JPH0148944B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to anthraquinone compounds and anthraquinone dyes for cellulose-containing fibers. Specifically, the present invention relates to cellulose-containing fibers,
In particular, the present invention relates to a reactive anthraquinone dye for cellulose-containing fibers that dyes cellulose fibers and mixed fibers consisting of polyester fibers and cellulose fibers in a strong blue color. The present invention will be explained in detail below. The present invention is based on the following general formula [] [In the formula, X represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom, and R ¹
and R ² is a hydrogen atom or an alkyl group, alkenyl group, cyclohexyl group, or aryl group which may be substituted with a cyano group, a hydroxyl group, a lower alkoxy group, a hydroxy lower alkoxy group, a lower alkoxy lower alkoxy group, or a dialkylamino group. or represents an aralkyl 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 18 or less. ] It concerns the anthraquinone compound shown by these and the anthraquinone dye for cellulose containing fibers. The compound represented by the above general formula [] is the compound represented by the following general formula [] [In the formula, X is the same as defined above. ] 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 with the compound shown below. Furthermore, the anthraquinone compound represented by the general formula [] is, for example, 1,5-dihydroxy-4,8
It can be easily obtained by condensing sodium -diamino-2,6-disulfonate with a phenol in sulfuric acid in the presence of boric acid, and then removing the sulfonic acid group. The present invention will be explained in detail below. Examples of lower alkyl groups represented by X in general formulas [] and [] include methyl group, ethyl group, n-propyl group, and isopropyl group, and examples of lower alkoxy groups include methoxy group, ethoxy group, n-propoxy group, An example is an isopropoxy group, and examples of the halogen atom include a chlorine atom and a bromine atom. Also, in the general formulas [] and [], R ¹
The alkyl group ^represented by 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-(N,N-dimethylamino)
Examples include alkyl groups substituted with a cyano group such as a propyl group, a hydroxyl group, a lower alkoxy group, a hydroxy lower alkoxy group, a lower alkoxy 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,
Substituted alkenyl groups include 3-cyanoallyl group,
Cyano groups such as 2-hydroxyallyl group, 3-methoxyethoxyallyl group, 1-methyl-3-(N,N-diethylamino)allyl group, hydroxy group,
Examples thereof include a lower alkoxy group, a lower alkoxy group, and an alkenyl group substituted with a lower alkoxy group. Examples of the aryl group include a phenyl group, a naphthyl group, an o-tolyl group, a p-butylphenyl group, and an aryl group substituted with a cyano group, a hydroxyl group, a lower alkoxy group, a lower alkoxy lower alkoxy group, or a dialkylamino group. Examples include m-cyanophenyl group, p-hydroxyphenyl group, p-methoxyphenyl group, p-
(2-methoxyethoxy)phenyl group, 2,5-
Examples include dimethoxyphenyl group and p-(N,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 number of carbon atoms of 6 to 12 is particularly desirable. To produce an anthraquinone compound represented by the general formula [], for example, in an organic solvent such as acetone, methyl ethyl ketone, toluene, nitrobenzene, dioxane, N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, etc. An anthraquinone 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 anthraquinone compound are added in an amount of 1 to 2 times the mole of the anthraquinone compound. Acid binders such as triethylamine, tributylamine, N,
It may be heated at room temperature to 90° C. for about 0.5 to 5 hours in the presence of a tertiary amine such as N-diethylaniline or an inorganic base such as potassium carbonate or potassium hydrogen carbonate. After cooling the obtained reaction product liquid, for example, by discharging it into water, the resulting precipitate is filtered,
The anthraquinone compound represented by the general formula [] can be obtained almost quantitatively by separation by a method such as centrifugation. 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 products or mixed fiber 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, for example, Pluronic type surfactant or an anionic dispersant, such as sodium ligninsulfonate or naphthalenesulfonic acid. Using a water-soluble dispersant such as sodium salt of formalin 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. , for example, alcohols such as ethyl alcohol, isopropyl alcohol, and polyethylene glycol, ketones such as acetone and methyl ethyl ketone, n-hexane,
In hydrocarbons such as toluene, 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 in a mixed solvent thereof. Examples include a method of finely dispersing it, 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 the optimum viscosity 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 the padding bath or printing dye paste prepared by the above method, and after drying at 160°C. ~30 seconds with hot air or superheated steam at 220℃~
Heat treatment for 10 minutes, or treatment in high-pressure saturated steam at 120℃ to 150℃ for 3 to 30 minutes, and washing with hot water containing a surfactant, or O/W where the oil layer is a halogenated hydrocarbon such as tetrachloroethylene. Or wash with W/O type emulsion washing bath,
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 anthraquinone dye represented by the formula, 15 parts of the 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 (PH8.0) was prepared, and a printing paste for polyester 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 seconds. After washing it 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 synthesized by the following method. 1,5-diamino-4,8-dihydroxy-
2-(4-hydroxyphenyl)anthraquinone
Dissolve 3.62 g in 50 ml of N-methyl-2-pyrrolidone, 2.0 g of triethylamine and 2.0 g of 2,4-difluoro-6-diethylaminotriazine.
was added and stirred at 40°C for 3 hours to carry out a condensation reaction. The resulting reaction solution was added dropwise to 500 ml of water, and the resulting precipitate was filtered out, washed with water, and then dried at room temperature in a vacuum dryer to obtain 4.9 g of a dark blue powder of the dye represented by the above structural formula. The λmax (acetone) of this dye was 628 nm. Example 2 Structural formula below 15 parts of anthraquinone dye, Pluronic type surfactant Pluronic L64 (Asahi Denka Co., Ltd.)
Co., Ltd.) and 75 parts of water.
A dye dispersion was prepared using a sand grinder as a fine dispersion machine. 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 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 1,5-diamino-
4,8-dihydroxy-2-(3-methyl-4-
Hydroxyphenyl)anthraquinone was obtained by reacting it with 2,4-difluoro-6-piperazinyltriazine in dimethyl sulfoxide using tri-n-butylamine as a deoxidizing agent. The λmax of this product was 629nm. Example 3 Structural formula below 10 parts of anthraquinone 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 laconditioner as a fine dispersion machine. 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. 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 1,5-diamino-
4,8-dihydroxy-2-(2-methoxy-4
-Hydroxyphenyl)anthraquinone in methyl ethyl ketone with triethylamine and potassium carbonate as deoxidizers (2,4-difluoro-6-)
(N,N-di-n-butylamino)triazine and
It was obtained by reacting at 60°C for 2 hours. The λmax (acetone) of this product was 628 nm. Example 4 Structural formula below Using a sand grinder, a dye composition consisting of 16 parts of the anthraquinone dye represented by the formula, 7 parts of polyoxyethylene glycol-nonyl phenyl ether (HLB13.3), 3 parts of naphthalene sulfonic acid-formaldehyde condensate, and 74 parts of water was milled using a sand grinder. A dye dispersion was prepared by dispersing the dye. 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, and reduce the squeezing rate to 45%.
After squeezing, 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 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 627 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 5/50) 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 When printing was carried out according to the method described in Example 1 using the anthraquinone dyes shown in Tables 1 and 2, the light fastness and wet color of the hues shown in Tables 1 and 2 were obtained. A print with good fastness was obtained.

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Claims (1)

[Claims] 1. General formula [In the formula, X represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom, and R ¹
and R ² is a hydrogen atom or an alkyl group, an alkenyl group, a cyclohexyl group, an aryl group that may be substituted with a cyano group, a hydroxyl group, a lower alkoxy group, a hydroxy lower alkoxy group, a lower alkoxy lower alkoxy group, or a dialkylamino group, or represents an aralkyl 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 in R ² is 18 or less. ] An anthraquinone compound represented by 2 General formula [In the formula, X represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom, and R ¹
and R ² is a hydrogen atom or an alkyl group, an alkenyl group, a cyclohexyl group, an aryl group that may be substituted with a cyano group, a hydroxyl group, a lower alkoxy group, a hydroxy lower alkoxy group, a lower alkoxy lower alkoxy group, or a dialkylamino group, or represents an aralkyl 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 in R ² is 18 or less. ] An anthraquinone dye for cellulose-containing fibers represented by: