JPH0372105B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the formula [In the formula, D is

[Formula] group (wherein X represents a nitro group or cyano group), R ₁ is a C ₁ to _{C 4} alkyl group, aryl group, cycloalkyl group, or allyl group, and R ₂ , R ₃ , and R ₄ are Indicates hydrogen or a lower alkyl group. ] The present invention relates to a monoazo compound shown in the following and a dyeing method using the same. The object of the present invention is to provide a method for dyeing or printing hydrophobic fibers, particularly polyester fibers, in a vivid blue color that has extremely good affinity, excellent color value, and various degrees of solidity. be. Anthraquinone-based blue disperse dyes have generally been used to dye polyester fibers bright blue. In recent years, dyed products are often subjected to various subsequent processes in order to increase their added value, and dyed products using conventionally used anthraquinone-based blue disperse dyes have a low level of firmness after subsequent processing. A problem has arisen in which the In addition, anthraquinone dyes have the disadvantage that they are generally expensive due to raw material problems. Under these circumstances, it has become necessary to give fibers the color tone of anthraquinone dyes using azo dyes, and various attempts have been made. Developed an azo dye that overcomes the drawbacks of the subsequent processing resistance of these anthraquinone blue disperse dyes, that is, a blue azo dye that has good dyeing properties for dyeing and various subsequent processing, stable dyeing reproducibility, and sufficient subsequent processing resistance. This is highly desired in the dyeing industry. In addition, polyester fibers are often used in the form of interweaving or blending with cellulose fibers, and dyeing of these blended fibers, that is, T/C (polyester/cotton)
In mixed dyeing, reactive dyes and direct dyes are often used in combination, and in this case, the dyeing stability of the disperse dye in neutral or alkaline conditions is important. Furthermore, T/C
Mixed dyeing requires characteristics such as minimal staining of the disperse dye on the cellulose side. The present inventors have conducted extensive research in order to meet the demands of the dyeing industry, and have discovered that satisfactory dyed products can be obtained when the present invention is followed. The monoazo dye of the present invention is synthesized as follows. An amine represented by the formula D-NH ₂ () [wherein D represents the above-mentioned meaning] is diazotized by a known method, and the obtained diazonium salt is formed by the formula It can be obtained by coupling with a coupling component represented by the formula [wherein R ₁ , R ₂ , R ₃ and R ₄ have the above-mentioned meanings] by a conventional method. Also, D is the base

When represented by the formula [wherein X represents the above-mentioned meaning], the monoazo compound of the present invention can also be obtained, for example, in the following manner. formula [In the formula, Y represents a cyano group, a nitro group, or a bromine atom, and Z represents a bromine atom] A diazonium salt obtained by diazotizing an aniline derivative represented by the following by a known method is converted into a tetrahydroquinoline derivative represented by the above formula () A monoazo compound represented by the following formula () is synthesized by coupling with the above in a conventional manner. Next, according to a known method, for example, the method described in Japanese Patent Publication No. 45-785, a cyanide such as cuprous cyanide and a monoazo compound of formula () are mixed in a polar aprotic solvent (for example, DMF, DMSO, pyridine, N-methylpyrrolidone, etc.) and stirred with heat.
The desired monoazo dye can be obtained by converting the bromine atom into a cyano group. [In the formula, Y, Z, R ₁ , R ₂ , R ₃ and R ₄ represent the above-mentioned meanings] In the present invention, the compound represented by the above formula () is 1,2,3,4-tetrahydroquinoline It can be easily synthesized by reacting a derivative with an alkylating agent such as an alkyl halide or tosyl ester. Examples of the diazo component represented by the above formula () include 2,6-dicyano-4-nitroaniline,
2,4-dinitro-6-cyanoaniline is mentioned. Further, specific examples of the aniline derivative represented by the formula () include the following compounds.

【formula】

【formula】

[Formula] Furthermore, typical examples of the coupling component represented by the above formula () include those shown in the following table. In the table, R ₁ , R ₂ , R ₃ and R ₄ are those in the above formula ().

【table】

[Table] When dyes are used as a mixture during dyeing, they can be obtained by coupling tetrahydroquinoline with a plurality of alkylating agents and using the method described above. It is also possible to react multiple diazo components. Furthermore, they can be mixed and used during dyeing or textile printing. The monoazo dye thus obtained can be used alone or as a mixture for dyeing or printing hydrophobic fibers such as polyester fibers, cellulose diacetate fibers, triacetate fibers, and polyamide fibers. In particular, it shows excellent dyeing properties, dyeing reproducibility and covering properties for polyester fibers, and provides dyed products with a clear blue tone. The following table shows the dyes of the present invention in which D is a base.

[Formula] [In the formula means the above] A monoazo dye according to Japanese Patent Publication No. 47-30410 containing 2,6-dicyano-4-nitroaniline as a diazo component as in the present invention, and a monoazo dye as in the present invention Like 1, 2, 3, 4-
The results of a comparative test with the monoazo dyes of Japanese Patent Publication No. 47-34680 and Japanese Patent Application Laid-open No. 55-65255, which use a tetrahydroquinoline derivative as a coupling component, are shown. The dye of the present invention is disclosed in Japanese Patent Publication No. 44-24707, No. 47-34680.
The dye of the present invention is particularly superior in fastness after subsequent processing, covering property, and pH dependence compared to the dyes of No. 1 and JP-A No. 55-65255, and the dye of the present invention is also good in other properties. Each test method in the table was performed using the following method. Judgments were made using ×, △, and 〇, with 〇 being the best in the order of ×<△<〇. (*1) Conducted in accordance with JISL-0842. (*2) PH of dye bath with dye concentration 2% owf bath ratio 1:30
5 Tetron cloth dyed at 130℃ x 60 minutes was dyed with Hydran F-24K (trade name,
Dainippon Ink's texture improver) After immersed in 1% water bath solution, squeezed to 80% and heated to 100℃.

【table】

【table】

[Table] After 5 minutes of intermediate drying, and then 3 minutes of heat setting, the degree of nylon contamination is determined by the Γ water test (method A: 37±2°C for 4 hours). Determine the degree of nylon contamination using the Γ washing test AATCCA method. (*3) Fabrics made of Tetoron yarns with different thermal histories are dyed with 0.2% owf, and streaks in the dyed material are visually determined. (*4) Dyeing is done under the conditions of 2% (owf) and bath ratio of 1:30, changing the pH of the dye bath to 5, 7, and 9, and determining the hue change and color intensity of the dyed fabric. (*5) A dye bath containing dye equivalent to 0.2 owf and adjusted to PH4.5 is pretreated at 130°C for 1 hour. Next, soak the Tetron white cloth in a bath ratio of 1:30.
Staining is carried out at 130°C for 1 hour, and the difference from normal staining is visually judged. To specifically dye or print hydrophobic fibers according to the present invention, a dispersant suitable for the monoazo compound represented by the above formula (), such as a formalin condensate of naphthalenesulfonic acid or an anionic dispersant such as ligninsulfonic acid, is used. , or a block copolymer of ethylene oxide and propylene oxide,
A nonionic surfactant such as an ethylene oxide adduct of alkylphenol and a small amount of water are added and thoroughly wet-pulverized using a ball mill or a side mill, and the resulting finely dispersed state is used for dyeing. The dyeing may be carried out by high temperature dyeing, carrier dyeing, thermosol dyeing, textile printing, etc. The present invention will be specifically described below with reference to Examples. In the examples, parts and % indicate parts by weight and % by weight, respectively. Example 1 2-Amino-3-bromo-5- to 47 parts of 70% sulfuric acid
Add 24.2 parts of nitrobenzonitrile, then cool to 0°C and add 31.0 parts of 43% nitrosyl sulfuric acid.
A diazotized solution was obtained by keeping the temperature at 0°C to 5°C for 3 hours. On the other hand, 2,2,4,7-tetramethyl-1,
18.9 parts of 2,3,4-tetrahydroquinoline to 15 parts of water
part plus 2.9 parts of magnesium oxide, p-toluenesulfonic acid β-allyloxyethyl ester
Add 31.0 parts and react at 85℃ for 10 hours, then cool, add 20 parts of methanol, 200 parts of water, and 60 parts of concentrated sulfuric acid.
1 part, and 0.5 part of amidosulfonic acid were added to form a solution. Ice was added thereto to bring the temperature to 5°C, and then the previously obtained diazotized liquid was added dropwise while keeping the temperature below 5°C by adding ice at appropriate times. Immediately upon dropping, dark blue crystals precipitate. After the addition is complete, the mixture is stirred for 2 hours at a temperature below 5°C, and then gradually heated to 60°C. After keeping at the same temperature for 2 hours, it was filtered and washed with hot water at the same temperature. By drying the crystals, 46.1 parts of a monoazo compound was obtained. 5.0 parts of the monoazo compound obtained above, 20 parts of DMF, and 1.2 parts of cuprous cyanide were mixed and reacted at 100°C for 8 hours, then cooled to room temperature, 15 parts of methanol was added, and stirred for 1 hour. The precipitated crystals were collected by filtration, washed with 20 parts of methanol, and then washed with water. 15 residue
The suspension was stirred with 100 parts of % ammonia water at room temperature for 4 hours, and then filtered. I did this same operation again. Next, the solid obtained above was stirred with 50 parts of a 5% aqueous sodium cyanide solution at room temperature for 2 hours, and then filtered. This operation was repeated once again to completely remove the copper compound. Finally, by thoroughly washing with water and drying, 4.0 parts of dark blue crystals represented by the following formula were obtained.
The λmax of this monoazo compound was 616 nm in a 75% acetone aqueous solution. The structure of this monoazo compound was confirmed by mass spectrometry. mp: 130-135℃ Mass spectrum M ⁺ : 472 30 parts of the above monoazo dye thus obtained was mixed with 40 parts of Demol N (dispersant manufactured by Kao Atlas) and 30 parts of Demol C (dispersant manufactured by Kao Atlas) in water. is added to form a slurry, wet-pulverized using a ball mill, and then dried using a spray dryer to obtain a dispersed dye. Two parts of the dispersed dye are added to 3,000 parts of water to form a dispersion liquid, and then the pH of the dye bath is adjusted to 5 with acetic acid and sodium acetate, and 100 parts of Tetron cloth is immersed in the dye bath at 130° C. under pressure and dyed for 1 hour. Cool and rinse, then reductively soap and then rinse. A bright blue dyed fabric was obtained. The various fastness properties were extremely excellent. Examples 2-27 The dyes shown in the following table were produced in the same manner as in Example 1. X, R ₁ , R ₂ , R ₃ and R ₄ in the table mean substituents of the following formula.

【table】

[Table] Example 28 20.8 parts of 2,4-dinitro-6-cyanoaniline was added to 120 parts of concentrated sulfuric acid cooled to below 5°C with stirring.
Add gradually. After adding the entire amount, 80 parts of a mixture containing 5 parts of acetic acid and 1 part of propionic acid was added at 10°C or below, and then 31.0 parts of 43% nitrosyl sulfuric acid was added and reacted for 5 hours to obtain a diazotized solution. On the other hand, 2,2,4,7-tetramethyl, 1,
18.9 parts of 2,3,4-tetrahydroquinoline to 15 parts of water
1 part, 2.9 parts of magnesium oxide and 27.6 parts of p-toluenesulfonic acid β-methoxyethyl ester were added, and the reaction was carried out at 85°C for 8 hours. 0.5 part of acid was added to form a solution. Ice was added to the mixture to bring the temperature to 5°C, then ice was added at appropriate times to maintain the temperature below 5°C, and the previously obtained diazotized liquid was added dropwise. Immediately upon dropping, dark blue crystals precipitated. then 5
Stir at below ℃ for 2 hours, then gradually heat to 60℃.
℃. After keeping at the same temperature for 2 hours, it was filtered and washed with hot water at the same temperature. When the crystals were dried, 32.6 parts of a monoazo compound represented by the following formula was obtained. λmax of this monoazo compound in 75% acetone aqueous solution
It was 603nm. This structure was confirmed by mass spectroscopy. mp: 153-160°C Mass spectrum M ⁺ : 466 The monoazo compound thus obtained was dyed according to the method of Example 1 to obtain various blue dyed polyester products with excellent viscosity. Examples 29-43 The following monoazo compounds were produced in the same manner as in Example 1. X, R ₁ , R ₂ , R ₃ and R ₄ in the table mean substituents of the following formula.

【table】

[Table] Example 44 Add 26.2 parts of 2,4-dinitro-6-bromoaniline to 40 parts of concentrated sulfuric acid, then add 43% nitrosyl sulfuric acid.
29.6 parts were added and stirred at 30°C for 5 hours to obtain a diazotized liquid. On the other hand, 2,2,4,7-tetramethyl-1,
18.9 parts of 2,3,4-tetrahydroquinoline and 15 parts of water
and 2.9 parts of magnesium oxide were heated and stirred at 85°C, and a mixture consisting of 15.4 parts of p-toluenesulfonic acid β-allyloxyethyl ester and 13.8 parts of p-toluenesulfonic acid β-methoxyethyl ester was added for 4 hours. It was dripped. Then stir at 90°C for 10 hours. After cooling, 200 parts of water, 50 parts of concentrated sulfuric acid, and 0.5 part of amidosulfonic acid were added to form a solution. Ice was added to the mixture to bring the temperature to 5°C, then ice was added at appropriate times to maintain the temperature below 5°C, and the previously obtained diazotized liquid was added dropwise. Dark blue crystals precipitate at the same time as dropping. After dripping, 5
Stir for 2 hours below ℃, then gradually heat to 60℃
shall be. After keeping at the same temperature for 2 hours, filter and wash thoroughly with hot water at the same temperature. After drying, 43 parts of a monoazo compound was obtained. This monoazo compound was subjected to cyano substitution of the bromine atom according to the method of Example 1 to obtain a mixture of monoazo dyes represented by the following formula. Its composition ratio was confirmed by high performance liquid chromatography, and its structure was confirmed by mass spectrometry. The monoazo dye composition obtained above was dyed in accordance with the method of Example 1 to obtain vivid blue dyed polyester fabrics with various degrees of firmness. Example 45 4 parts of the dispersed dye obtained in Example 1, 60 parts of Celpar SM-100 (product name: guar gum-based glue manufactured by Adachi Paste Co., Ltd.), 0.5 parts of sodium chlorate, 0.2 parts of tartaric acid Inbruva 880 (product name) Add 2.0 parts of leveling agent (manufactured by Yokohama Polymer Research Institute) to 33.3 parts of lukewarm water and mix thoroughly with a homomixer. This color paste is printed on a polyester cloth, and after intermediate drying, HT with heated steam at 175℃ for 5 minutes.
Steaming, then water washing, descaling, hot water washing,
Reduction cleaning, washing with water and drying. A blue dyed cloth was obtained. Various degrees of verticality were good.

Claims (1)

[Claims] 1 formula [In the formula, D represents a [formula] group (wherein, X represents a nitro group or a cyano group), and R ₁ is a C ₁
~ _C4 alkyl group, aryl group, cycloalkyl group, or allyl group, and _R2 , _R3 , and _R4 represent hydrogen or a lower alkyl group. ] A water-insoluble monoazo compound represented by 2 formulas [In the formula, D represents a [formula] group (wherein, X represents a nitro group or a cyano group), and R ₁ is a C ₁
~ _C4 alkyl group, aryl group, cycloalkyl group, or allyl group, and _R2 , _R3 , and _R4 represent hydrogen or a lower alkyl group. ] A method for dyeing or printing hydrophobic fiber materials, characterized in that a monoazo compound represented by the following is used alone or in a mixture of two or more.