JPH0458508B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to disazo compounds and disazo dyes. Specifically, the present invention relates to a reactive disazo dye for dyeing cellulose-containing fibers, particularly cellulose fibers, and mixed fibers consisting of polyester fibers and cellulose fibers, in orange to blue colors with excellent color fastness including light fastness. be. The present invention will be explained in detail below. The gist of the present invention is the following general formula [] (wherein D is a substituted or unsubstituted phenyl group,
Represents a pyridyl group, thiazolyl group or benzothiazolyl group, R ¹ represents a cyano group or alkoxycarbonyl group, R ² and R ³ represent a substituted or unsubstituted alkyl group or alkenyl group, Y is -NR ⁴ R ⁵ or −OR ⁶ ;
R ⁴ and R ⁵ represent a hydrogen atom, an alkyl group optionally substituted with a cyano group, a hydroxyl group, a lower alkoxy group, or a dialkylamino group, a cyclohexyl group, an aryl group, or an aralkyl group, or NR ₄ R ⁵ represents represents a 5- or 6-membered nitrogen-containing heterocycle formed by linking R ⁴ and R ⁵ , R ⁶ represents an alkyl group or an aryl group optionally substituted with a lower alkoxy group or a dialkylamino group, X
represents a fluorine atom or a chlorine atom. ) are the disazo compounds and disazo dyes. The substituted or unsubstituted phenyl group, pyridyl group, thiazolyl group or benzothiazolyl group represented by D in the above general formula [] includes phenyl group; fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, trifluoro Methyl 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 substituted with phenyl group, etc.; pyridyl group; chlorine atom, bromine atom, nitro group, methyl group, methylsulfonyl group, pyridyl group substituted with cyano group, etc.; thiazolyl group; methyl group, chlorine atom, bromine atom, nitro group, lower alkoxycarbonyl group,
Thiazolyl group substituted with methoxyethoxycarbonyl group, ethoxyethoxycarbonyl group, trifluoromethyl group, methylsulfonyl group, etc.;
Benzothiazolyl group; methyl group, chlorine atom, bromine atom, nitro group, lower alkoxycarbonyl group,
Examples include benzothiazolyl groups substituted with trifluoromethyl groups, methylsulfonyl groups, etc.
Examples of the unsubstituted alkyl group represented by R ² or R ³ include methyl group, ethyl group, linear or branched propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, etc. , Substituted alkyl groups include lower alkoxy groups such as methoxyethyl, ethoxyethyl and butoxyethyl groups; lower alkoxyalkoxyalkyl groups such as methoxyethoxyethyl and ethoxyethoxyethyl groups; phenoxyalkyl groups such as phenoxyethyl; ;Optionally substituted aralkyloxy lower alkyl groups such as benzyloxyethyl group and chlorobenzyloxyethyl group;Hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, hydroxyhexyl group, 2-hydroxy-3-methoxypropyl group optionally substituted hydroxyalkyl groups such as; cyanomethyl group,
Cyano lower alkyl groups such as cyanoethyl group; optionally substituted acyloxy lower alkyl groups such as acetyloxyethyl group, chloroacetyloxyethyl group, chloropropionyloxyethyl group, benzoyloxyethyl group; methoxycarbonyloxyethyl group, methoxy Alkoxycarbonyloxy lower alkyl groups such as ethoxycarbonyloxyethyl group; carbamoyl lower alkyl groups such as carbamoylmethyl group and carbamoylethyl group; methoxycarbonylmethyl group, ethoxycarbonylmethyl group, methoxyethoxycarbonylmethyl group, benzyloxycarbonylmethyl group, etc. optionally substituted alkoxycarbonyl lower alkyl group; optionally substituted aralkyl group such as benzyl group, phenethyl group, chlorobenzyl group; allyloxycarbonyl lower such as allyloxycarbonylethyl group, allyloxycarbonylmethyl group Alkyl group; tetrahydrofurfuryl group; succinimide lower alkyl group such as succinimideethyl group; phthalimide lower alkyl group such as phthalimidoethyl group; cyanoalkoxy lower alkyl group such as cyanoethoxyethyl group, cyanomethoxyethyl group, Examples include halogenated lower alkyl groups such as chloroethyl group, and nitrogen-containing heterocyclic groups 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,
Examples thereof include 1-imidazolyl group, morpholino group, piperidino group, 2,6-dimethylpiperidino group, 1-piperazinyl group, and 4-methyl-1-piperazinyl group. NR ⁴ R ⁵ is preferably a di-substituted amino group having a total of 6 to 12 carbon atoms. The disazo compound represented by the above general formula [] is obtained by diazotizing the amine represented by the following formula [] D-NH ₂ ... [] (wherein D is the same as the above definition) to form the following formula [] (In the formula, R ¹ is the same as defined above.) The following formula obtained by coupling amines [] (wherein D and R ¹ are the same as defined above) is diazotized to form the following general formula [] It can be produced by coupling with an aniline represented by the formula (wherein, X, Y, R ² and R ³ are the same as defined above). Anilines represented by the general formula [] are represented by the following general formula [] (In the formula, R ² and R ³ are the same as defined above.) Anilines represented by 2,4,6-trihalogenotriazine and decomposition of triethylamine, sodium carbonate, etc. in a solvent such as N-methylpyrrolidone or acetone. The following general formula obtained by reacting at 0 to 10°C for 2 to 10 hours in the presence of an acid agent [] (In the formula, R ² , R ³ and X are the same as defined above.)
and alcohols or amines represented by the following general formula [] YH...[] (in the formula, Y is the same as defined above) and the decomposition of triethylamine, sodium carbonate, etc. in a solvent such as N-methylpyrrolidone or acetone. It is produced by reacting in the presence of an acid agent at room temperature for 2 to 10 hours. As the amine represented by the general formula D- _NH2 ,
Benzene amines such as aniline, O-, m
- or P-fluoroaniline, O-, m- or P-chloroaniline, O-, m- or P-bromoaniline, 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-dimethylaminocarbonylaniline, P
-N-ethylaminocarbonylaniline, P-N
-allylaminocarbonylaniline, 2-chloro4-methoxycarbonylaniline, P-N,N-
Dimethylaminosulfonylaniline, m-N,N
-diethylaminosulfonylaniline, P-N-
Examples of pyridine-based amines include ethylaminosulfonylaniline and P-phenylaniline. -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-based amines include 2-aminothiazole, 2-amino-4-methylthiazole, 2-amino-4-methyl-5-ethoxycarbonylthiazole, and 2-amino-4-methyl-5-ethoxycarbonylthiazole. -5-nitrothiazole, 2-amino-5-bromothiazole, 2
-amino-5-chloro-thiazole, 2-amino-4-trifluoromethylthiazole, 2-amino-4-methyl-5-methoxyethoxycarbonylthiazole and 2-amino-4-methyl-5
Examples of benzothiazole-based amines include 2-aminobenzothiazole, 2-amino-4,6-dibromobenzothiazole, 2-amino-6-sulfomethylbenzothiazole, and 2-amino-6-sulfomethylbenzothiazole. Examples include 5,6-dichlorobenzothiazole and 2-amino-6-nitrobenzothiazole. 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-formamide. A method of finely dispersing in water using a water-soluble dispersant such as a sodium salt of a condensate using a pulverizer such as a sand grinder or a mill, and a method of finely dispersing compounds such as sulfosuccinates, nonylphenols, etc. with a low molar addition of ethylene oxide. Use a poorly water-soluble or water-insoluble dispersant and a solvent other than water, such as alcohols such as ethyl alcohol, isopropyl alcohol, and polyethylene glycol, ketones such as acetone and methyl ethyl ketone, ketones such as acetone and methyl ethyl ketone, n-hexane, and toluene. , hydrocarbons such as xylene and mineral turpentine, halogenated hydrocarbons such as tetrachloroethylene, esters such as ethyl acetate and butyl acetate, ethers such as dioxane and tetraethylene glycol dimethyl ether, or mixed solvents thereof. Examples include a method of dispersing, and a method of finely dispersing in a mixed system of water and a solvent optionally miscible with water among the above-mentioned solvents. 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 type emulsion or a W/O type 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 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. The amount of these used is usually sufficient so that the padding bath or textile dyeing paste has a pH of 7.5 to 8.5. As an organic epoxy compound, ethylene glycol diglycidyl ether, average molecular weight
Examples of the organic vinyl compound include ethylene glycol diacrylate, polyethylene glycol diacrylate or dimethacrylate having an average molecular weight of 150 to 400, and the like. The amount of these used is about 3 to 6% by weight based on the putting bath or textile dyeing paste. In addition, a thickener, for example, 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 textile printing methods. . 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. Any cellulose fiber swelling agent can be used as long as it has a boiling point of 150°C or higher and has the effect of swelling cellulose fibers. For example, N, N,
Examples include ureas such as N,N',N'-tetramethylurea, 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. 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. By the above method, it is possible to obtain a dyed product which is vividly 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 unless the gist thereof is exceeded. 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 diaz dye represented by the 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 glycol dimethyl ether with an average molecular weight of 400 9 parts water 29.5 100 parts (PH 8.0). 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.). A blue dyeing with excellent light fastness and wet fastness was obtained. The dye used in this example was produced by the following method. That is, 9.12 g of 2-amino-3-cyano-5-phenylazothiophane was mixed with 160 ml of 85% phosphoric acid.
and 200 ml of glacial acetic acid, cooled to below 5° C., and 17.0 g of 40% nitrosyl sulfuric acid 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-cyanoethyl-N
-Ethyl-m-[2-fluoro-4-(N,N-diethylamino)-6-triazinyl]aminoaniline (14.3 g) was dissolved in 300 ml of methanol and added dropwise. The resulting precipitate was separated, washed with water, and then dried at room temperature to obtain 18 g (yield: 75%) of a blue powder of the dye represented by the above structural formula. The λmax (in acetone) of the present invention was 615 nm. Example 2 Structural formula below 15 parts of disazo dye shown by Pluronic type surfactant Pluronic L64 (manufactured by Asahi Denka Kogyo Co., Ltd.)
A dye dispersion was prepared from a dye composition consisting of 10 parts and 75 parts of water using a sand grinder as a fine disperser. This dye dispersion was used to make the following composition: Dye dispersion 7 parts 5% sodium alginate aqueous solution 55 parts Polypropylene glycol diacetate with an average molecular weight of 300 10 parts Polyethylene glycol diglycidyl ether with an average molecular weight of 200 3 parts Water 25 parts 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 greenish blue dyed product with excellent light fastness and wet fastness was obtained. The dye used in this example was produced by the following method. That is, 2-amino-3-cyano-5
-(4-nitrophenyl)azothiophene 11.0g
was added to a mixture of 160 ml of 85% phosphoric acid and 200 ml of glacial acetic acid, cooled to below 5°C, and mixed with 40% nitrosyl sulfate.
17.0g was added gradually. The mixture was heated at 0-2°C.
The diazo solution was mixed with 2 g of urea and N-
12.2 g of cyanoethyl-N-ethyl-m-(2-fluoro-4-methoxy-6-triazinyl)aminoaniline was dissolved in 300 ml of methanol and added dropwise. The resulting precipitate was separated, washed with water, and then dried at room temperature to obtain 17.6 g (yield: 75%) of blue powder of the dye represented by the above structural formula. The λmax (in acetone) of the present invention was 644 nm. Example 3 Structural formula below A dye composition consisting of 10 parts of a disazo dye shown by A dye ink was prepared. After mixing 10 parts of this dye ink and 55 parts of mineral turpentine, this was stirred with a homomixer (5000~
7000 RPM), gradually pour into 35 parts of an aqueous solution with the following composition and stir until homogeneous.
A W-type emulsion colored paste was prepared. Water 31 parts Lepitol G (trademark, Daiichi Kogyo Seiyaku Co., Ltd., special nonionic surfactant) 3.8 parts Sodium trichloroacetate 0.1 parts 34.9 parts Next, use this color paste to make a polyester/cotton (mixing ratio 65/35) blended fabric. It 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. then washed in a hot tetrachloroethylene bath containing a small amount of water;
After drying, a blue dyed product with excellent light fastness and wet fastness and free from spot staining was obtained. The dye used in this example was synthesized according to the method described in Example 1. The λmax of this product was 665 nm. Example 4 Structural formula below A dye composition consisting of 16 parts of the disazo dye shown by, 7 parts of polyoxyethylene glycol nonyl phenyl ether (HLB13.3), 3 parts of naphthalene sulfonic acid-formaldehyde condensate, and 74 parts of water was finely dispersed using a sand grinder. A dye dispersion was prepared. 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. The λmax (acetone) of this product was 625 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 red print with good wet fastness and light fastness was obtained. Example 6 Printing was carried out according to the method described in Example 1 using the diazo dyes shown in Tables 1 to 7. 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. General formula (wherein D is a substituted or unsubstituted phenyl group,
represents a pyridyl group, thiazolyl group or benzothiazolyl group, R ¹ represents a cyano group or an alkoxycarbonyl group, R ² and R ³ represent a substituted or unsubstituted alkyl group or alkenyl group, Y represents -NR ⁴ R ⁵ or −OR ⁶ , R ⁴
and R ⁵ is a hydrogen atom or an alkyl group optionally substituted with a cyano group, hydroxyl group, lower alkoxy group or dialkylamino group,
NR ⁴ R ⁵ represents a 5- or 6-membered nitrogen-containing heterocycle formed by linking R ⁴ and R ⁵ , and R ⁶ represents a lower alkoxy group or It represents an alkyl group or an aryl group which may be substituted with a dialkylamino group, and X represents a fluorine atom or a chlorine atom. ) A disazo compound represented by 2 General formula (wherein D is a substituted or unsubstituted phenyl group,
represents a pyridyl group, thiazolyl group or benzothiazolyl group, R ¹ represents a cyano group or an alkoxycarbonyl group, R ² and R ³ represent a substituted or unsubstituted alkyl group or alkenyl group, Y represents -NR ⁴ R ⁵ or −OR ⁶ , R ⁴
and R ⁵ is a hydrogen atom or an alkyl group optionally substituted with a cyano group, hydroxyl group, lower alkoxy group or dialkylamino group,
NR ⁴ R ⁵ represents a 5- or 6-membered nitrogen-containing heterocycle formed by linking R ⁴ and R ⁵ , and R ⁶ represents a lower alkoxy group or It represents an alkyl group or an aryl group which may be substituted with a dialkylamino group, and X represents a fluorine atom or a chlorine atom. ) Disazo dyes.