JPH0429704B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel disazo compounds and disazo dyes. Specifically, the present invention relates to a disazo compound and a disazo dye that have a high coupling yield. Furthermore, the present invention relates to a disazo dye for cellulose-containing fibers that dyes cellulose-containing fibers, particularly mixed fibers containing cellulose fibers and polyester fibers, in blue color with excellent color fastness including light fastness. It is something. Dyes having a thiophene disazo group in their chemical structure are described, for example, in JP-A-51-41734 as dyes for dyeing polyamide fibers and polyethylene fibers. However, conventional heterocyclic disazo dyes such as thiophene disazo dyes have unsatisfactory coupling yields in the dye manufacturing process. An object of the present invention is to provide a heterocyclic disazo compound exhibiting a high coupling yield. Another object of the present invention is to provide a disazo dye that dyes cellulose-containing fibers, particularly mixed fibers containing cellulose fibers and polyester fibers, in blue color with excellent color fastness including light fastness. It is something to do. That is, the dye according to the present invention has the following general formula [] (In formula [], D represents a substituted or unsubstituted phenyl group, pyridyl group, thiazolyl group, or benzothiazolyl group, and X represents a cyano group or alkoxycarbonyl group) A monoazo compound represented by the following general formula is diazotized. [] (In the formula [], Y represents a hydrogen atom, a chlorine atom, a methyl group, or an acylamino group, and R ¹ represents a substituted or unsubstituted alkyl group, cyclohexyl group, alkenyl group, or aryl group,
R ² and R ³ represent −NR ⁴ R ⁵ or −OR ⁶ ;
R ⁴ , R ⁵ and R ⁶ represent a hydrogen atom, an unsubstituted alkyl group, cyanoalkyl group, dialkylaminoalkyl group, alkenyl group, cyclohexyl group, aryl group or aralkyl group, or
NR ⁴ R ⁵ represents a 5- or 6-membered nitrogen-containing heterocycle formed by linking R ⁴ and R ⁵ , and A is -
CH ₂ CH ₂ − group,

[Formula] group or

[Formula] represents a group, Z represents an oxygen atom or -NH- group) The following general formula can be obtained by coupling with an aniline represented by [] (In formula [], D, X, Y, R ¹ , R ² , R ³ , A
and Z are the same as defined above) and are a disazo compound and a disazo dye. Below, the general formulas [], [], and [] will be explained in detail. The substituted or unsubstituted phenyl group, pyridyl group, thiazolyl group or benzothiazolyl group represented by D in the above general formulas [] and [] include phenyl group; fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group , trifluoromethyl group, methoxy group, ethoxy group, phenylazo group,
Cyano group, nitro group, methylsulfonyl group, ethylsulfonyl group, allylsulfonyl group, lower alkoxycarbonyl group, lower alkoxyethoxycarbonyl group, allyloxyethylcarbonyl group,
Mono-lower alkylaminocarbonyl group, di-lower alkylaminocarbonyl group, diallylaminocarbonyl group, monoallylaminocarbonyl group, dimethylaminosulfonyl group, diethylaminosulfonyl group, monomethylaminosulfonyl group, monoethylaminosulfonyl group, acetyl group, phenyl group Phenyl group substituted with etc.; Pyridyl group;
Pyridyl group substituted with chlorine atom, bromine atom, nitro group, methyl group, methylsulfonyl group, cyano group, etc.; thiazolyl group; methyl group, chlorine atom,
Thiazolyl group substituted with bromine atom, nitro group, lower alkoxycarbonyl group, methoxyethoxycarbonyl group, ethoxyethoxycarbonyl group, trifluoromethyl group, methylsulfonyl group; benzothiazolyl group; methyl group, chlorine atom,
Examples include benzothiazolyl groups substituted with a bromine atom, a nitro group, a lower alkoxycarbonyl group, a trifluoromethyl group, a methylsulfonyl group, and the like. In addition, in the general formulas [] and [] shown above, Y
Examples of the acylamino group represented by R ¹ , R ⁴ include an acetylamino group, a chloroacetylamino group, a benzoylamino group, a methylsulfonylamino group, a chloropropionylamino group, an ethoxycarbonylamino group, and an ethylaminocarbonylamino group. , R ⁵ and R ⁶ include methyl group, ethyl group, linear or branched propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, etc. Examples of substituted alkyl groups represented by R ¹ include lower alkoxyalkyl groups such as methoxyethyl, ethoxyethyl, butoxyethyl; lower alkoxyalkoxyalkyl groups such as methoxyethoxyethyl and ethoxyethoxyethyl; phenoxyethyl, etc. Phenoxyalkyl group; optionally substituted aralkyloxy lower alkyl group such as benzyloxyethyl group, chlorobenzyloxyethyl group; hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, hydroxyhexyl group, 2-hydroxy- Optionally substituted hydroxyalkyl groups such as 3-methoxypropyl group; cyano lower alkyl groups such as cyanomethyl group and cyanoethyl group; acetyloxyethyl group, chloroacetyloxyethyl group, chloropropionyloxyethyl group, benzoyloxyethyl group optionally substituted acyloxy lower alkyl groups such as; methoxycarbonyloxyethyl group; alkoxycarbonyloxy lower alkyl groups such as methoxyethoxycarbonyloxyethyl group; carbamoyl lower alkyl groups such as carbamoylmethyl group and carbamoylethyl group; methoxycarbonyl Optionally substituted alkoxycarbonyl lower alkyl groups such as methyl group, ethoxycarbonylmethyl group, methoxyethoxycarbonylmethyl group, benzyloxycarbonylmethyl group;
Optionally substituted aralkyl groups such as benzyl group, phenethyl group, and chlorobenzyl group; allyloxycarbonyl lower alkyl groups such as allyloxycarbonylethyl group and allyloxycarbonylmethyl group; tetrahydrofurfuryl group; succinimidoethyl group, etc. succinimide lower alkyl groups; phthalic acid imide lower alkyl groups such as phthalic acid imidoethyl group; cyanoalkoxy lower alkyl groups such as cyanoethoxyethyl group and cyanomethoxyethyl group; halogen lower alkyl groups such as chloroethyl group; Examples of the aryl group include phenyl group, chlorophenyl group, methylphenyl group, etc., and examples of the nitrogen-containing heterocyclic group represented by NR ⁴ R ⁵ include 1-pyrrolidinyl group, 3-methyl-1
-pyrrolidinyl group, 2-hydroxyethyl-1-
pyrrolidinyl group, 2,5-dimethyl-1-pyrrolidinyl group, 3-thiazolidinyl group, 1-pyrrolyl group, 1-pyrazolyl group, 1-imidazolyl group, morpholino group, piperidino group, 2,6-dimethylpiperidino group, 1-piperazinyl group, 4-methyl-
Examples include 1-piperazinyl group. As NR ⁴ R ⁵ , a di-substituted amino group having a total of 6 to 12 carbon atoms is particularly desirable. The monoazo compound represented by the above general formula [] can be obtained, for example, by diazotizing an amine represented by the following general formula [] D-NH ₂ ... [] (wherein D is the same as defined above) to form the following formula []. ] (In the formula, X is the same as defined above) by coupling with an amine. In addition, the anilines represented by the general formula [] shown above are represented by the following general formula [] (wherein Y, R ¹ , A and Z are the same as defined above) and the following general formula [] (In the formula, Hal represents a fluorine atom, a chlorine atom, or a bromine atom, and R ² and R ³ are the same as defined above.)
A triazine compound represented by N-methylpyrrolidone, triethylamine, in a solvent such as acetone,
2 at 40-100℃ in the presence of a deoxidizing agent such as soda carbonate.
Produced by reacting for ~10 hours. As the amine represented by the general formula [],
Benzene-based amines, such as aniline, o-, m
- or p-fluoroaniline, o-, m- or p-chloroaniline, o-, m or p-promoaniline, 2,4-dichloroaniline, 2,3
-dichloroaniline, 2-chloro-4-bromoaniline, 2,4-difluoroaniline, 2,4,
6-trichloroaniline, o-, m- or p-
Toluidine, o-, m- or p-ethylaniline, o-, m- or p-anisidine, m-trifluoromethylaniline, 4-phenylazoaniline, o- or p-cyanoaniline, o-, m
- or p-nitroaniline, 2-chloro-4-
Nitroaniline, 2-bromo-4-nitroaniline, 2-cyano-4-nitroaniline, 2-chloro-4-methoxyaniline, o-, m- or p
-methylsulfonylaniline, o-, m- or p-ethylsulfonylaniline, o-, m- or p-methoxycarbonylaniline, o-, m-
or p-ethoxycarbonylaniline, p-butoxycarbonylaniline, p-allyloxycarbonylaniline, p-allyloxyethoxycarbonylaniline, o-, m- or p-methoxyethoxycarbonylaniline, p-N,N-dimethylaminocarbonyl Aniline, p-N-ethylaminocarbonyl group Aniline, p-N-allylaminocarbonylaniline, 2-chloro-4-methoxycarbonylaniline, p-N,N-dimethylaminosulfonylaniline, m-N,N-diethylaminosulfonyl Examples of pyridine-based amines include aniline, p-N-ethylaminosulfonylaniline, p-phenylaniline, etc.
3-aminopyridine, 3-amino-6-bromopyridine, 3-amino-5-bromopyridine, 3-
Amino-6-chloropyridine, 4,6-dichloro-3-aminopyridine, 3-amino-6-nitropyridine, 3-amino-4-cyanopyridine, 3
-amino-5-methylpyridine, 3-amino-6
-methylsulfonylpyridine, 3-amino-4-
Chloro-6-nitropyridine, 3-amino-5-
Examples of thiazole amines include methyl-6-bromopyridine, 2-aminothiazole, 2-amino-4-methylthiazole, 2-amino-4-methyl-5-ethoxycarbonylthiazole, and 2-amino-4-methylthiazole. 5-nitrothiazole, 2
-amino-5-bromothiazole, 2-amino-
Examples include 5-chloro-thiazole, 2-amino-4-trifluoromethylthiazole, 2-amino-4-methyl-5-methoxyethoxycarbonylthiazole, and 2-amino-4-methyl-5-bromothiazole; Examples of thiazole amines include 2-aminobenzothiazole, 2
-amino-4,6-dibromobenzothiazole,
Examples include 2-amino-6-sulfomethylbenzothiazole, 2-amino-5,6-dichlorobenzothiazole, and 2-amino-6-nitrobenzothiazole. Furthermore, the dyeing method using the dye of the present invention will be explained in detail. Cellulose-containing fibers dyed with the dye represented by the general formula [] include natural fibers such as cotton and linen, semi-synthetic fibers such as viscose rayon and copper ammonia rayon, and partially aminated or partially acylated modified fibers. Examples include fibers such as cellulose fibers, woven and knitted fabrics, and nonwoven fabrics thereof.
In addition, the above fibers, polyester fibers, cationically dyeable polyester fibers, anionically dyeable polyester fibers, polyamide fibers, wool, acrylic fibers,
Examples include blended or woven products with other types of fibers such as urethane fibers, diacetate fibers, and triacetate fibers. Among these, it is particularly effective for cellulose fibers and blended or woven products of cellulose fibers and polyester fibers. When carrying out dyeing, please follow the general formula shown above []
It is desirable to finely disperse the dye represented by 0.5 to 2 μ in a medium using a nonionic surfactant such as a Pluronic type surfactant or an anionic dispersant such as sodium ligninsulfonate or naphthalenesulfonic acid-formaldehyde. A method of finely dispersing in water using a water-soluble dispersant such as a sodium salt of a condensate using a grinder such as a sand grinder or a mill; Carbonization of solvents other than water, such as alcohols such as ethyl alcohol, isopropyl alcohol, and polyethylene glycol, ketones such as acetone and methyl ethyl ketone, n-hexane, toluene, xylene, and mineral turpentine, using a poorly water-soluble or water-insoluble dispersant. A method of finely dispersing hydrogen, halogenated hydrocarbons such as tetrachloroethylene, esters such as ethyl acetate and butyl acetate, ethers such as dioxane and tetraethylene glycol dimethyl ether, or a mixed solvent thereof; Examples include a method of finely dispersing it in a mixed system with a solvent that can be arbitrarily mixed with water. Furthermore, in the above-mentioned fine dispersion process, a polymer compound soluble in each dispersion medium or a surfactant having a function other than the dispersion effect may be added. This dye fine dispersion can be used as it is as a padding bath in padding dyeing method and as printing dyeing paste in textile printing method, but when used as a normal padding bath and printing dyeing paste, the above dye fine dispersion can be mixed with water or optionally with water. A mixed system of solvent and water that can be mixed with water, or an O/W emulsion or W/O emulsion system in which the oil layer is a petroleum hydrocarbon such as mineral turpentine or a halogenated hydrocarbon such as tetrachloroethylene, is applied to the desired dyeing density. It is used after diluting it to the appropriate ratio. In preparing padding baths and printing dyeing pastes, alkali metal compounds, organic epoxy compounds, organic vinyl compounds, etc. are used as cellulose fiber swelling agents or acid binders for the purpose of promoting the reaction between dyes and cellulose fibers in order to carry out dyeing advantageously. It can be added as Any cellulose fiber swelling agent can be used as long as it has the effect of swelling cellulose fibers with a boiling point of 150°C or higher, such as N,N,N',N'-tetramethylurea, etc. Examples include ureas, polyhydric alcohols such as polyethylene glycol, polypropylene glycol, and derivatives thereof. Particularly preferred as the cellulose fiber swelling agent are polyhydric alcohol derivatives having an average molecular weight of about 200 to 500, such as polyethylene glycol and polypropylene glycol, in which the hydroxyl groups at both ends are dimethylated or diacetylated and do not react with the reactive groups of the dye. The appropriate amount of the cellulose fiber swelling agent to be used is about 5 to 25% by weight, preferably about 8 to 15% by weight, based on the padding bath or textile dyeing paste. Alkali metal compounds include, in addition to alkali metal carbonates, alkali metals such as alkali metal bicarbonates, alkali metal phosphates, alkali metal borates, alkali metal silicates, alkali metal hydroxides, and alkali metal acetates. Fatty acid salts or alkali precursor compounds that generate alkali when heated in the presence of water, such as sodium trichloroacetate and sodium acetoacetate, can be used. These usage amounts are usually determined by the amount of padding bath or printing paste.
An amount that brings the pH to 7.5 to 8.5 is sufficient. Examples of organic epoxy compounds include ethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether with an average molecular weight of 150 to 400. Examples of organic vinyl compounds include ethylene glycol diacrylate and polyethylene glycol diacrylate with an average molecular weight of 150 to 400. Or dimethacrylate etc. are mentioned. The amount of these used is 3 to 6 for padding bath or textile dyeing paste.
It is about % by weight. The preparation of the padding bath or printing dyeing paste is not limited to the above method, and the cellulose fiber swelling agent and acid binding agent do not necessarily need to be present in the padding bath or printing dyeing paste.
It may also be present on the fiber side. In addition, a thickener such as a water-soluble polymer such as sodium alginate may be added to prevent dry migration during padding dyeing or to adjust the viscosity of the color paste to be optimal for various printing methods. In order to dye the above-mentioned fibers with the dye represented by the general formula [], the cellulose fiber-containing material is impregnated or printed with a padding bath or printing dyeing paste prepared by the above method, dried, and then 30 seconds to 10 with 220℃ hot air or superheated steam
Heat treatment for 3 to 30 minutes in high pressure saturated steam at 120 to 150°C and washing with hot water containing a surfactant, or O/W type where the oil layer is a halogenated hydrocarbon such as tetrachlorethylene. This is completed by cleaning with a W/O type emulsion cleaning bath or with a conventional dry cleaning method. In this way, the dyes of the invention can be obtained with high coupling yields. Furthermore, the dye of the present invention can be obtained by the above method.
It is possible to obtain a dyed product that is bright and uniformly dyed and has good light fastness and wet fastness. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples. In addition, "parts" in the examples indicate "parts by weight." Example 1 The following structural formula A dye dispersion was prepared from a dye composition consisting of 15 parts of the disazo dye represented by the following formula, 15 parts of a naphthalene sulfonic acid-formaldehyde condensate, and 70 parts of water using a paint shaker as a fine dispersion machine. This dye dispersion was used to prepare a printing paste with the following composition: Dye dispersion 6.5 parts 5% sodium alginate aqueous solution 55 parts Polyethylene with an average molecular weight of 400 9 parts Glycol dimethyl ether 29.5 parts water 100 parts (PH8.0) Polyester /Cotton (mixing ratio 65/35) blended fabric was printed using a screen printing machine, dried at 80℃ for 3 minutes, and then dried at 215℃ for 90 minutes.
It was fixed by dry heat for seconds. After washing with water, soaping was performed at 80°C for 20 minutes at a bath ratio of 1:30 using a cleaning solution containing 2 g of a nonionic surfactant (Score Roll #900 (trademark), manufactured by Kao Soap Co., Ltd.) to ensure light resistance. A blue dyeing with excellent fastness and wet fastness was obtained. The dye used in this example was 9.12 g of 2-amino-3-cyano-5-phenylazothiophene (85%).
Add to a mixture of 160 ml of phosphoric acid and 200 ml of glacial acetic acid, cool to below 5°C, and add 17.0 ml of 40% nitrosyl sulfuric acid.
g was gradually added. The mixture was stirred at 0-2°C for 4 hours, and the diazo solution was mixed with 2 g of urea and N-ethyl-N-[2,4-di(N,N-diethylamino)].
-6-triazinyloxy]ethylaniline 15.0
g was dissolved in 300 ml of methanol. The obtained precipitate was separated, washed with water, and then dried at room temperature to obtain a blue powder of the dye represented by the above structural formula (pure yield: 90%). This yield was at a very high level for thiophene disazo dyes. The λmax (acetone) of this dye was 614 nm. Example 2 Structural formula below A dye dispersion was prepared from a dye composition consisting of 15 parts of the disazo dye represented by, 10 parts of Pluronic type surfactant Pluronic L64 (manufactured by Asahi Denka Kogyo Co., Ltd.), and 75 parts of water using a sand grinder as a fine dispersion machine. . This dye dispersion was used to make the following composition: Dye dispersion 7 parts 5% sodium alginate aqueous solution 55 parts Polypropylene with an average molecular weight of 300 10 parts Glycol diacetate Polyethylene with an average molecular weight of 200 3 parts Glycol diglycidyl ether 25 parts water 100 parts ( PH6.5) was prepared, printed on mercerized broadcloth (number 40) using a screen printing machine, dried at 80℃ for 3 minutes, and then dried at 185℃ for 7 minutes.
Treatment was carried out using superheated steam for 1 minute. Thereafter, washing treatment was carried out according to the method described in Example 1, and a blue dyed product with excellent light fastness and wet fastness was obtained. The dye used in this example was synthesized according to the method described in Example 1 (purity yield: 88%). The λmax (acetone) of this dye was 649 nm. Example 3 Structural formula below 10 parts of disazo dye represented by polyoxyethylene glycol nonylphenyl ether (HLB
8.9) A dye ink was prepared by grinding a dye composition consisting of 2 parts and 88 parts of diethylene glycol diacetate using a paint conditioner as a fine disperser. After mixing 10 parts of this dye ink and 55 parts of mineral turpentine, this was stirred with a homomixer (5000 ~
7000RPM), gradually pour into 35 parts of an aqueous solution with the following composition and stir until homogeneous to form a viscous O/
A W-type emulsion colored paste was prepared. Water 31 parts Lepitol G 3.8 parts (trademark, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., special nonionic surfactant) Sodium trichloroacetate 0.1 parts 34.9 parts Next, use this color paste to blend polyester/cotton (mixing ratio 65/35) The cloth was printed using a screen printing machine, dried at 100°C for 2 minutes, and then treated with superheated steam at 175°C for 7 minutes. Thereafter, the dyed product was washed in a hot tetrachloroethylene bath containing a small amount of water and dried to obtain a blue dyed product with excellent light fastness and wet fastness and no white spot staining. The dye used in this example was synthesized according to the method described in Example 1 (purity yield: 87%). The λmax (acetone) of this product was 645 nm. Example 4 Structural formula below 16 parts of disazo dye represented by polyoxyethylene glycol nonyl phenyl ether (HLB
13.3) A dye composition consisting of 7 parts of naphthalene sulfonic acid-formaldehyde condensate and 74 parts of water was finely dispersed using a sand grinder to prepare a dye dispersion. Using this dye dispersion, make the following composition: Dye dispersion 6 parts Tetraethylene glycol dimethyl ether
Prepare a padding bath of 15 parts water, 79 parts water, 100 parts (PH8.0), impregnate a polyester/cotton (mixing ratio 65/35) blended fabric, squeeze it to a squeezing rate of 45%, and dry it at 100℃ for 2 minutes. It was fixed by dry heat at 200°C for 1 minute. By washing this product in a hot ethanol bath, a blue dyed product with excellent light fastness and wet fastness was obtained. The dye used in this example was synthesized according to the method described in Example 1 (pure yield: 90%). The λmax (acetone) of this product was 614 nm. Example 5 Printing was carried out in the same manner as in Example 1 except that the fiber was changed to a nylon/rayon (mixing ratio 50/50) blended fabric and the dry heat fixation temperature was changed to 185°C. A blue print with good wet fastness and light fastness was obtained. Example 6 Example 1 using the disazo dyes shown in Table 1
Printing was carried out according to the method described in . The light fastness and wet fastness of the dyed fabric obtained were both good. Table 1 shows the hue of the dyed fabric and the λmax (acetone) of the dye.

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Claims (1)

[Claims] 1. The following general formula (In the formula, D represents a substituted or unsubstituted phenyl group, pyridyl group, thiazolyl group, or benzothiazolyl group, X represents a cyano group or alkoxycarbonyl group, Y represents a hydrogen atom, a chlorine atom,
represents a methyl group or an acylamino group, R ¹ represents a substituted or unsubstituted alkyl group, cyclohexyl group, alkenyl group or aryl group,
R ² and R ³ represent −NR ⁴ R ⁵ or −OR ⁶ ;
R ⁴ , R ⁵ and R ⁶ are hydrogen atoms, unsubstituted alkyl groups, cyanoalkyl groups, hydroxyalkyl groups,
5 represents a lower alkoxyalkyl group, dialkylaminoalkyl group, alkenyl group, cyclohexyl group, aryl group or aralkyl group, or -NR ⁴ R ⁵ is formed by linking R ⁴ and R ⁵
represents a nitrogen-containing or 6-membered nitrogen-containing heterocycle, and A is -
CH ₂ -CH ₂ - group, [Formula] group or [Formula] group, Z represents an oxygen atom or -NH- group). 2 General formula below (In the formula, D represents a substituted or unsubstituted phenyl group, pyridyl group, thiazolyl group, or benzothiazolyl group, X represents a cyano group or alkoxycarbonyl group, Y represents a hydrogen atom, a chlorine atom,
represents a methyl group or an acylamino group, R ¹ represents a substituted or unsubstituted alkyl group, cyclohexyl group, alkenyl group or aryl group,
R ² and R ³ represent −NR ⁴ R ⁵ or −OR ⁶ ;
R ⁴ , R ⁵ and R ⁶ are hydrogen atoms, unsubstituted alkyl groups, cyanoalkyl groups, hydroxyalkyl groups,
5 represents a lower alkoxyalkyl group, dialkylaminoalkyl group, alkenyl group, cyclohexyl group, aryl group or aralkyl group, or -NR ⁴ R ⁵ is formed by linking R ⁴ and R ⁵
represents a nitrogen-containing or 6-membered nitrogen-containing heterocycle, and A is -
CH ₂ -CH ₂ - group, [Formula] group or [Formula] group, Z represents an oxygen atom or -NH- group).