JPH0150260B2 - - 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, it 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 robust purple to blue color. The present invention will be explained in detail below. The gist of the present invention is the following general formula [] (In the formula, X and Y represent a hydrogen atom, a hydroxyl group, a nitro group, or an amino group, and Z is -O
- or -S- represents a linking group, R ¹ and
R ² is a hydrogen atom, a cyano group, a hydroxyl group,
NR 1 R 2 represents an alkyl group, alkenyl group, cyclohexyl group, aryl group or aralkyl group which may be substituted with a lower alkoxy group, a hydroxy lower alkoxy group, a lower alkoxy lower alkoxy group or a dialkylamino group, or NR ¹ R ² is R It represents a 5- or 6-membered nitrogen-containing heterocycle formed by linking ¹ and R ² , and the total number of carbon atoms of R ¹ and R ² is 18 or less. ) and anthraquinone dyes for cellulose-containing fibers. The compound represented by the above general formula [] is the following general formula [] (In the formula, X, Y and Z are 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 a compound represented by the following formula. Specific compounds represented by the general formula [] include 1-(2-hydroxyanilino)-4-
Hydroxyanthraquinone, 1-(3-hydroxyanilino)-4-hydroxyanthraquinone,
1-(4-hydroxyanilino)-4-hydroxyanthraquinone, 1-(3-thioxyanilino)-
4-hydroxyanthraquinone, 1-(3-hydroxyanilino)-4,5-dihydroxy-8-
Nitroanthraquinone, 1-(4-hydroxyanilino)-4,8-dihydroxy-5-nitroanthraquinone, 1-(3-hydroxyanilino)-
4,8-dihydroxy-5-aminoanthraquinone, 1-(4-thioxyanilino)-4,5-dihydroxy-8-aminoanthraquinone, 1-(3
-hydroxyanilino)-4-hydroxy-8-
Examples include nitroanthraquinone. 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, and a linear or branched alkyl group having 3 to 18 carbon atoms. is a 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 include alkyl groups substituted with a cyano group such as a (N,N-dimethylamino)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,
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 thereof include lower alkoxy groups and alkenyl groups substituted with dialkylamino groups. 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 the aralkyl group include a benzyl group, phenethyl group, m-methylbenzyl group, p-methylphenethyl group, and examples of the substituted aralkyl group include m-cyanobenzyl group, p-hydroxybenzyl group, p-hydroxyphenethyl group. group, o-anisyl group, etc. 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 anthraquinone compound represented by the general formula [], the anthraquinone compound represented by the general formula An anthraquinone compound represented by the 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 mixed with an acid in an amount of 1 to 2 times the mole of the anthraquinone compound. Binders such as triethylamine, tributylamine, N,
It may be heated at 40°C to 90°C for 0.5 to 2 hours in the presence of a tertiary amine such as N-diethylaniline, or an inorganic base such as potassium carbonate or potassium bicarbonate. 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 an anthraquinone compound represented by the general formula [] almost quantitatively. Can be done. In Japanese Patent Application Laid-open No. 56-22352, (where m is 1 or 2) Anthraquinone dye for cellulose-containing fibers is disclosed, but in the method for producing the dye, the reaction between difluoroaminotriazine and hydroxyl group is very slow, and the reaction time is 2 hours or more.
In order to increase the yield with a reaction time of 10 hours (at room temperature), difluoroaminotriazine has the disadvantage of requiring several equivalents of the anthraquinone. In the present invention, by changing the substituent at the 1-position to a hydroxyanilino group or a mercaptoanilino group, difluoroaminotriazine reacts almost stoichiometrically with the hydroxyl group or mercapto group of the anilino group, and the reaction time is also long. It has manufacturing advantages such as being able to shorten the width. Cellulose-containing fibers that can be dyed with the dye represented by the general formula [] include natural fibers such as cotton and linen, semi-synthetic fibers such as piscose 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, 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, and triacetate fibers are also available. 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 preferable 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-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 ketone, hydrocarbons such as n-hexane, toluene, xylene, mineral turpentine, halogenated hydrocarbons such as tetrachloroethylene, esters such as ethyl acetate, butyl acetate, ethers such as dioxane, tetraethylene glycol dimethyl ether, etc. Examples include a method in which the compound is finely dispersed in a mixture of water and a solvent which is 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 emulsion or W/O 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 In addition to alkali metal carbonates, alkali metal compounds include alkali metal fatty acids such as alkali metal bicarbonates, alkali metal phosphates, alkali metal borates, alkali metal silicates, alkali metal hydroxides, and alkali metal acetates. 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 150
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 anthraquinone 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. Using this dye dispersion, 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 parts 100 parts (PH8.0) 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 seconds. After washing this 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 purple dyeing with excellent light fastness and wet fastness was obtained. The dye used in this example was synthesized by the following method. 3.15 g of 1-(4-hydroxyanilino)-4-hydroxyanthraquinone in 100 ml of acetone;
1.9 g of 2,4-difluoro-6-diethylaminotriazine, 1.1 g of triethylamine and 1.4 g of anhydrous potassium carbonate were added, and the mixture was heated under reflux for 1 hour and 30 minutes to carry out a condensation reaction. Add the resulting reaction solution to 1000ml of water.
The resulting precipitate was separated, washed with water, and then dried in a vacuum dryer to obtain 4.5 g of dark red powder (yield: 93%). The λmax acetone of this product was 557 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 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 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 prepared by combining 1-(4-hydroxyanilino)-4,8-dihydroxy-5-nitroanthraquinone and 2,4-difluoro-6-di-(n-butylamino)triazine with triethylamine. was used as a deoxidizing agent, N-methyl-2
- Obtained by reaction in pyrrolidone at 50°C. The λmax (acetone) of this product was 582 nm. 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 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 (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 obtain a blue dyed product with excellent light fastness and wet fastness and no white spot staining. The dye used in this example was 2,4-difluoro- Obtained by reacting with 6-(1-pyrrolidinyl)triazine. The λmax (acetone) of this product was 607 nm. Example 4 Structural formula below Using a sand grinder, a dye composition consisting of 16 parts of anthraquinone dye represented by the formula, 7 parts of polyoxyethylene glycol nonyl phenyl ether (HLB13.3), 3 parts of a naphthalene sulfonic acid-formaldehyde condensate, and 74 parts of water was finely ground 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, 79 parts of water, and 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 purple dyed product with excellent light fastness and wet fastness was obtained. The dye used in this example was obtained by reacting 1-(3-mercaptoanilino)-4-hydroxyanthraquinone with 2,4-difluoro-6-(β-cyanoethyl)aminotriazine in tetrahydrofuran using triethylamine as a deoxidizing agent. Obtained by letting The λmax (acetone) of this product was 554 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 purple print with good wet fastness and light fastness was obtained. Example 6 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. The hue of the dyed fabric and the λmax (acetone) of the dye are shown in Tables 1 to 3.

【table】

【table】

【table】

【table】

【table】

【table】

Claims (1)

[Claims] 1. General formula (In the formula, X and Y represent a hydrogen atom, a hydroxyl group, a nitro group, or an amino group, and Z is -O
- or -S- represents a linking group, R ¹ and
R ² is a hydrogen atom, a cyano group, a hydroxyl group,
NR 1 R 2 represents an alkyl group, alkenyl group, cyclohexyl group, aryl group or aralkyl group which may be substituted with a lower alkoxy group, a hydroxy lower alkoxy group, a lower alkoxy lower alkoxy group or a dialkylamino group, or NR ¹ R ² is R It represents a 5- or 6-membered nitrogen-containing heterocycle formed by linking ¹ and R ² , and the total number of carbon atoms of R ¹ and R ² is 18 or less. ) Anthraquinone compound represented by. 2 General formula (In the formula, X and Y represent a hydrogen atom, a hydroxyl group, a nitro group, or an amino group, and Z is -O
- or -S- represents a linking group, R ¹ and
R ² is a hydrogen atom, a cyano group, a hydroxyl group,
NR 1 R 2 represents an alkyl group, alkenyl group, cyclohexyl group, aryl group or aralkyl group which may be substituted with a lower alkoxy group, a hydroxy lower alkoxy group, a lower alkoxy lower alkoxy group or a dialkylamino group, or NR ¹ R ² is R It represents a 5- or 6-membered nitrogen-containing heterocycle formed by linking ¹ and R ² , and the total number of carbon atoms of R ¹ and R ² is 18 or less. ) Anthraquinone dye for cellulose-containing fibers.