JPH0217585B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a water-insoluble anthraquinone compound, an anthraquinone dye, and an anthraquinone dye for dyeing cellulose-containing fibers, particularly cellulose fibers or mixed fibers consisting of cellulose fibers and polyester fibers, in a strong bluish red to reddish purple color, and an anthraquinone dye. . JP-A No. 55-135164 describes the general formula Anthraquinone dyes for cellulose-containing fibers are disclosed, but 1-amino-
In the method for producing the above dye by reacting 2-hydroxyalkyloxy-4-hydroxyanthraquinone with difluoroaminotriazine,
The disadvantage is that the yield is very low because difluoroaminotriazine also reacts with the amino group at the 1-position or the hydroxyl group at the 4-position of the anthraquinone nucleus. The present inventors conducted various studies to improve the above-mentioned drawbacks, and found that by changing the substituent at the 2-position of the anthraquinone nucleus to a hydroxyphenyloxy group or a hydroxyphenylthio group, difluoroaminotriazine can be formed on the phenyl group. discovered that it reacts almost stoichiometrically with the hydroxyl group of
We have arrived at the present invention. That is, the gist of the present invention is the following general formula [] ⁽ wherein ^, an alkyl group which may be substituted with a hydroxyl group, a lower alkoxy group or a dialkylamino group; a cyclohexyl group; a phenyl group which may be substituted with a methyl group, a methoxy group or a hydroxyl group; a phenethyl group; or a benzyl group optionally substituted with a methoxy group, or NR ¹ R ² represents a 5- or 6-membered nitrogen-containing heterocycle formed by linking R ¹ and R ² ;
The total number of carbon atoms in R ¹ and R ² is 14 or less. ) Anthraquinone compound, anthraquinone dye and general formula [] (In the formula, X, n and Y are the same as defined above.) An anthraquinone compound represented by the general formula [] (In the formula, R ¹ and R ² are the same as defined above.) A method for producing an anthraquinone dye represented by the above general formula [], characterized by reacting it with a difluorotriazine represented by the following. The present invention will be explained in detail below. In the method of the present invention, specific examples of anthraquinone compounds represented by the general formula [] include 1-
Amino-2-(2-hydroxyphenyloxy)
-4-hydroxyanthraquinone, 1-amino-
2-(3-hydroxyphenyloxy)-4-hydroxyanthraquinone, 1-amino-2-(4
-hydroxyphenyloxy)-4-hydroxyanthraquinone, 1-amino-2-(4-hydroxyphenylthio)-4-hydroxyanthraquinone, 1-amino-2-(4-hydroxyphenyloxy)-4-hydroxy -5-chloroanthraquinone, 1-amino-2-(3-hydroxyphenyloxy)-4-hydroxy-8-bromoanthraquinone, 1-amino-2-(3-hydroxyphenylthio)-4-hydroxy- 6,7-
Examples include dichloroanthraquinone. 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 14 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, 3-
Isopropoxypropyl group, 3-(2-methoxyethoxy)propyl group, 2,2-diethoxyethyl group, 2-(N,N-diethylamino)ethyl group, 2-(N,N-dimethylamino)ethyl group,
Examples include alkyl groups substituted with a cyano group such as a 3-(N,N-dimethylamino)propyl group, a hydroxyl group, a lower alkoxy group, or a dialkylamino group. Examples of the phenyl group which may be substituted with a methyl group, methoxy group or hydroxyl group include phenyl group, o-tolyl group, 2,4-dimethylphenyl group, p-methoxyphenyl group, 2,5-dimethoxyphenyl group. enyl group, p-hydroxyphenyl group, etc., phenethyl group which may be substituted with methyl group, phenethyl group, p-methylphenethyl group, etc., and benzyl group which may be substituted with methoxy group. , p-methoxybenzyl group, and the like. 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. The anthraquinone dye of the present invention is represented by the above-mentioned general formula [], and more specifically, the anthraquinone-based compound represented by the above-mentioned general formula [] and its substituents are specifically exemplified. This is a group of compounds obtained by reaction with difluorotriazines represented by the general formula []. In order to produce an anthraquinone compound represented by the general formula [] by the method of the present invention, acetone, toluene, nitrobenzene, dioxane, N,N-
In an organic solvent such as dimethylformamide, N-methyl-2-pyrrolidone, or dimethyl sulfoxide, an anthraquinone compound represented by the general formula
1.2 times the mole of the difluorotriazine represented by the general formula [] is mixed with an acid binder, such as triethylamine, tributylamine, N,N-diethylaniline, etc., in an amount of 1 to 2 times the mole of the anthraquinone compound. What is necessary is just to heat it from room temperature to 70 degreeC for about 0.5 to 2 hours in the presence of a class amine. After cooling the resulting reaction product liquid, it is discharged into water, and the resulting precipitate is separated by a method such as filtration or centrifugation, and almost quantitatively the general formula []
An anthraquinone compound represented by can be obtained. Cellulose-containing fibers that can be dyed with the dye of the present invention represented by the general formula Examples include fibers such as modified cellulose fibers, woven and knitted fabrics, and nonwoven 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, 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 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,
A method of finely dispersing in water using a pulverizer such as a sand grinder or a mill, or a solvent other than water using a poorly water-soluble or water-insoluble dispersant such as a compound with a low molar addition of ethylene oxide to sulfosuccinate, nonylphenol, etc. , alcohols such as ethyl alcohol, isopropyl alcohol, polyethylene glycol, acetone,
Ketones such as methyl ethyl kent, hydrocarbons such as n-hexane, toluene, xylene, mineral turpentine, halogenated hydrocarbons such as tetrachloroethylene, esters such as ethyl acetate, butyl acetate, dioxane, tetraethylene glycol dimethyl ether, etc. Examples include a method of finely dispersing it in ethers or a mixed solvent thereof, and a method of finely dispersing it 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 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 fibers with the dye of the present invention represented by the general formula [], the cellulose fiber-containing material is impregnated or printed with a padding bath or printing dye paste prepared by the above method, and then dried. With hot air or superheated steam at 160℃~220℃
Heat treatment for 30 seconds to 10 minutes, or treatment in high pressure saturated steam at 120℃ to 150℃ for 3 to 30 minutes, and wash with hot water containing a surfactant, or if the oil layer is a halogenated hydrocarbon such as tetrachloroethylene. The cleaning is completed by cleaning with an O/W type or 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 the examples, "parts" or "parts by weight" are indicated. Example 1 The following structural formula The dye represented by was synthesized by the following method. Dissolve 3.47 g of 1-amino-2-(4-hydroxyphenyloxy)-4-hydroxyanthraquinone in 30 ml of N-methyl-2-pyrrolidone, and add 1.1 g of triethylamine and 1.9 g of 2,4-difluoro-6-diethylaminotriazine. Add
The condensation reaction was carried out by stirring at 20°C for 30 minutes. The resulting reaction solution was dropped into 500 ml of water, the resulting precipitate was separated, washed with water, and dried at room temperature in a vacuum dryer to obtain a deep red powder of the dye represented by the above structural formula.
5.0 g (yield 97%) was obtained. The λmax (acetone) of this dye was 516 nm, and no impurities were observed in analysis by thin layer chromatography. A dye dispersion was prepared from the obtained dye composition consisting of 15 parts of anthraquinone dye, 15 parts of 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 with an average molecular weight of 400 , 29.5 parts of glycol dimethyl ether water, 100 parts (PH8.0) was prepared, and a printing paste was prepared for 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 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.). A bluish red dyeing with excellent light fastness and wet fastness was obtained. Comparative example 1 Structural formula below The dye represented by was produced according to the method of Example 1. That is, 1-amino-2-(2-hydroxyethoxy)-4-hydroxyanthraquinone
A condensation reaction was carried out in the same manner as in Example 1 except that 2.86 g was used. The obtained reaction solution was developed using a mixed solvent of toluene/ethyl acetate (volume ratio 4/1) on a thin layer chromatogram (silica gel).
When the yield of the dye represented by the above structural formula was determined using Chromoscan 200, it was less than 5% and a large amount of starting material remained, so the same reaction was repeated with the reaction time extended to 20 hours. Summer. As a result, the yield of the dye represented by the above structural formula was about 40%. Example 2 3.47 g of 1-amino-2-(3-hydroxyphenyloxy)-4-hydroxyanthraquinone was dissolved in 30 ml of dimethyl sulfoxide, and 3.5 g of tributylamine and 2,4-difluoro-6-
2.4 g of (N-methylanilino)triazine was added and a condensation reaction was carried out in the same manner as in Example 1, followed by the following structural formula. 5.4 g (yield: 95%) of anthraquinone dye powder was obtained. The λmax (acetone) of this dye is
It was 516nm. 15 parts of the obtained anthraquinone dye, Pluronic type surfactant Pluronic L64 (Asahi Denka Kogyo Co., Ltd.)
A dye dispersion was prepared using a sand grinder as a fine dispersion machine using a dye composition consisting of 10 parts of A. This dye dispersion was used to make the following composition: Dye dispersion 7 parts 5% aqueous sodium alginate solution 55 parts Polypropylene with an average molecular weight of 300 10 parts Polyethylene with an average molecular weight of 200 Glycol diacetate 3 parts Glycol diglycidyl ether 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 bluish-red dyed product with excellent light fastness and wet fastness was obtained. Example 3 3.63 g of 1-amino-2-(3-hydroxyphenylthio)-4-hydroxyanthraquinone was dissolved in 100 ml of acetone, 1.2 g of triethylamine and 2.0 g of 2,4-difluoro-6-(1-pyrrolidinyl) triazine. g was added thereto, and the mixture was heated under reflux for 2 hours to carry out a condensation reaction. The reaction solution was treated in the same manner as in Example 1 to obtain the following structural formula at λmax (acetone) of 540 nm. 5.0g of anthraquinone dye (yield 91%)
was gotten. 10 parts of the obtained anthraquinone dye, 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 Lepitol G 3.8 parts (trademark, Daiichi Kogyo Yakuhin 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. After washing in a hot tetrachloroethylene bath containing a small amount of water and drying, a reddish-purple dyed product with excellent light fastness and wet fastness and no spot staining was obtained. Example 4 3.82 g of 1-amino-2-(2-hydroxyphenyloxy)-4-hydroxy-5-chloroanthraquinone was dissolved in 50 ml of tetrahydrofuran,
1.7 g of N,N-diethylaniline and 2,4-
A condensation reaction was carried out in the same manner as in Example 3 by adding 1.85 g of difluoro-6-(β-cyanoethyl)aminotriazine, and the reaction solution was treated in the same manner as in Example 1 to obtain the following structural formula. 5.3 g (yield: 93%) of anthraquinone dye (λmax (acetone) = 527 nm) represented by the formula was obtained. A dye composition consisting of 16 parts of the obtained anthraquinone dye, 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, prepare a padding bath with the following composition: 6 parts of dye dispersion, 15 parts of tetraethylene glycol , 79 parts of dimethyl ether water, 100 parts (PH8.0), and prepare a padding bath with the following composition: Polyester/cotton (mixing ratio 65/35) blended fabric After squeezing to a squeezing rate of 45%, it was dried at 100°C for 2 minutes and fixed by dry heat at 200°C for 1 minute. By washing this product in a hot ethanol bath, a rubine dyed product with excellent light fastness and wet fastness was obtained. Example 5 Anthraquinone dyes listed in Tables 1 to 3 were produced according to Example 1, and a polyester/cotton (mixing ratio 65/35) blend fabric was printed in the same manner as in Example 1. The light fastness and wet fastness of the dyed fabric obtained were both good. Tables 1 to 3 show the hue of the dyed fabric and the λmax (acetone) of the dye.

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Claims (1)

[Claims] 1. General formula ⁽ wherein ^, a hydroxyl group, an alkyl group optionally substituted with a lower alkoxy group or a dialkylamino group; a cyclohexyl group;
represents a phenyl group which may be substituted with a methyl group, a methoxy group or a hydroxyl group; a phenethyl group which may be substituted with a methyl group; or a benzyl group which may be substituted with a methoxy group, or NR ¹ R ² represents a 5- or 6-membered nitrogen-containing heterocycle formed by linking R ¹ and R ² , and the total number of carbon atoms of R ¹ and R ² is 14 or less. ) Anthraquinone compound represented by. 2 General formula ⁽ wherein ^, a hydroxyl group, an alkyl group optionally substituted with a lower alkoxy group or a dialkylamino group; a cyclohexyl group;
represents a phenyl group which may be substituted with a methyl group, a methoxy group or a hydroxyl group; a phenethyl group which may be substituted with a methyl group; or a benzyl group which may be substituted with a methoxy group, or NR ¹ R ² represents a 5- or 6-membered nitrogen-containing heterocycle formed by linking R ¹ and R ² , and the total number of carbon atoms of R ¹ and R ² is 14 or less. ) is an anthraquinone dye. 3 General formula (In the formula, X represents a chlorine atom or a bromine atom, n is 0, 1 or 2, and -Y- represents a linking group -O- or -S-.) An anthraquinone compound represented by the general formula (In the formula, R ¹ and R ² are hydrogen atoms; cyano group,
Alkyl group optionally substituted with hydroxyl group, lower alkoxy group or dialkylamino group; cyclohexyl group; phenyl group optionally substituted with methyl group, methoxy group or hydroxyl group; optionally substituted with methyl group represents a phenethyl group; or a benzyl group optionally substituted with a methoxy group, or NR ¹ R ²
represents a 5- or 6-membered nitrogen-containing heterocycle formed by linking R ¹ and R ² , and the total number of carbon atoms of R ¹ and R ² is 14 or less. ) General formula characterized by reacting with a difluorotriazine represented by (In the formula, X, n, Y, R ¹ and R ² are the same as defined above.) A method for producing an anthraquinone dye represented by the following.