JPH0334504B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to disazo compounds and azo dyes for cellulose-containing fibers. Specifically, the present invention relates to a reactive disazo dye for dyeing cellulose-containing fibers, cellulose fibers, and mixed fibers consisting of polyester fibers and cellulose fibers in an orange color with excellent color fastness including 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 phenyl group which may be substituted with a lower alkyl group, a lower alkoxy group, a halogen atom, a trifluoromethyl group or a cyano group, and R ¹ and R ² are a hydrogen atom, a cyano group, a hydroxyl group, a lower an alkyl group optionally substituted with an alkoxy group, a lower alkoxy lower alkoxy group or a dialkylamino group,
represents an alkenyl group, cyclohexyl group, aryl group or aralkyl group, or NR ¹ R ² represents R ¹
A 5-membered or 6-membered member formed by the combination of and R ²
represents a membered nitrogen-containing heterocycle, the total number of carbon atoms of R ¹ and R ² is 18 or less,

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

[Formula] represents a lower alkyl group, a lower alkoxy group, or a phenyl group optionally substituted with a halogen atom. ] The disazo compounds and disazo dyes for cellulose-containing fibers include: The compound represented by the above general formula [] is, for example, the following general formula [] [During the ceremony,

【formula】

【formula】

[Formula] is the same as the above definition. ] The compound represented by the following general formula [] [In the formula, R ₁ and R ₂ are the same as defined above. ] It can be easily produced by reacting the compound represented by the above in a solvent such as N-methyl-2-pyrrolidone. The present invention will be explained in detail below. In the general formula [] and []

[expression] or

[expression] and

Examples of the lower alkyl substituent of the phenyl group represented by the formula include a methyl group, ethyl, 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, a linear or branched alkoxy group having 3 to 4 carbon atoms, and examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. In addition, examples of the alkyl group represented by R ¹ and R ² in the general formula [] include a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 18 carbon atoms, and substituted alkyl groups. 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, isopropoxypropyl group, 3-(2-methoxyethoxy)propyl group, 2,2-diethoxyethyl group,
2-(N,N-diethylamino)ethyl group, 2-
(N,N-dimethylamino)ethyl group, 3-(N,
Cyano groups such as N-dimethylamino)propyl groups,
Examples include alkyl groups substituted with a hydroxyl group, a lower alkoxy group, or a dialkylamino 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, and substituted alkenyl groups include 3-cyanoallyl group, 2-methylallyl group, and linear or branched alkenyl group having 4 to 18 carbon atoms. Examples include alkenyl groups substituted with cyano groups, hydroxy groups, and lower alkoxy groups, such as hydroxyallyl groups, 3-methoxyethoxyallyl groups, and 1-methyl-3-(N,N-diethylamino)allyl 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 NR ¹ R ² includes a 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 NR ¹ R ² , a di-substituted amino group having a total of 6 to 12 carbon atoms is particularly desirable. 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, tributylamino, N,N-diethylaniline, an inorganic base such as potassium carbonate, potassium bicarbonate, etc.
It may be heated for ~5 hours. After cooling the obtained reaction product liquid, for example, by discharging it into water, the resulting precipitate is separated by a method such as filtration or centrifugation to obtain a disazo compound represented by the general formula [] almost quantitatively. Can be done. Cellulose-containing fibers that can be dyed with the dye represented by the general formula [] include natural fibers such as cotton and hemp, semi-synthetic fibers such as viscose rayon and cuprammonium rayon, and partially aminated or partially acylated modified fibers. Examples include fibers such as quality cellulose fibers, woven or knitted fabrics, non-woven fabrics, etc. thereof. Also, blended or woven products of the above fibers and other types of fibers such as polyester fibers, cationic dyeable polyester fibers, anionic 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, 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 Brulonik type surfactant or an anionic dispersant such as sodium ligninsulfonate or naphthalenesulfonic acid-formalin. Using a water-soluble dispersant such as a sodium salt of a condensate,
Method of finely dispersing in water using a grinder such as a sand glider or mill, sulfosuccinate ester,
Use a poorly water-soluble or water-insoluble dispersant such as a compound with a low mole of ethylene oxide added to nonyl phenyl, etc. Solvents other than water, such as celluloses 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 turbines, halogenated hydrocarbons such as tetrachloroethylene, esters such as ethyl acetate, butyl acetate,
A method of finely dispersing it in ethers such as dioxane and tetraethylene glycol dimethyl ether or a mixed solvent thereof, a method of finely dispersing it in a mixed system of water and a solvent that can be arbitrarily mixed 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 liquid can be used as it is as a padding bath in the padding dyeing method and as a printing dyeing paste in the textile printing method, but when used as a normal padding bath and printing dyeing paste, the above dye fine dispersion liquid can be mixed with water or optionally with water. Target dyeing of O/W emulsion or W/O emulsion systems in which water is mixed with a solvent that can be mixed with water, or the oil layer is a petroleum-based hydrocarbon such as mineral turbene, or a halogenated hydrocarbon such as tetrachloroethylene. A diluted product is used depending on the concentration. 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 In addition to alkali metal carbonates, alkali metal compounds include 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 acrylate, diacrylate or dimethacrylate of polyethylene glycol 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 that has a boiling point of 150°C or higher and has the effect of swelling cellulose fibers can be used. For example, 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. Clean with a W/O type emulsion cleaning bath, or
Alternatively, it can be completed by washing using a normal 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: 6.5 parts of dye dispersion, 55 parts of 5% sodium alginate aqueous solution, 9 parts of polyethylene glycol dimethyl ether with an average molecular weight of 400, 29.5 parts of water, 100 parts (PH8.0) was prepared, and polyester /cotton (mixing ratio 65/35) blended fabric was printed using a screen printing machine, dried at 80°C for 3 minutes, and then dry-heat-fixed at 215°C for 90 seconds. After washing it with water, use a nonionic surfactant (Scoreroll #900 (trademark), Kao Soap Co., Ltd.).
The bath ratio was 1: using a cleaning solution containing 2 g/
Sowing was carried out at 30°C for 20 minutes at 80°C to obtain an orange dyeing with excellent light fastness and wet fastness. The dye used in this example was prepared by dissolving 2.13 g of 4-amino-4'-hydroxyazobenzene in 50 ml of a 50% (volume) acetic acid aqueous solution, adding 3 ml of hydrochloric acid, and stirring at 5°C.
Cooled down to below. Next, 0.7 g of sodium nitrite was added. At this time, the temperature did not exceed 5°C, and the resulting diazonium salt solution was mixed with acetoacetic acid-2,4-
The mixture was added to an aqueous solution of 2.4 g of dimethoxyanilide at 5° C. or lower while adjusting the pH to 10. The precipitated disazo compound was collected by filtration, washed with water, and dried. 4.61 g of this dye, 2.1 g of 2,4-difluoro-6-(diethylamino)triazine, 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 dropped into 1000 ml of water, and the resulting precipitate was filtered, washed with water, and dried at room temperature to give 6.1 g of a dark yellow powder of the dye represented by the above structural formula (yield:
92%). The λmax (acetone) of this dye was 409 nm. Example 2 Structural formula below 15 parts of disazo dye represented by Pluronik L64, a Pluronik type surfactant (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 glider as a fine disperser. This dye dispersion was used to make the following composition: Dye dispersion 7 parts 5% aqueous sodium alginate 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 performed 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-5-methyl-4'-hydroxyazobenzene as described in Example 1 and coupling it with acetoacetanilide.
It was obtained by reacting with 2,4-difluoro-6-[di-(n-propyl)amino]triazine in pyrrolidone using triethylamino as a deoxidizing agent. The λmax (acetone) of this product was 409 nm. Example 3 Structural formula below 10 parts of disazo dye represented by, 2 parts of polyoxyethylene glycol nonylphenyl 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 Levitol G (trademark, Daiichi Kogyo Seiyaku Co., Ltd., special nonionic surfactant) 3.8 parts Sodium trichloroacetate 0.1 part 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 2'-acetylamino-4'-amino-3-hydroxyazobenzene according to Example 1, and producing acetoacetic acid-2-
It was obtained by coupling with ethoxyanilide and reacting the obtained dye with 2,4-difluoro-6-piperidinotriazine according to Example 1. The λmax (acetone) of this product was 413 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 100 parts (PH8.0), impregnate a polyester/cotton (mixing ratio 65/35) blended fabric, squeeze to a squeezing rate of 45%, and dry 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, an orange 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 412 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-orange 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 disazo dyes shown in Tables 1 to 3. The light fastness and wet fastness of the dyed fabric obtained were both good. The hue of the dyed fabric and the λmax (acetone) of the dye are shown in Tables 1 to 3.

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Claims (1)

[Claims] 1. General formula [Wherein, [Formula] represents a phenyl group which may be substituted with a lower alkyl group, a lower alkoxy group, a halogen atom, a trifluoromethyl group or a cyano group, and R ¹ and R ² are a hydrogen atom, a cyano group, an alkyl group optionally substituted with a hydroxyl group, a lower alkoxy group, a lower alkoxy lower alkoxy group or a dialkylamino group,
represents an alkenyl group, cyclohexyl group, aryl group or aralkyl group, or NR ¹ R ² represents R ¹
A 5-membered or 6-membered member formed by the combination of and R ²
represents a nitrogen-containing heterocycle in which the total number of carbon atoms of R ¹ and R ² is 18 or less, and [Formula] is substituted with a naphthylene group, a lower alkyl group, a lower alkoxy group, a halogen atom, or an acetylamino group. represents a phenylene group which may be
[Formula] represents a lower alkyl group, a lower alkoxy group, or a phenyl group optionally substituted with a halogen atom. ] A disazo compound represented by 2 General formula [Wherein, [Formula] represents a phenyl group which may be substituted with a lower alkyl group, a lower alkoxy group, a halogen atom, a trifluoromethyl group or a cyano group, and R ¹ and R ² are a hydrogen atom, a cyano group, an alkyl group optionally substituted with a hydroxyl group, a lower alkoxy group, a lower alkoxy lower alkoxy group or a dialkylamino group,
represents an alkenyl group, cyclohexyl group, aryl group or aralkyl group, or NR ¹ R ² represents R ¹
A 5-membered or 6-membered member formed by the combination of and R ²
represents a nitrogen-containing heterocycle in which the total number of carbon atoms of R ¹ and R ² is 18 or less, and [Formula] is substituted with a naphthylene group, a lower alkyl group, a lower alkoxy group, a halogen atom, or an acetylamino group. represents a phenylene group which may be
[Formula] represents a lower alkyl group, a lower alkoxy group, or a phenyl group optionally substituted with a halogen atom. ] A disazo dye for cellulose-containing fibers.