sawing. When applying various anti-discharge printing methods as described above to polyester fiber fabrics, multicolor designs can also be formed by adding alkali-resistant dyes such as those listed below to the anti-discharge printing paste.

Alkali-resistant disperse dyes that can be combined with the dyes of general formula [1] above to form multicolored designs are the common dyes from the group of azo, azomethine, quinophthalo, nitro, and anthraquinone dyes.

Some examples of alkali-resistant disperse dyes are as follows. For example, a disperse dye is represented by the following structural formula [■] 2
-Amino-4,5-dicyanoimidazole is diazotized, and the following general formula [■] (in the formula, R2, R3, R4 and R
5 is the same as the above definition.

) obtained by coupling with amines represented by the general formula [■] (wherein R2, R3, R4 and R5 are the same as defined above).

) is represented by the following general formula [V] Δ (where x represents a halogen atom and R1 is the same as defined above).

) or the following general formula [■] (In the formula, Y represents a hydrogen atom or a methyl group, and R1 is the same as defined above.

) can be produced by alkylation with an alkylating agent shown in

Hereinafter, the method of the present invention will be explained in more detail with reference to Examples.

Example 1 A dye 30' represented by the following structural formula was finely dispersed in 945 ml of water,
A padding solution containing 20 y of a 10% Fine Gum L3 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) aqueous solution and 5 y of citric acid was added.

This padding liquid was used to pad a polyester fiber fabric, and after squeezing to a dye liquid absorption rate of 60%,
It was dried at 00°C. After drying, sodium carbonate 50y1 Color Fine, AD (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 50f, 25
%Texprint LB (manufactured by Grunau) aqueous solution 600y
Overprinting was carried out using an anti-discharge dyeing paste containing 300 ml of water and 300 ml of water. Very good fastness properties after fixation in superheated steam at 175°C for 7 minutes, reductive work-up, soap treatment and subsequent rinsing and drying, especially good light fastness, sublimation fastness, water fastness and washability. A vivid bluish-red print with good fastness was obtained.

In the area where the anti-discharge dyeing paste containing sodium carbonate was printed,
A very good white background dyeing with a sharp ring was obtained. Example 2 A polyester fiber fabric was printed using an anti-discharge dyeing paste containing 60 g of sodium carbonate 60y1 Color Fine AD (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), 600 y of 25% Texprint LB (manufactured by Grunau) aqueous solution and 280 mt of water. 80
Dry at ~100°C.

After drying, a dye 30y represented by the following structural formula was finely dispersed to obtain Cellcoal PBL, -600 (manufactured by Adachi Paste Co., Ltd.) 24.
y1 Kiprogum P-20N (manufactured by Nippon Deka Chemical Co., Ltd.) 45.5y
, tartaric acid 1.5y, MS powder (manufactured by Meisei Chemical Co., Ltd.) 10
．． 2y1 May Printer Y-75 (manufactured by Meisei Chemical Co., Ltd.) 30
Overprinting was carried out using a printing paste prepared by adding Y and 858.8 ml of water.

After fixing in superheated steam for 6 minutes at 175°C, reducing post-treatment, soaping and subsequent rinsing and drying, very good fastness properties, especially good light fastness, sublimation fastness, water fastness and A bright red color that is washable and fast
A print was obtained.

In the area where the anti-discharge dyeing paste containing sodium carbonate was printed,
A very favorable white background dyeing with a sharp ring was obtained. Example 3 Dye 30y represented by the following structural formula was finely dispersed, and further Cellcol PBL-600 (manufactured by Adachi Pasteur Co., Ltd.) 24y1 Kipro Gum P
-20N (manufactured by Nippon Star Chemical Co., Ltd.) 45.5y, tartaric acid 1.5y
, MS powder (manufactured by Meisei Chemical Co., Ltd.) 10.2y1 May Printer Y-75 (manufactured by Meisei Chemical Co., Ltd.) 30y and water 858
．． Added 8ml.

This printing paste is used to print a polyester fiber fabric, and
Dry at 0-100°C. After drying, 50y of potassium carbonate
1 color fine oil (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 50y, 25
%Texprint LB (manufactured by Grunau) aqueous solution 6009
and 300 mt of water. Overprinting was performed using a discharge-proof dyeing paste containing . After fixation in superheated steam for 7 minutes at 175°C, reductive after-treatment, soaping and subsequent rinsing and drying, very good fastness properties, especially good lightfastness, sublimation fastness, waterfastness and A bright red print with washfastness was obtained.

In the areas where the anti-discharge dyeing paste containing potassium carbonate was printed, a very good white ground dyeing with a sharp ring was obtained. Example 4 A polyester cloth was dyed in the same manner as in Example 1 except that dye 20y represented by the following structural formula was used in place of dye 30y in Example 1.

As a result, it has very good fastness, especially good light fastness, sublimation fastness, water fastness and washing fastness, and has a sharp ring in the area where the anti-discharge printing paste is printed. A clear bluish red print with very good white background dyeing was obtained. Example 5 A polyester cloth was dyed in the same manner as in Example 1, except that dye 30y represented by the following structural formula was used in place of 30 g of the dye in Example 1.

As a result, it has very good fastness properties, especially good light fastness, sublimation fastness, water fastness and washing fastness,
In the area printed with the anti-discharge dyeing paste, a bright red print with a sharp ring and very good white background dyeing was obtained. Example 6 A polyester cloth was dyed in the same manner as in Example 1 except that dye 25y represented by the following structural formula was used in place of dye 30y in Example 1.

As a result, it has very good fastness properties, especially good light fastness, sublimation fastness, water fastness and washing fastness,
In the area printed with the anti-discharge dyeing paste, a clear bluish-red print with a sharp ring and very good white background dyeing was obtained. Example 7 A polyester cloth was dyed in the same manner as in Example 1 except that the dyes listed in Table 1 were used instead of the dyes in Example 1.

Claims (1)

[Claims] 1. In forming various printing patterns on polyester fiber fabrics, the following general formula ▲ mathematical formula, chemical formula, table, etc. are used as dyes ▼ (wherein, R^1 is an alkyl group; lower alkoxyalkyl group; lower alkoxyalkoxyalkyl group; phenoxyalkyl group; aralkyloxyalkyl group; cyano lower alkyl group; hydroxy lower alkyl group; acyl lower alkyl group; acyl lower alkyl group optionally substituted with a chlorine atom; carbamoyl lower alkyl group; Alkylaminocarbonyl lower alkyl group; alkoxycarbonyl lower alkyl group optionally substituted with an alkoxy group; alkoxycarbonyloxy lower alkyl group optionally substituted with an alkoxy group; allyloxy lower alkyl group; allyloxycarbonyl lower alkyl group; allylamino lower Carbonyl lower alkyl group; aralkyl group optionally substituted with a chlorine atom; or alkenyl group, where R^2 and R^3 are each a hydrogen atom; alkyl group; lower alkoxy optionally substituted with a hydroxyl group or a cyano group Alkyl group; lower alkoxyalkoxyalkyl group; lower alkoxyalkoxyalkoxyalkyl group; phenoxyalkyl group optionally substituted with a hydroxyl group or nitro group; aralkyloxyalkyl group; cyano lower alkyl group; hydroxy lower alkyl group; acyloxy lower alkyl group ; carbamoyl lower alkyl group; alkylaminocarbonyl lower alkyl group; alkoxycarbonyl lower alkyl group optionally substituted with an alkoxy group or phenyl group; tetrahydrofurfuryloxycarbonyl lower alkyl group; alkenyloxy lower alkyl group; an allyloxy lower alkyl group which may be substituted; an allyloxycarbonyl lower alkyl group; a tetrahydrofurfuryl group; a succinimide lower alkyl group; an aralkyl group which may be substituted with an alkyl group, an alkoxy group, a hydroxyl group or a nitro group; an alkenyl group; or represents a cyclohexyl group, R^4 represents a hydrogen atom; a chlorine atom; a bromine atom; an alkyl group; an alkoxy group which may be substituted with an alkoxy group, an alkoxyalkoxy group, a chlorine atom, or a cyano group; or an alkenyl group; R^5
is a hydrogen atom; a chlorine atom; a bromine atom; an alkyl group; an alkoxy group; a hydroxyl group; an acylamino group which may be substituted with a chlorine or bromine atom; an alkoxycarbonylamino group; an aralkyloxycarbonylamino group;
It represents an alkylsulfonylamino group; a phenylsulfonylamino group; or an alkylaminocarbonylamino group. ) is used, and at least one base selected from alkali metal and alkaline earth metal hydroxides, organic weak acid salts and inorganic weak acid salts, ammonia, and aliphatic amines is used as a discharge printing agent. An anti-discharge printing method for polyester fibers characterized by: