JPH0332586B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to disazo compounds and disazo dyes for cellulose-containing fibers. Specifically, the present invention relates to a reactive disazo dye that dyes disazo compounds and cellulose-containing fibers, particularly cellulose fibers or mixed fibers consisting of polyester fibers and cellulose fibers, orange and has excellent color fastness, particularly light fastness. . The present invention will be explained in detail below. The gist of the present invention is the following general formula [] [During the ceremony,

[Formula] represents a phenylene group optionally substituted with a lower alkyl group, a lower alkoxy group, a halogen atom or a trifluoromethyl group,

[Formula] represents a naphthylene group, or a phenylene group optionally substituted with a lower alkyl group, a lower alkoxy group, or an acetylamino group,

[Formula] represents a phenyl group optionally substituted with a halogen atom, a sulfamoyl group or a lower alkylsulfamoyl group, -X- represents a linking group of -O- or -S-, and Y ¹ and Y ² represents a hydrogen atom or an alkyl group, an alkenyl group, a cyclohexyl group, an aryl group, or an aralkyl group which may be substituted with a cyano group, a hydroxyl group, a lower alkoxy group, a lower alkoxy group, or a dialkylamino group, or
NY ¹ Y ² represents a 5- or 6-membered nitrogen-containing heterocycle formed by linking Y ¹ and Y ² , and the total carbon atoms of Y ¹ and Y ² are 18 or less. ] The disazo compounds and disazo dyes for cellulose-containing fibers include: The compound represented by the above general formula [] is the following general formula (In the formula,

【formula】,

【formula】,

[Formula] and X are the same as defined above. ) is represented by the following general formula [] (In the formula, Y ¹ and Y ² are the same as defined above.) It can be easily produced by reacting with a compound represented by the above formula. The present invention will be explained in detail below. In the general formula [] and []

[expression] or

Examples of the lower alkyl group as a substituent in [Formula] include a methyl group, an ethyl group, and a linear or branched alkyl group having 3 to 4 carbon atoms, and examples of the lower alkoxy group include a methoxy group, an ethoxy group, Examples include straight-chain or branched alkoxy groups having 3 to 4 carbon atoms.

[expression] or

Examples of the halogen atom as a substituent in the formula include a fluorine atom, a chlorine atom, and a bromine atom.

As the lower alkylsulfamoyl group which is a substituent of [Formula], methylsulfamoyl group,
Ethylsulfamoyl group, isopropylsulfamoyl group, n-propylsulfamoyl group, n-
Examples include butylsulfamoyl group, dimethylsulfamoyl group, diethylsulfamoyl group, di-n-propylsulfamoyl group, and the like. In addition, the alkyl group represented by Y ¹ and Y ² in the general formula [] includes a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 18 carbon atoms, and a substituted alkyl group. Examples include cyanomethyl group, 2-cyanoethyl group, 3-cyanopropyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 2-(2-hydroxyethoxy)ethyl group. , tris(hydroxymethyl)methyl group, 2-ethoxyethyl group, 3-isopropoxypropyl group, 3-(2-methoxyethoxy)propyl group, 2,2-diethoxyethyl group, 2-(N,N-diethylamino ) ethyl group,
2-(N,N-dimethylamino)ethyl group, 3-
Examples thereof include an alkyl group substituted with a cyano group such as a (N,N-dimethylmino)propyl group, a hydroxyl group, a lower alkoxy group, a lower alkoxy group, or an alkylamino group. Examples of the alkenyl group include allyl group, 2-methylallyl group, 3-methylallyl group, linear or branched alkenyl group having 4 to 18 carbon atoms,
As the substituted alkenyl group, 3-cyanoallyl group,
Cyano groups such as 2-hydroxyallyl group, 3-methoxyethoxyallyl group, 1-methyl-3-(N,N-diethylamino)allyl group, hydroxy group,
Examples include alkenyl groups substituted with lower alkoxy groups. Examples of the aryl group include phenyl group, naphthyl group, o-tolyl group, p-butylphenyl group, and examples of the aryl group substituted with a cyano group, hydroxyl group, lower alkoxy group, or dialkylamino group include m-cyanophenyl group. group, p-hydroxyphenyl group, p-methoxyphenyl group, p-(2-methoxyethoxy)phenyl group, 2,5-dimethoxyphenyl group, p-(N,
Examples include N-dimethylamino)phenyl group. Examples of aralkyl groups include benzyl group, phenethyl group, m-methylbenzyl group, p-methylphenethyl group, etc. Substituted aralkyl groups include:
Examples include m-cyanobenzyl group, p-hydroxybenzyl group, p-hydroxyphenethyl group, and o-anisyl group. In addition, the nitrogen-containing heterocyclic group represented by NY ¹ Y ² includes 1-pyrrolidinyl group, 3-methyl-1-pyrrolidinyl group, 2-hydroxyethyl-1-pyrrolidinyl group, and 2,5-dimethyl-1-pyrrolidinyl group. 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-1-
Examples include piperazinyl group. As NY ¹ Y ² , a di-substituted amino group having a total of 6 to 12 carbon atoms is particularly desirable. Further, when n is 0, the light fastness is particularly excellent. To produce the disazo compound represented by the general formula [], for example, acetone, methyl ethyl ketone, toluene, nitrobenzene, dioxane,
N,N-dimethylformamide, N-methyl-2
- In an organic solvent such as pyrrolidone or dimethyl sulfoxide, a disazo compound represented by the general formula [] and a difluorotriazine represented by the general formula [] in an amount of 1 to 1.2 times the mole of the disazo compound are added as described above. 1 to 2 for disazo compounds
0.5 to 90°C in the presence of twice the molar amount of an acid binder, e.g., a tertiary amine such as triethylamine, tributylamine, N,N-diethylaniline, an inorganic base such as potassium carbonate, potassium hydrogen carbonate, etc.
It may be heated for ~5 hours. The resulting reaction product liquid is cooled and then discharged into water, for example, and the resulting precipitate is separated by a method such as filtration or centrifugation to obtain the disazo dye represented by the general formula [] almost quantitatively. can. 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 non-woven fabrics thereof. In addition, blended or blended products of the above fibers and other types of fibers such as polyester fibers, cationically dyeable polyester fibers, anionically dyeable polyester fibers, polyamide fibers, wool, acrylic fibers, urethane fibers, diacetate fibers, triacetate fibers, etc. can be mentioned. Among these, it is particularly effective for cellulose fibers and blended or woven products of cellulose fibers and polyester fibers. When carrying out dyeing, it is desirable to finely disperse the dye represented by the general formula [] in a medium to a particle size of about 0.5μ to 2μ. A method in which a water-soluble dispersant such as anionic dispersant such as sodium ligninsulfonate or sodium salt of a naphthalenesulfonic acid-formalin condensate is used and finely dispersed in water using a pulverizer such as a sand grinder or a mill, or a sulfosuccinate ester. , using a poorly water-soluble or water-insoluble dispersant such as a compound with a low mole of ethylene oxide added to nonylphenol, etc., and a solvent other than water, such as alcohols such as ethyl alcohol, isopropyl alcohol, and polyethylene glycol, and ketones such as acetone and methyl ethyl ketone. hydrocarbons such as n-hexane, toluene, xylene, mineral turpentine, halogenated hydrocarbons such as tetrachloroethylene, esters such as ethyl acetate, butyl acetate,
A method of finely dispersing dioxane, tetraethylene glycol dimethyl ether in ethers or a mixed solvent thereof, a method of finely dispersing it in a mixed system of water and a solvent optionally miscible with water among the above solvents, etc. can be given. 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 a padding dyeing method and as a printing dyeing paste in a textile printing method, but when used as a normal padding bath and printing dyeing paste, the above dye fine dispersion can be further mixed with water or water. Targeted dyeing of O/W emulsion or W/O emulsion systems in which the solvent and water that can be mixed arbitrarily are mixed or the oil layer is a petroleum hydrocarbon such as mineral turbene or a halogenated hydrocarbon such as tetrachloroethylene. A diluted product is used depending on the concentration. Acid bonds are added to alkali metal compounds, organic epoxy compounds, organic vinyl compounds, etc. for the purpose of promoting the reaction between cellulose fiber swelling agents or dyes and cellulose fibers in order to advantageously carry out dyeing in the preparation of padding baths and printing dyeing pastes. It can be added as an agent. 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 pH of the padding bath or textile dyeing paste is 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 padding bath or textile dyeing paste. 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. The preparation of the padding bath or printing dyeing paste is not limited to the above method, and the cellulose swelling agent and acid binder do not necessarily need to be present in the padding bath or printing dyeing paste, but are applied to the fiber side in advance. It may be left to exist. 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, such as N, N,
Examples include ureas such as 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 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. Using this dye dispersion, a printing dyeing 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 parts 100 parts (Hz 8.0) was prepared. /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 a few 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 nonionic surfactant (Score Roll #900 (trademark), manufactured by Kao Soap Co., Ltd.). An orange dyeing with excellent light fastness and wet fastness was obtained. 2.13 g of the dye 4-amino-4'-hydroxylazobenzene used in this example was dissolved in a 50% acetic acid aqueous solution, 3 ml of hydrochloric acid was added, and the mixture was cooled to below 5°C. Next, 0.7 g of sodium nitrite was added. . At this time, the temperature was kept not to exceed 5°C. The obtained diazonium salt solution was added to a solution of 1.73 g of 1-phenyl-3-methyl-5-pyrazolone dissolved in a dilute aqueous sodium hydroxide solution at 5° C. or lower while adjusting the frequency to 8 to 9 Hz. The precipitated disazo compound was removed, washed with water, and dried. This dye 3.97
g, 2.1 g of 2,4-difluoro-6-(diethyl)aminotriazine, 1.0 g of triethylamine and 1.0 g of anhydrous potassium carbonate were added to 100 ml of acetone and heated under reflux for 3 hours to carry out a condensation reaction.
The resulting reaction solution was added dropwise to 1000 ml of water to separate the formed precipitate, which was washed with water and dried at room temperature to obtain 5.2 g of yellow powder of the dye represented by the above structural formula (yield: 92
%) was obtained. The λmax (acetone) of this dye was 422 nm. Example 2 Structural formula below 15 parts of disazo dye shown by Pluronik type surfactant Bluronik 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. Using this dye dispersion, we used the following composition: Dye dispersion 7 parts 5% aqueous sodium alginate solution 55 parts Polypropylene with an average molecular weight of 300 10 parts Glycol diacetate 3 parts Polyethylene with an average molecular weight of 200 Glycol diglycidyl ether 25 parts Water 100 parts ( Hz6.5) 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 an orange dyed product with excellent light fastness and wet fastness was obtained. The dye used in this example was obtained by diazotizing 4-amino-4'-hydroxylazobenzene as described in Example 1 and coupling it with 1-(m-chlorophenyl)-3-methyl-5-pyrazolone. It was obtained by reacting with 2,4-difluoro-6-[di-(n-propyl)amino]triazine in N-methyl-2-pyrrolidone using triethylamine as a deoxidizing agent. The λmax (acetone) of this product was 416 nm. Example 3 Structural formula below 10 parts of disazo dye represented by, 2 parts of polyoxyethylene glycol-nonyl phenyl ether (HLB8.9) and diethylene glycol-
A dye ink was prepared by grinding a dye composition consisting of 88 parts of 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~
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 3.8 parts (trademark, Daiichi Kogyo Seiyaku Co., Ltd., special nonionic surfactant) 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. Thereafter, the dyed product was washed in a hot tetrachloroethylene bath containing a small amount of water and dried to give an orange dyed product with excellent light fastness and wet fastness and no white spot staining. The dye used in this example was obtained by diazotizing 4-amino-2'-chloro-4-hydroxyazobenzene as described in Example 1 and coupling it with 1-phenyl-3-methyl-5-pyrazolone. It was obtained by reacting with 2,4-difluoro-6-piperidinotriazine according to Example 1. The λmax (acetone) of this product was 427 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, prepare a padding bath with the following composition: Dye dispersion 6 parts Tetraethylene glycol 15 parts Dimethyl ether Water 79 parts 100 parts (Hz 8.0) Polyester/cotton (mixing ratio 65/35) blended fabric The material was impregnated with water, squeezed to a squeezing rate of 45%, dried at 100℃ for 2 minutes, and fixed under dry heat at 200℃ for 1 minute. This product was washed in a hot ethanol bath to achieve excellent light fastness and wet fastness. An orange dyed product 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 431 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 reddish-yellow print with good wet fastness and light fastness was obtained. Example 6 Example 1 using the disazo dye 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. General formula [In the formula, [Formula] represents a lower alkyl group, a lower alkoxy group, a phenylene group optionally substituted with a halogen atom or a trifluoromethyl group, and [Formula] represents a naphthylene group, or a lower alkyl group, a lower alkoxy group. or represents a phenylene group which may be substituted with an acetylamino group, [Formula] represents a phenyl group which may be substituted with a halogen atom, a sulfamoyl group or a lower alkylsulfamoyl group, and -X- represents -O - or -S- represents a linking group, and Y ¹ and Y ² are a hydrogen atom or a cyano group, a hydroxyl group, a lower alkoxy group,
Lower alkoxy represents an alkyl group, alkenyl group, cyclohexyl group, aryl group or aralkyl group which may be substituted with a lower alkoxy group or a dialkylamino group, or
NY ¹ Y ² represents a 5- or 6-membered nitrogen-containing plural ring formed by linking Y ¹ and Y ² , and the total number of carbon atoms of Y ¹ and Y ² is 18 or less. ) A disazo compound represented by 2 General formula [In the formula, [Formula] represents a lower alkyl group, a lower alkoxy group, a phenylene group optionally substituted with a halogen atom or a trifluoromethyl group, and [Formula] represents a naphthylene group, or a lower alkyl group, a lower alkoxy group. or represents a phenylene group which may be substituted with an acetylamino group, [Formula] represents a phenyl group which may be substituted with a halogen atom, a sulfamoyl group or a lower alkylsulfamoyl group, and -X- represents -O - or -S- represents a linking group, and Y ¹ and Y ² are a hydrogen atom or a cyano group, a hydroxyl group, a lower alkoxy group,
Lower alkoxy represents an alkyl group, alkenyl group, cyclohexyl group, aryl group or aralkyl group which may be substituted with a lower alkoxy group or a dialkylamino group, or
NY ¹ Y ² represents a 5- or 6-membered nitrogen-containing plural ring formed by linking Y ¹ and Y ² , and the total number of carbon atoms of Y ¹ and Y ² is 18 or less. ) Disazo dye for cellulose-containing fibers.