JPH0252658B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel water-insoluble monoazo compound and a method for dyeing hydrophobic fibers using the same. More particularly, the present invention relates to a novel water-insoluble monoazo compound and a method using the same for dyeing hydrophobic fibers, particularly polyester fibers, in strong purple to deep blue to greenish blue colors. In recent years, in the dyeing industry, there has been an extremely pronounced trend toward high added value as well as resource and energy conservation, particularly in the field of dyeing and processing hydrophobic fibers such as polyester fibers. For this reason, there is a demand for dyes used for dyeing that are easy to dye, have a good dyeing rate, and are also excellent in fastness. In particular, when dyeing from purple to dark blue to greenish blue, there are many problems such as deep dyeing and poor dyeing properties and poor fastness. Conventionally, introducing polar groups or increasing the molecular weight to improve fastness has led to problems such as decreased dyeability and dye bath stability. Also, when the number of polar groups is reduced, there is a problem that the fastness to sublimation etc. decreases. As a result of intensive studies on these problems, the present inventors have found that the above problems can be solved at once by using a novel monoazo compound represented by the above general formula [], which is virtually undescribed in the literature. We found this and solved the problem according to the present invention. That is, the present invention is based on the general formula [] [Wherein, X represents a hydrogen atom or a halogen atom, Y represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkoxy-lower alkoxy group, and R represents a lower alkyl group or a phenyl group. ] This is a method for dyeing hydrophobic fibers, which is characterized by using the water-insoluble monoazo compound represented by the following and one or a mixture of two or more thereof. The term "lower" as used in the present invention refers to a group having 1 to 4 carbon atoms. In the general formula [], examples of the halogen atom represented by X include a chlorine atom, a bromine atom, and an iodine atom. Examples of the lower alkyl group represented by Y include methyl group, ethyl group, propyl group, and butyl group, and examples of the lower alkoxy group include methoxy group, ethoxy group, propoxy group, and butoxy group.
Lower alkoxy Examples of the lower alkoxy group include a methoxyethoxy group and an ethoxyethoxy group, and preferred as Y are a methoxy group, an ethoxy group, and a methoxyethoxy group. Examples of the lower alkyl group represented by R include a methyl group, an ethyl group, a propyl group, and a butyl group, but preferred as R are a methyl group and an ethyl group. The monoazo compound represented by the general formula [] of the present invention is, for example, a monoazo compound represented by the general formula [] [In the formula, X represents the same meaning as above. ] The diazo component represented by is diazotized by a known method to form the general formula [] [In the formula, Y and R represent the above meanings. ] It is obtained by coupling reaction with the coupling component shown in the following. In addition, the coupling component represented by the general formula [] is the coupling component represented by the general formula [] [In the formula, Y and R represent the meanings as defined above. ] By alkylating the amine compound represented by with 2-phenoxyethyl ester of 2-phenoxy-1-halogenoethane or p-toluenesulfonic acid in the presence of a deoxidizing agent such as sodium carbonate or potassium carbonate. can get. The diazo component represented by the general formula [] is
2,4-dinitroaniline, 2-chloro-4,6
-dinitroaniline, 2-bromo-4,6-dinitroaniline, 2-iodo-4,6-dinitroaniline, and the like. The amine compounds represented by the general formula [] include 3-acetylaminoaniline, 3-propionylaminoaniline, 3-benzoylaminoaniline, 3-butyrylaminoaniline, 2-methoxy-5-acetylaminoaniline, 2-ethoxy -5-acetylaminoaniline, 2-methoxyethoxy-5-acetylaminoaniline, 2-ethoxy-5-propionylaminoaniline, 2-ethoxy-5-benzoylaminoaniline, 2-methoxyethoxy-5-benzoylaminoaniline, 2 -methoxy-5-butyrylaminoaniline, 2-methyl-5-acetylaminoaniline,
Examples include 2-ethyl-5-propionylaminoaniline. Specifically, the monoazo compound of the present invention is produced, for example, as follows. The diazo component represented by the general formula [] is dissolved or dispersed in a mineral acid such as sulfuric acid or hydrochloric acid or an organic acid such as acetic acid or propionic acid, and diazotized using nitrosyl sulfuric acid at 30 to 50°C. On the other hand, the coupling component represented by the general formula [] is combined with sulfuric acid,
The solution is dissolved in a mineral such as hydrochloric acid, an organic acid such as acetic acid or propionic acid, or an organic solvent such as methanol or ethanol, and the diazo liquid is added thereto at a temperature of 10° C. or lower for coupling. After the reaction is completed, the precipitated product is separated, washed with water, and dried to obtain a monoazo compound represented by the general formula []. In the present invention, hydrophobic fibers include polyester fibers, polyamide fibers, polyolefin fibers, cellulose ester fibers, and blends of these fibers. The compound of the present invention exhibits excellent dyeing properties particularly for polyester fibers and blends thereof. When dyeing hydrophobic fibers using the monoazo compound of the present invention, first, one or more monoazo compounds represented by the general formula [] are prepared into fine particles in an aqueous medium together with a suitable dispersant. crush,
Decentralize. The dispersed dye can be used as a liquid or as a powder by spray drying. Dyeing is carried out by a method known per se, in which a dye bath is prepared by dispersing the dispersed dye in an aqueous medium, and the hydrophobic fibers are immersed and heated at 105°C or higher under pressure.
Dyeing is preferably done at 110-140°C, or at a relatively high temperature, for example at boiling water, in the presence of a carrier such as O-phenylphenol or trichlorobenzene, or the dye dispersion is butted onto the fabric and Dyeing is done by the so-called thermosol dyeing method, which involves drying at ~230°C for 30 to 90 seconds, or in the case of textile printing, the dye dispersion is kneaded with a suitable sizing agent, and this is applied to the fabric, followed by steaming or thermosol dyeing. It can be treated and dyed. Further, a solvent dyeing method using an organic solvent such as trichlorethylene or perchloroethylene as a dyeing medium is also possible. The monoazo compound of the present invention has excellent dyeing properties, especially dyeing properties, decomposition resistance, and PH sensitivity, and has excellent color fastness properties such as sublimation fastness, water fastness, washing fastness, light fastness, and massaging fastness. It showed good performance. In the following, features of the present invention will be described in relation to the prior art. As dyes similar to the dyes used in the present invention, the following dyes are described in Japanese Publication No. 45-9914. Further, the following dyes are described in Japanese Patent Publication No. 47-4912. Compared to these dyes, the dye of the present invention exhibits superior performance in all aspects such as dyeing properties and fastness. The results of the comparative test are shown below. (Table 1)

[Table] The present invention will be described in detail below with reference to Examples, but the present invention is not limited to these Examples.
In the examples, parts and % represent parts by weight and % by weight unless otherwise specified. Example 1 2-methoxy-5-acetylaminoaniline 18
After heating and melting 10.6 parts of sodium carbonate, 48.2 parts of 2-phenoxy-1-promoethane was added dropwise at 100 to 110°C, and the mixture was reacted at the same temperature for 3 hours to form 2-methoxy-5-acetylamino. -N,N
-42 parts of -bis(2-phenoxyethyl)aniline were obtained. This was dissolved in 100 parts of methanol to obtain a coupling component. Separately, 26.2 parts of 2-bromo-4,6-dinitroaniline was diazotized with nitrosyl sulfuric acid at 30 to 40°C, and this was added to the above coupling component while cooling with 500 parts of ice water to 5°C or less to perform a coupling reaction. Ivy. The precipitated crystals were separated, washed with water, and dried to obtain 62.4 parts of the dye represented by formula (1). 90% yield for diazo component λ _nax (in DMF) 596 nm Example 2 1 part of the dye of formula (1) obtained in Example 1 was atomized and dispersed together with 1 part of formalin condensate of naphthalene-β-sulfonic acid and 1 part of sodium ligninsulfonate, and this and higher alcohol sulfuric ester were dispersed. 3 parts with water
Prepare a dyebath by uniformly dispersing it in 3000 parts. Tetron spun yarn (polyester fiber,
After soaking 100 parts of Toray Industries' product and dyeing at 130℃ for 60 minutes, the dyed product was soaked in a treatment solution consisting of 3 parts of caustic soda, 3 parts of hydrosulfite, 3 parts of a petaine type amphoteric surfactant, and 3000 parts of water. Then, reduction cleaning treatment was performed at 85°C for 10 minutes. Thereafter, it was washed with water and dried to obtain a dark blue dyed product with high density and excellent fastness. Example 3 After heating and melting 15 parts of 3-acetylaminoaniline and adding 13.8 parts of potassium carbonate, the mixture was heated to 110 to 115°C.
70.1 parts of p-toluenesulfonic acid 2-phenoxyester was added thereto, and the mixture was reacted for 3 hours at the same temperature.
39 parts of -acetylamino-N,N-bis(2-phenoxyethyl)aniline were obtained. This was dissolved in 100 parts of methanol to obtain a coupling component. On the other hand, 2-bromo-4,6-dinitroaniline
26.2 parts were diazotized in the same manner as in Example 1, and this was subjected to a coupling reaction with the coupling component to obtain 61 parts of the dye represented by formula (2). 92% yield based on diazo component λ _nax (in DMF) 563 nm Example 4 A dye bath was prepared in the same manner as in Example 2 using 1 part of the dye of formula (2), and dyeing was carried out to obtain a purple dyed product with high density and excellent fastness. Examples 5 to 13 The following dyes were produced in the same manner as in Example 1, and dyed in the same manner as in Example 2, and the results shown in Table 2 were obtained.

【table】

[Table] Example 14 A dye of the above formula (3) was produced in the same manner as in Example 1, and a part of it was atomized and dispersed together with 1 part of a formalin condensate of naphthalene-β-sulfonic acid and 0.5 part of sodium ligninsulfonate. Add the dye composition prepared above to 95 parts of a printing base paste having the composition shown below and mix well to prepare a colored paste. Printing paste 12% Maypro Gum NP60 (Locust Bean Gum) 63 parts Sodium chlorate 0.6 parts Tartaric acid 0.4 parts Water 36 parts Total 100 parts This dyeing paste is printed on polyester processed fiber,
After drying, it was steamed for 30 minutes using a high-pressure steamer (temperature 130-135°C, gauge pressure 3-4 Kg/cm ² ). Thereafter, it was washed with water, subjected to a reduction washing treatment in the same manner as in Example 2, washed with water, and dried to obtain a dyed product of a dark blue color with high density and fastness. Example 15 0.5 part of the dye of formula (1) obtained in Example 1 and 0.5 part of the dye of formula (2) obtained in Example 3 were mixed with naphthalene-β.
- Atomize and disperse with 1 part of formalin condensate of sulfonic acid and 1 part of sodium lignin sulfonate, and uniformly disperse this and 3 parts of higher alcohol sulfate in 3000 parts of water to prepare a dye bath. 100 parts of Tetoron spun yarn (polyester fiber, manufactured by Toray Industries, Inc.) was immersed in this dye bath and dyed at 130°C for 60 minutes. 3 parts of agent and water
Reduction cleaning treatment was performed at 85° C. for 10 minutes using 3000 parts of a treatment solution. Thereafter, it was washed with water and dried to obtain a blue dyed product with high density and excellent fastness.

Claims (1)

[Claims] 1. General formula [] [Wherein, X represents a hydrogen atom or a halogen atom, Y represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkoxy-lower alkoxy group, and R represents a lower alkyl group or a phenyl group. ] A water-insoluble monoazo compound represented by 2 General formula [] [Wherein, X represents a hydrogen atom or a halogen atom, Y represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkoxy-lower alkoxy group, and R represents a lower alkyl group or a phenyl group. ] A method for dyeing hydrophobic fibers, characterized by using a water-insoluble monoazo compound shown in the following.