JPS6229463B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel dispersed monoazo dyes useful for dyeing synthetic fiber materials, particularly aromatic polyester fiber materials. The monoazo dye according to the present invention has the formula () [In formula (), X is a hydrogen atom or a cyano group; when X represents a cyano group, Y represents a hydrogen atom or a bromine atom; and when X represents a hydrogen atom, Y represents a hydrogen atom. T represents a hydrogen atom or a lower alkoxy group, Z represents a lower alkyl group, and R ₁ represents a lower alkyl group or a lower alkoxyalkyl group. ], and when synthetic fibers or semi-synthetic fibers are dyed using this dye, good dyed products can be obtained. In particular, the dye of the present invention is easily converted into a water-soluble dicarboxylic acid type dye by alkali treatment.
It has excellent alkaline discharge dyeing properties and excellent suitability as a dye for thermosol dyeing of synthetic fibers, and is also well-balanced in various fastnesses such as water resistance and washing fastness. The azo dye according to the present invention has the formula () [In formula (), X and Y represent the same meanings as above. ] is diazotized, and the resulting diazotized compound is expressed by the formula () [In formula (), T, Z and R ₁ represent the same meanings as above. ] can be obtained by coupling with the coupling component. In the above formula (), when T is a lower alkoxy group, examples include a methoxy group, an ethoxy group, etc., and the lower alkyl group of Z is a methyl group, an ethyl group,
Examples include propyl group. Further, when R ₁ is a lower alkyl group, examples include a methyl group, ethyl group, propyl group, etc., and when R ₁ is a lower alkoxyalkyl group, examples include a methoxyethyl group, an ethoxyethyl group, etc. The process according to the invention advantageously involves, for example, adding the amine to a solution of nitrosyl sulfuric acid or adding an aqueous solution of sodium nitrite to an aqueous solution of the amine in hydrochloric acid, and optionally dispersing any residual nitrite present by adding sulfamic acid or the like. , the resulting solution or suspension of the diazo compound is added to a solution of the coupling component in water containing an acid and/or a water-soluble organic liquid, e.g. acetone, and if necessary the PH value of the mixture is adjusted to promote coupling. This can be carried out by isolating the obtained dye by a conventional method. Examples of the amines include 4-nitroaniline, 2-cyano-4-nitroaniline, and 2-bromo-4-nitro-6-cyanoaniline. Examples of the coupling component include 3-acetylamino-N,N-di[(ethoxycarbonyl)methyl]aniline, 3-acetylamino-N,N-di[(methoxycarbonyl)methyl]aniline, 3-acetylamino-N,N-di[(methoxycarbonyl)methyl]aniline, Acetylamino-N,N-
Di[(propoxycarbonyl)methyl]aniline, 2-methoxy-5-acetylamino-N,N
-di[methoxycarbonyl)methyl]aniline,
2-Ethoxy-5-acetylamino-N,N-di[methoxycarbonyl)methyl]aniline, 3-
Examples include propionylamino-N,N-di[(methoxyethoxycarbonyl)methyl]aniline and 2-ethoxy-5-acetylamino-N,N-di[(methoxyethoxycarbonyl)methyl]aniline. In order to dye synthetic fibers and semi-synthetic fibers using the dye of the present invention, it is used as a dye composition which is dispersed with a dispersant and mixed with a dyeing aid according to a conventional method. That is, the azo dye according to the invention in the form of a conventional aqueous dispersion can be applied to synthetic fiber materials, such as cellulose acetate, nylon and polyester fiber materials, as well as blended materials with cotton, under the normally employed conditions and other additives. It is carried out by dip dyeing, padding or printing method using a material. Usually, at the end of such a dyeing process, the dyed textile material is rinsed in water and a washing treatment is carried out, advantageously to remove any unfixed dyestuff from the surface of the textile material; is carried out by immersing the hydrosulfite in a warm aqueous alkaline solution. However, when using the dye of the present invention, the presence of hydrosulfite is not necessary, and the washing is actually carried out by washing the dyed textile material at a pH of 8 to 12 and at a temperature of 60°C.
This can be done by immersion for several minutes in an alkaline solution (e.g. a solution of sodium carbonate or sodium hydroxide) at ~85°C. When the dye of the present invention is used, unfixed dye is very easily removed by such alkali treatment. In addition, thermosol dyeing (drying treatment) is usually applied to dye polyester/cotton blended products, but in this case there is little staining on the cotton. Application of the dyes according to the invention to synthetic fiber materials in this manner gives dyeings in the orange to blue range which have excellent fastness properties to the tests commonly applied to dyed synthetic fiber materials. In addition, the dye of the present invention changes into a dye that does not easily adhere to synthetic fibers when exposed to alkali, so it has excellent suitability as a dye for ground dyeing in so-called alkali discharge printing. These dyeing properties are shown in Table 1 along with comparative examples using similar known dyes.

[Table] Next, the present invention will be explained with reference to Examples. Example 1 1.4g of sodium nitrite was dissolved in 98% sulfuric acid at 20-25℃
It is added to a mixed solution of 28 g and 3.67 g of 2-cyano-4-nitroaniline, and the mixture is stirred at the same temperature for 30 minutes. Next, this diazo liquid was converted into 3-acetylamino-N,N-di[(ethoxycarbonyl)methyl]
Aniline 5.6g, sulfamic acid 1g, acetone
50 g of ice and 500 g of water and add sodium acetate to adjust the PH of the mixture to 5. The mixture was stirred for 30 minutes, and then the precipitated dye was filtered off, washed with water, and dried to obtain the raw dye of formula (1). The λmax (acetone solution, same hereinafter) of this dye was 534 mμ. 40 g of atomized dye obtained by treating 30 g of this dye raw material with 70 g of Demol N (product of Kao Setsuken Co., Ltd., naphthalene sulfonic acid formalin condensate)
, citric acid 5g/and sodium alginate 2
A dispersion of 1.5 g/g was prepared, padded onto a polyester cloth, and then dried at 80°C. soda ash 50
g/, glycerin 50g/, polyethylene glycol #400 50g/, locust bean gum type glue 66g/ were mixed, and water was added to make 1.
The discharge printing paste prepared in this way was printed on the previously padded dry polyester cloth, dried at 80℃, steamed for 6 minutes at 175℃ with a high-temperature steamer, washed with water, and soaped at 80℃ for 10 minutes {Monogen ( Daiichi Pharmaceutical product, nonionic surfactant) 2
After treatment with an aqueous solution containing g/, washing with water and drying, a dyed product was obtained in which only the area where the discharge printing paste was printed was pure white and the other areas were rubine-colored. The fastness of this dyed product was as follows. Light resistance (JIS L0842-1971 carbon arc lighting method): Class 7, sublimation (JIS L0879-1975B): 4
Washing fastness (according to AATCC A method) after antistatic, water-repellent, and oil-repellent processing (using Sumitex Range UN-1 manufactured by Sumitomo Chemical Co., Ltd.): (Nylon contamination) Grade 4, (Acetate contamination) 4th grade. Furthermore, the dye had excellent affinity and dyeing properties for polyethylene terephthalate fiber materials, so that deep hues could be readily obtained. Example 2 13.8 g of 4-nitroaniline was mixed with 20 g of concentrated hydrochloric acid and 50 g of water.
20 g containing 7.0 g of sodium nitrite.
% aqueous solution was added dropwise at 0 to 5°C to diazotize. The diazo solution was then converted into 3-acetylamino-N,N-
Di[(ethoxycarbonyl)methyl]aniline
33.8g, sulfamic acid 4g, acetone 200g,
Add to a mixture of 1000 g of ice and water and 20 g of concentrated hydrochloric acid, and adjust the pH of the mixture to 5 with sodium acetate. The mixture was stirred for 30 minutes, and the precipitated dye was filtered off, washed with water, and dried to obtain the raw dye of formula (2). The λmax of this dye was 486 mμ. 6g of atomized dye obtained by treating 30g of this dyestuff with 70g of Demol N, sodium alginate
A dye dispersion consisting of 0.2 g and 100 g of water was padded onto a polyester cloth. After intermediate drying at 90 to 100℃, thermosol treatment (dry heat treatment) is performed at 200℃ for 90 seconds, and caustic soda 3
g, padded with a solution of 3 g of hydrosulfite dissolved in 100 g of water, and treated with saturated steam at 100°C. After washing with water, 1 g of glacial acetic acid, 1 g of 30% hydrogen peroxide solution
Dissolved in 100g of water and treated at 40℃ for 3 minutes. Further wash with water, Sozo ash 0.3g, Monogen 0.3
After washing for 1 minute at 80° C. in 100 g of an aqueous solution consisting of 100 g, an orange dyed product was obtained by washing with water and drying. This dyed product had good light fastness (6th grade) and sublimation (4th grade) fastness. In addition, this dye can be used with polyester
When applied to cellulose blend fibers, it was possible to obtain a dyed product with extremely little contamination of the cellulose portion even without reduction treatment with hydrosulfite after dry heat treatment. Example 3 After adding 100 g of glacial acetic acid to 100 g of nitrosyl sulfuric acid prepared with 7 g of sodium nitrite and 93 g of 98% sulfuric acid, 24.3 g of 2-cyano-4-nitro-6-bromoaniline was added at 15°C or below, Stir for 2 hours to perform diazotization. Dissolve 30.6 g of 2-ethoxy-5-acetylamino-N,N-di[(methoxyethoxycarbonyl)methyl]aniline in an acetic acid aqueous solution, add ice, cool to 0°C, and add diazo solution. Adjust the pH of the mixture to 5 with sodium acetate. The mixture was stirred for 30 minutes, and then the precipitated dye was filtered off, washed with water, and dried to obtain the raw dye of formula (3). The λmax of this dye was 607 mμ. Add 25g of this raw dye to 75g of Sunextract NB (product of Sanyo Pulp Co., Ltd., sodium lignin sulfonate).
5 g of polyester yarn was immersed in a dyeing bath consisting of 0.1 g of the atomized dye obtained by the treatment, 150 g of water, and 0.40 g of Disper TL (a product of Meisei Chemical Co., Ltd., a nonionic surfactant), and heated to 130°C under pressure for 60 minutes. After keeping it for a minute, take it out and wash it with water, add 2g of caustic soda,
2g of hydrosulfite and 2g of score roll (product of Kao Soap Co., Ltd., cleaning agent) dissolved in 1000g of water are subjected to reduction cleaning at 70-80℃ for 10 minutes, further washed with water, dried, and dyed with SUMITEX RESIN UN.
-1 was used for post-processing padding, dried at 80°C for 5 minutes, and then baked at 150°C for 3 minutes. The very deep greenish-blue dyeing thus obtained was fast to wet processing and washing according to the AATCC-A method. Examples 4 to 8 Other dyes represented by formula (1) were synthesized in a similar manner, and the color tones obtained when polyester fibers were dyed by the same dyeing method as in Example 1 are shown in Table 2.
In each case, dyed products with varying fastness levels were obtained.

【table】

Claims (1)

[Claims] 1 Formula () [In formula (), X is a hydrogen atom or a cyano group, when X represents a cyano group, Y represents a hydrogen atom or a bromine atom, and when X represents a hydrogen atom, Y represents a hydrogen atom. T represents a hydrogen atom or a lower alkoxy group, Z represents a lower alkyl group, and R ₁ represents a lower alkyl group or a lower alkoxyalkyl group. ] Monoazo disperse dye.