JPS6146591B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for dyeing or printing hydrophobic fibers using a novel water-insoluble monoazo dye represented by formula (1). [In formula (1), Z is a methyl group, ethyl group, benzyl group, or allyl group, R ₁ is a hydrogen atom, methyl group, methoxy group, or methoxyethoxy group, R ₂ and R ₃ are each independently a cyanoethyl group, R 4 represents an acetoxyethyl group, an alkoxyalkyl group, a phenoxyethyl group, an alkoxyalkoxyalkyl group or an allyl group, and R ₄ represents a methyl group, an ethyl group, a methoxyethyl group or a phenyl group. ] This new dye has the following formula [In the formula, Z represents the same meaning as above] A 2-amino-1,3,4-thiadiazole represented by the following is diazotized in a mineral acid, optionally in the presence of a lower fatty acid such as acetic acid or propionic acid, to obtain the formula [In the formula, R ₁ , R ₂ , R ₃ and R ₄ have the same meanings as above. ] It can be easily obtained by coupling to the amines shown in the following in an acidic medium. Thus, an object of the present invention is to provide a method for dyeing hydrophobic fibers, particularly fibers made of polyethylene terephthalate (hereinafter referred to as polyester fibers), to make them extremely clear and durable. All of the dyes represented by formula (1) give scarlet to purple dyed products. The resulting dyed product not only has excellent sublimation fastness and is extremely durable against post-dyeing processing, but also has a small decline in sunlight fastness, which is often seen in azo dyes composed of heterocyclic rings, making it suitable for industrial use. It is worth noting that it has sufficient value. The present invention will be explained in further detail. The formula that is the diazo component of the new dye represented by formula (1)
The 2-aminothiazoles in (2) are, for example, 2-amino-5-mercabuto-1,3,4-thiadiazole, ethyl halide, benzyl chloride,
Allyl halide, methyl sulfate, ethyl sulfate, p
-Easily obtained by the action of an alkylating agent such as methyl toluenesulfonate or ethyl p-toluenesulfonate. Also, a formula that is a katsu puller
The compound represented by (3) can be produced by various methods; for example, by reacting 3-aminoacetanilide with an alkylating agent such as tosyl esters of alkoxyalkyl or alkoxyalkoxyalkyl in the presence of a suitable neutralizing agent; Either acrylonitrile is first added to 3-aminoacetanilide and then an alkylating agent as described above is added to the 3-aminoacetanilide.
It is produced by adding ethylene oxide to aminoacetanilide and then esterifying it. Specific examples of R ₂ and R ₃ in the dye represented by formula (1) are as follows. Cyanoethyl group, acetoxyethyl group, 2-methoxyethyl group, 2-butoxyethyl group, 3-methoxybutyl group, phenoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group,
Butoxyethoxyethyl group, allyl group In order to dye hydrophobic fibers according to the present invention,
A dye bath or printing paste is prepared by dispersing the dye represented by the formula (1) in water using a conventional method, and dipping, printing or thermosol dyeing is carried out by a generally known method.
In addition to the above-mentioned polyester fibers, examples of hydrophobic fibers include acetate fibers and nylon textile printing methods, and the dye of the present invention provides fast and clear dyed products to these fibers as well. The present invention will be explained below with reference to Examples. Example 1 Formula 3 g of the dye represented by was treated with Demol N (product of Kao Atlas Co., Ltd., dispersant) and Demol C (product of Kao Atlas Co., Ltd., dispersant) in a wet state for 5 hours to obtain a finely divided dye. After dispersing 0.1 g of this micronized dye in 100 c.c. of water and adjusting the pH to 5 with acetic acid, 5 g of cloth made of polyester fiber was added and kept at 130°C for 60 minutes under pressure. The tray was taken out and washed with water.
Inside is 2g of caustic soda and hydrosulfite.
Reduction cleaning was performed at 80° C. for 15 minutes using 100 c.c. of a solution prepared by dissolving 2 g and 1 g of Monogen (manufactured by Daiichi Kogyo Yakuhin). After that, it was washed with water and dried. A bright red dyeing with a slight bluish tinge was obtained, which exhibited excellent sublimation fastness and sunlight fastness. Furthermore, the fastness to washing after antistatic treatment was extremely excellent. The dyeing used in this example was produced as follows.
44% (weight ratio) nitrosyl sulfate sulfuric acid solution 19.8g
At below 10°C, 30 c.c. of concentrated sulfuric acid and 60 c.c. of a solution consisting of propionic acid and glacial acetic acid (1:4, volume ratio) were gradually added dropwise, followed by 5-ethylthio-2 at below 5°C.
-Amino-1,3,4-thiadiazole (9.6 g) was gradually added. Subsequently, stirring was continued for 2 hours at 5°C or lower. The resulting transparent 5-ethylthio-2-
The diazotized solution of amino-1,3,4-thiadiazole was converted into 3-N,N-di-(β-methoxyethyl)-
16 g of m-acetylaminoaniline and 0.7 g of sulfamic acid were gradually dropped into a solution consisting of 50 c.c. of concentrated hydrochloric acid and 50 c.c. of ice water at a temperature below 5°C. After the dropwise addition was completed, a 10% aqueous solution of caustic soda was gradually added at 10°C or lower to make it slightly acidic. The precipitated crystals were separated, washed with water, and then dried to obtain 20.5 g of the compound of formula (4). The melting point of this substance is 117-119℃
It was hot. Example 2 0.03g of micronized dye obtained in Example 1
was dispersed in 90 c.c. of water and treated with acetic acid and sodium acetate.
Adjust the pH to 4.5 and add 3g of cloth made of nylon fibers.
Treated at 99°C for 60 minutes. Next, monogen in water 1
It was treated with 150 c.c. of water containing 2 g at 60°C for 10 minutes. After washing with water and drying, a bright red dyed product was obtained. This dyed fabric showed excellent light fastness. Example 3 Formula The dye represented by was made into fine particles in the same manner as in Example 1. Disperse 0.04g of this micronized dye in 100c.c. of water, add 0.2g of Polyescar DL (methylnaphthalene carrier, SsangYong Chemical), stir evenly, then add 2g of polyester fiber cloth and gradually raise the temperature. The mixture was brought to boiling and treated for 60 minutes. Thereafter, the same reduction cleaning as in Example 1 was performed, followed by water washing. A slightly bluish red dyeing with excellent sublimation fastness and sunlight fastness was obtained. The dye used in this example was produced as follows.
16.5 g of 44% nitrosyl sulfate sulfuric acid solution and 25 c.c. of concentrated sulfuric acid.
and 45 c.c. of a solution consisting of propionic acid and glacial acetic acid (1:4) at 10°C or below, followed by adding 11.2 g of 5-benzylthio-2-amino-1,3,4-thiadiazole at 5°C or below. was added gradually. Subsequently, the mixture was maintained at this temperature for 2 hours to obtain a yellow transparent diazotized liquid. N,N-di-(β-methoxyethyl)-m-acetylaminoaniline 13.3g sulfamic acid 0.6g
was dissolved in a mixture of 45 c.c. of concentrated hydrochloric acid and 50 c.c. of ice water, and the above diazotization solution was gradually added dropwise to this solution. During this time, ice pieces were occasionally added to keep the temperature below 5°C. After the addition was completed, a 10% aqueous solution of caustic soda was gradually added dropwise to neutralize the mixture until it became slightly acidic. The precipitated crystals had a slightly tarry taste, but were completely hardened by raising the temperature to 75°C and treating for 1 hour. The precipitated crystals were separated and washed with water. After drying, 19.5 g of the dye represented by the above formula (5) was obtained. The melting point of this substance is 134-7℃
It was hot. Example 4 0.1 g of the dye obtained in Example 3 was added to 100 c.c. of water.
The pH was adjusted to 5 with acetic acid, 5 g of polyester fiber cloth was added, and the mixture was heated at 130°C under pressure.
Time processed. Next, reduction cleaning similar to that in Example 1 was performed. A bright red dyed product with a slight bluish tinge was obtained, which had excellent sublimation fastness and sunlight fastness, and the dyed fabric with antistatic treatment had excellent washing fastness. Example 5 Formula A finely divided dye was prepared in the same manner as in Example 1 using the dye shown below. Using this finely divided dye, colored paste was prepared according to the following composition. Micronized dye of formula (6) 10g Warm water 73g Carboxymethyl cellulose paste 60g Sodium chlorate 0.5g Tartaric acid 0.2g Leveling agent 2g Total about 100g This color paste was used for printing and drying at 80℃. After dyeing, the cloth was divided into three equal parts and dyed according to the following methods (i) to (iii). (i) The sample was kept in steam at 130°C for 30 minutes, then washed with water, and subjected to reduction washing in the same manner as in Example 1. After washing with water, the sample was dried. A brighter red dyed product with a slightly more yellow tinge than the dyed product obtained in Example 3 was obtained. (ii) It was kept in superheated steam at 175°C for 5 minutes, and then washed with water, reduced, washed with water, and dried. A bright red dyeing was obtained as in (i). (iii) Dry heat treatment at 190℃ for 60 seconds and washing with water;
Reduction cleaning, water washing, and drying. A clear dyeing similar to (i) was obtained. The dyed products obtained in (i), (ii), and (iii) exhibited excellent sublimation fastness and sunlight fastness, and had excellent washing fastness after antistatic treatment. Thereafter, polyester fibers were dyed in the same manner as in the above examples to give bright red to purple dyed products with excellent fastness. In the following examples, X, Z, R ₁ ,
R ₂ , R ₃ , R ₄ and Y are specific examples in the following formula (1), and the color is the color of the dyed product on the polyester fiber. 【table】

Claims (1)

[Claims] 1. A method for dyeing or printing hydrophobic fibers, characterized by using a water-insoluble monoazo dye represented by formula (1) [In formula (1), Z is a methyl group, ethyl group, benzyl group, or allyl group, R ₁ is a hydrogen atom, methyl group, methoxy group, or methoxyethoxy group, and R ₂ and R ₃ are each independently a cyanoethyl group, acetoxy R 4 represents an ethyl group, an alkoxyalkyl group, a phenoxyethyl group, an alkoxyalkoxyalkyl group, or an allyl group, and R ₄ represents a methyl group, an ethyl group, a methoxyethyl group, or a phenyl group. ]