JPH051825B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to quinophthalone compounds and reactive quinophthalone dyes. In particular, the present invention relates to reactive quinophthalone dyes capable of dyeing cellulose (cotton) and mixed fibers of cellulose and polyester. Conventional technology Conventionally, the following structural formulas [A] and [B] have been used as dyes that can dye mixed fibers of cotton and polyester.
Reactive quinophthalone dyes are known. (Unexamined Japanese Patent Publication No. 151064/1983) (JP-A-58-109688) However, the reactive quinophthalone dyes represented by the above structural formulas [A] and [B] had poor abrasion fastness. Problems to be Solved by the Invention The present invention particularly relates to a reactive quinophthalone dye for dyeing cellulose (cotton) and mixed fibers of cellulose and polyester fibers yellow with excellent rub fastness. Means for solving the problems The present invention is based on the general formula [] (In the formula, -X represents a halogen atom, -R ¹ and -R ² represent a hydrogen atom or a C ₁ to C ₅ alkyl group) and reactive quinophthalone dyes. It is something. The halogen atom represented by -X in the general formula [] includes a fluorine atom, a chlorine atom, or a bromine atom, with a fluorine atom being particularly preferred. Examples of the alkyl group represented by R ¹ and R ² include a methyl group, an ethyl group, and a linear or branched alkyl group having 3 to 5 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms. can give. The reactive quinophthalone compound of the present invention represented by the above general formula [] can be produced by the following method. In an organic solvent in the presence of an acid binder, the following general formula [] Quinophthalone compound represented by and the following general formula [] (In the formula, -X, -R ¹ and -R ² are the general formula []
The dihalogenotriazine represented by (same as the definition in ) is heated at 40 to 90°C for 0.5 to 5 hours. After the resulting reaction product liquid is cooled, it is discharged into water, for example, and the resulting precipitate is separated by a method such as filtration or centrifugation to obtain the reactive quinophthalone compound of the present invention represented by the above general formula []. can be obtained. Examples of the organic solvent used in the above production method include acetone, methyl ethyl ketone, toluene, nitrobenzene, dioxane, N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, etc., and the acid binder includes triethylamine. , N,N-diethylaniline, and other tertiary amines; and potassium carbonate, potassium hydrogen carbonate, and other inorganic bases. In addition, the amount of the acid binder used is 1 for the quinophthalone compound represented by the general formula [].
The amount of the dihalogenotriazine represented by the general formula [] to be used is 1.0 to 1.2 times the mole of the quinophthalone compound represented by the general formula []. be able to. Next, a dyeing method using the dye according to the present invention will be explained. Examples of fibers dyed with the dye according to the present invention include cellulose (cotton), hemp, etc., piscose rayon, copper ammonia rayon, etc., partially aminated or partially acylated modified cellulose, polyethylene terephthalate, or polybutylene terephthalate. Fibers such as polyester, polyamide, nylon, wool, silk, urethane, diacetate, triacetate, etc., or fabrics, blended fabrics, blended woven fabrics, woven and knitted fabrics, etc. (hereinafter referred to as fibers, etc.) manufactured from these. can be mentioned. Among these, it is particularly effective for cellulose and mixed fibers of cellulose and polyester. When carrying out dyeing, it is desirable to finely disperse the reactive quinophthalone dye of the present invention represented by the general formula [] in a medium to a particle size of about 0.5-2μ, and the method is as follows: (1) A water-soluble dispersant such as a nonionic surfactant such as a Pluronic surfactant or an anionic dispersant such as sodium ligninsulfonate or a sodium salt of naphthalenesulfonic acid-formalin condensate is used, and a pulverizer such as a sand grinder is used. (2) A method of finely dispersing in water, (2) using a compound with a low molar addition of ethylene oxide to a sulfosuccinate, nonylphenol, etc., in a solvent other than water, such as alcohols, ketones, hydrocarbons, halogenated hydrocarbons. (3) A method of finely dispersing it in a mixed system of water and a solvent optionally miscible with water among the above solvents; etc. 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 fine dye dispersion can be used as it is by dyeing dyeing method.
It can be used as each dyeing bath in the padding dyeing method and as a color paste in the dyeing dyeing method. Generally, the dye fine dispersion produced as described above is converted into an O/W type or W/O type emulsion of water, an aqueous organic solvent solution, or a petroleum hydrocarbon, halogenated hydrocarbon, etc., and water. Dilute to a dyeing concentration and use as a dyeing bath, padding bath, or textile dyeing paste. In preparing the dyeing bath, padding bath and printing paste, an alkali metal compound or an alkali precursor compound which generates an alkali when heated in the presence of water can be added as an acid binder. The amount of these acid binders used is usually
The padding bath or printing dyeing paste may be used in an amount within the range of PH of 7.5 to 9.0. Furthermore, when dyeing fibers containing cellulose, it is preferable to include a cellulose fiber swelling agent in the dye bath or color paste. The amount of the cellulose fiber swelling agent used can be in the range of 5 to 25% by weight, preferably 8 to 15% by weight, based on the dye bath or colored paste. In order to dye the fibers etc. with the reactive quinophthalone dye represented by the above general formula [] of the present invention, the fibers etc. are impregnated or printed in a dye bath or color paste prepared by the above method according to a conventional method, After drying, heat treatment may be performed, followed by washing with hot water containing a surfactant. The relationship between the preferred dyeing method using the reactive quinophthalone dye of the present invention represented by the above general formula [] and fibers, etc. is as follows with reference to Table 1.

[Table] By dyeing the above-mentioned various fibers, etc. using the dye of the present invention, orange fibers, etc., which are vividly and uniformly dyed, have excellent fastness to rubbing, and have excellent fastness to light can be obtained. I can do it. EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples. Example 1 The following structural formula of the present invention 15 g of quinophthalone dye shown, 15 g of naphthalene sulfonic acid-formaldehyde condensate and water
A dye dispersion liquid was prepared by finely dispersing 70 ml of the dye composition using a paint shaker as a fine dispersion machine. Using this dye dispersion, a textile dyeing paste (PH8.0) with the following composition: 6.5 g of 5% sodium alginate aqueous solution, 9 g of polyethylene glycol dimethyl ether with an average molecular weight of 400, 9 g of water, and a remaining amount of 100 g was prepared.
Cotton (mixing ratio 65/35) blended fabric was printed using a screen printing machine, and after intermediate drying at 80℃ for 3 minutes,
Dry heat fixation was performed at 215°C for 90 seconds. After washing this with water,
Nonionic surfactant (Scoreroll #900 (trademark),
Soaping was carried out at 80°C for 20 minutes at a bath ratio of 1:30 using a cleaning solution containing 29/ (manufactured by Kao Soap Co., Ltd.) to obtain a yellow dyed product with a rub fastness grade of 5.
The dyed product thus obtained also had an excellent light fastness of grade 5-6. The dye used in Example 1 was produced by the following method. Structural formula below Quinophthalone compound 3.0g, 2,4-
2.9 g of difluoro-6-(di-n-butylamino)triazine, 1.0 g of triethylamine and 0.7 g of anhydrous potassium carbonate were added to 50 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 ice water, and the resulting precipitate was filtered, washed with water, and then dried at room temperature to obtain 5.0 g of the quinophthalone dye represented by the above structural formula (yellow powder, yield 94%). . The λmax (acetone) of this dye was 442 nm. Comparative Examples 1 and 2 The dyes shown in Table 2 below were measured for their fastness to rubbing, fastness to light, and cotton staining properties. The results are shown in Table 2 below.

[Table] ** Cotton stain fastness: Excellent cotton stain fastness means that the white part of the printed fabric is not contaminated and a high quality printed fabric can be obtained.
[Evaluation method] A cotton cloth of equal area is attached to a dyed cloth that has been dry-heat-fixed at 215°C for 90 seconds, and immediately washed with a cleaning solution (bath bath) containing 2 g/L each of Na ₂ CO ₃ and Score Roll #900 (trademark). (ratio 1:200) at 80°C for 15 minutes, and staining of the attached cotton cloth was evaluated by gray scale. Example 2 A dye composition consisting of 16 g of quinophthalone dye represented by the formula, 7 g of polyoxyethylene glycol nonyl phenyl ether (HLB13.3), 3 g of naphthalene sulfonic acid-formaldehyde condensate, and 74 ml of water was finely dispersed using a sand grinder to form a dye dispersion. was prepared. Using this dye dispersion, prepare a padding bath (PH8.0) with the following composition: 6 g of dye dispersion, 15 g of tetraethylene glycol dimethyl ether, and 100 g of remaining water , and impregnate it into a polyester/cotton (mixing ratio of 65/35) blended fabric. After squeezing to a squeezing rate of 45%, dry at 100℃ for 2 minutes and then dry at 200℃.
The film was fixed with dry heat for 1 minute. By washing this product in a hot ethanol bath, a yellow dyed product with a friction fastness (dry) grade 5 was obtained. The dyed product thus obtained also had an excellent light fastness of grade 5-6. The dye used in this Example 2 was obtained according to the method described in Example 1. The λmax (acetone) of this product was 442 nm. Example 3 Structural formula below 10g of quinophthalone dye shown, 25g of naphthalenesulfonic acid-formaldehyde condensate, 65ml of water
A dye composition consisting of the following was finely dispersed using a sand grinder as a fine dispersion machine to prepare a dye dispersion. Using this dye dispersion, prepare a dyeing bath (PH8.0) with the following composition: 2 g of dye dispersion, 300 g of water , and add nylon taffeta 10.
g was placed in a dye bath and gradually heated from room temperature to 130°C, and dyed at this temperature for 1 hour. When the washing treatment was carried out in accordance with the method described in Example 1, a yellow dyed product with excellent abrasion fastness was obtained. The obtained dyed product was also excellent in various fastnesses, including a 5th grade light fastness and a 5th grade dry cleaning fastness. The dye used in this example was synthesized according to the method described in Example 1. The λmax (acetone) of this dye was 442 nm. Example 4 A dye composition consisting of 15 g of quinophthalone dye represented by , 10 g of Pluronic type surfactant Pluronic L64 (manufactured by Asahi Denka Kogyo Co., Ltd.) and 75 ml of water was finely dispersed using a sand grinder as a fine dispersion machine to form a dye dispersion. Prepared. Using this dye dispersion, prepare a textile dyeing paste (PH8.0) with the following composition: Dye dispersion 7g 5% sodium alginate aqueous solution 55g Polypropylene glycol diacetate with an average molecular weight of 300 10g Water Remaining weight 100g and mercerized. The printed material was printed on broad cotton (number 40) using a screen printing machine, and after drying at 80℃ for 3 minutes,
Treatment was carried out using heated steam at 185° C. for 7 minutes.
Thereafter, washing treatment was carried out according to the method described in Example 1, and a yellow dyed product with excellent rub fastness was obtained. The obtained dyed product was also excellent in various fastnesses, with a light fastness of grade 5 and a washing fastness of grade 4-5. The dye used in this example was synthesized according to the method described in Example 1. The λmax (acetone) of this dye was 442 nm. Example 5 Structural formula below 10 g of quinophthalone dye represented by 10 g of naphthalene sulfonic acid-formaldehyde condensate, 80 g of water
ml of the dye composition was finely dispersed using a paint shaker as a fine dispersion machine to prepare a dye dispersion. Using this dye dispersion, prepare a printing dyeing paste (PH8.0) with the following composition: Dye dispersion 10g Triethylene glycol dimethyl ether 40g 6% sodium alginate aqueous solution 550g Water Residual meter 1000g Polyester/Wool (mixing ratio 80/ 20) The blended fabric was printed using a screen printing machine, intermediately dried at 80°C for 3 minutes, and then treated with superheated steam at 180°C for 6 minutes. When this was washed according to the method described in Example 1, a yellow dyed product was obtained which was uniformly dyed and had excellent abrasion fastness. The dyed product obtained also had excellent dry cleaning fastness of grade 5. The dye used in this example was synthesized according to the method described in Example 1. The λmax (acetone) of this dye was 442 nm. Example 6 Structural formula below A dye composition consisting of 16 g of quinophthalone dye represented by the formula, 7 g of polyoxyethylene glycol nonyl phenyl ether (HLB13.3), 3 g of naphthalene sulfonic acid-formaldehyde condensate, and 74 ml of water was finely dispersed using a sand grinder to form a dye dispersion. was prepared. Using this dye dispersion, prepare a padding bath with the following composition: 6 g water, 100 g remaining , impregnate a polyester fiber cloth, squeeze to a squeezing rate of 45%, and dry at 100°C for 2 minutes. After fixing for 7 minutes in superheated steam at 185°C, reduction washing was carried out by a conventional method to obtain a yellow dyed cloth with excellent abrasion fastness. The λmax (acetone) of this dye was 442 nm. Example 7 Polyester/
Cotton (65/35) blended fabric was printed (however, x=C1
In this case, the colored glue was adjusted to PH9.0). The obtained dyed product had no staining in the white part and had excellent abrasion fastness. It was also excellent in light fastness and wet fastness. The quinophthalone dye was synthesized according to the method of Example 1. Table 3 shows the hue of the dyed product and the λmax (acetone) of the dye.

[Table] Example 8 A polyester/cotton (65/35) blend fabric was padded and dyed using the quinophthalone dyes listed in Table 4 according to the method described in Example 2 (provided that when X=Br was carried out using padding liquid pH 9.0). The dyed product obtained has excellent rubbing fastness,
It was also excellent in light fastness and wet fastness. The quinophthalone dye was synthesized according to the method of Example 1. Table 4 shows the hue of the dyed product and the λmax (acetone) of the dye.

【table】

Claims (1)

[Claims] 1. General formula [] (In the formula, -X represents a halogen atom, and -R ¹ and -R ² represent a hydrogen atom or a C ₁ to C ₅ alkyl group). 2 General formula [] (In the formula, -X represents a halogen atom, and -R ¹ and -R ² represent a hydrogen atom or a C ₁ to C ₅ alkyl group). 3. The reactive quinophthalone dye according to claim 2, wherein X in the general formula [] is a fluorine atom. 4. The reactive quinophthalone dye according to claim 2, wherein X in the general formula [] represents a fluorine atom, and R ¹ and R ² represent a C ₂ to C ₄ alkyl group. .