JPS6363593B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the formula (In the formula, Y represents nitro, cyano, or lower alkoxycarbonyl, and X represents hydrogen, methyl, ethyl, or lower alkoxycarbonylmethyl. However, when Y is nitro, X represents hydrogen, methyl, ethyl,
When it represents lower alkoxycarbonylmethyl and Y is cyano or lower alkoxycarbonyl, X represents lower alkoxycarbonylmethyl. A,
B and C represent hydrogen, chloro, bromo, nitro, cyano, lower alkoxycarbonyl, lower alkylsulfonyl, NN-lower alkylsulfamide, lower alkyl, lower alkoxy, or lower acylamino; D and E represent hydrogen, methyl, chloro, Indicates lower alkoxy or lower acylamino. _R1 ,
R ₂ is hydrogen, lower alkyl, lower alkoxyalkyl, cyanoethyl, hydroxy lower alkyl,
Indicates lower acyloxyalkyl or lower alkoxycarbonylalkyl. However, "lower" means one having 1 to 4 carbon atoms. ) and a method for dyeing or printing hydrophobic fibers using the disazo compound. The disazo compound of the formula () is obtained by diazotizing the aromatic amine of the following formula () and coupling it to the amino-thiophene of the following formula ().
It can be obtained by converting the aminoazo compound into an aminoazo compound, which is further diazotized and coupled to an aniline derivative of the following formula ().

【formula】

【formula】

[Formula] As the aromatic amine of formula (), for example, aniline, 2,3 or 4-chloroaniline, 3,4-
Dichloroaniline, 2,3 or 4-bromoaniline, 2,3 or 4-nitroaniline, 4.nitro-
2-Chloraniline, 2-nitro-4-chloroaniline, 2,3- or 4-cyanoaniline, 4-
Chlor-3-cyano-aniline, 4-nitro-2
- cyano-aniline, 2,3 or 4-carbomethoxyaniline, 2,3 or 4-carbobutoxyaniline, 2,3- or carboethoxyaniline,
2,5-bis-carbomethoxy-aniline, 4-
Methylsulfonylaniline, NN-dimethylsulfamideaniline, 2,3 or 4-methyl-aniline, 2,3 or 4-ethoxy-aniline, 2,
Examples include 3- or 4-acetylamino-aniline, 4-chloro-3-acetylaniline, and the like.
In addition, as the aminothiophene of formula (), for example, 2-amino-3-nitrothiophene, 2-
amino-3-nitro-4-methyl-thiophene,
2-Amino-3-nitro-4-methoxycarbonylmethyl-thiophene, 2-amino-3-nitro-4-ethoxycarbonylmethylthiophene, 2
-amino-3-nitro-4-butoxycarbonylmethylthiophene, 2-amino-3-cyano-4
-ethoxycarbonylmethylthiophene, 2-amino-3-carbomethoxy-4-ethoxycarbonylmethyl-thiophene, 2-amino-3-carbobutoxy-4-methoxycarbonylmethyl-thiophene, and the like. Also, examples of the aniline derivatives of formula () include:
DE is hydrogen, methyl, chloro, methoxy,
Examples include ethoxy, formylamino, acetylamino, and propionylamino, and R ₁ and R ₂ include methyl, ethyl, butyl, methoxyethyl,
Butoxyethyl, cyanoethyl, β-hydroxy-ethyl, β-hydroxy-γ-methoxy-propyl, β-acetyloxyethyl, β-carboethoxyethyl, β-carbomethoxymethyl, β-
Examples include carbbutoxyethyl,
These are known materials commonly used as coupling components for disperse dyes. The amine of the formula () is easily diazotized by the action of sodium nitrite, nitrosyl sulfuric acid, etc. in an aqueous hydrochloric acid solution or sulfuric acid by a conventional method, and the diazotized solution is mixed with water of the amino-thiophene compound of the formula (),
Alternatively, by mixing with a solution of acetone, methanol, pyridine, DMF, etc., it can be easily coupled to produce an amino-azo compound of formula (). At this time, if necessary, use soda ash, sodium acetate, etc.
It is desirable to use a PH regulator in combination to promote coupling. After separating the precipitated amino-azo compound, washing with water and drying, this compound is dissolved or dispersed in sulfuric acid, phosphoric acid, acetic acid, propionic acid, or a mixture thereof, and a diazotizing agent such as nitrosyl sulfate, etc. is added at a low temperature, preferably below 0°C. It is diazotized by the action of sodium nitrite or nitrosoesters of alcohol. When the final diazotized solution is mixed with the coupling component solution of formula () at a low temperature, coupling will proceed easily and the disazo compound of formula () will precipitate, so it is removed. The disazo compound according to the present invention is suitable for dyeing or printing synthetic fibers, especially polyester fibers, and provides strong purple, blue, and green dyed products. In this case, it is preferable to use a dyeing composition prepared by dispersing the disazo compound of formula () with a dispersant and mixing it with other dyeing aids if necessary. That is, the disazo compound is a formalin condensate of naphthalenesulfonic acid,
The presence or absence of an anionic dispersant such as sulfated creosote oil, lignin sulfonic acid, or a nonionic activator such as a block copolymer of ethylene oxide and propylene oxide, or an ethylene oxide adduct of an alkylphenol, and a small amount of water. The dye composition is prepared by sufficiently wet grinding using a ball mill or sand mill, or by further spray drying. Conventional high-temperature dyeing using this composition;
Performs carrier dyeing, thermosol dyeing, textile printing, etc. In the case of textile printing, it is desirable to use a natural lake agent, a synthetic lake agent, a PH regulator, and a deep dye agent in combination.Also, after printing, a lake agent containing a discharging agent such as tin chloride or an alkali is applied to the dye of the present invention. By overprinting and steaming a color lake containing , it is possible to perform sharp discharge dyeing. The disazo compound of the present invention has a deep purple to green hue, which is deeper than conventional benzene-based and naphthalene-based disazo dyes, and has excellent light fastness, and has various wet fastness properties. It also has good heat resistance. Furthermore, the disazo compound having a lower alkoxycarbomethyl group at the 4-position of the thiophene in the present invention is hydrolyzed by the action of an alkali, so the dye staining the surface after dyeing is easy to wash and has little staining. It also has properties suitable for alkali discharge printing. The present invention will be specifically explained below using Examples.
In the text, parts refer to parts by weight. Example 1 3.3 parts of ethyl 4-amino-benzoate 6 parts of concentrated hydrochloric acid 200 parts of water were stirred and added with 1.5 parts of sodium nitrite at 0±2°C.
Add 10 parts of an aqueous solution containing 10 parts of the solution and stir for 1 hour to diazotize. Add 0.3 parts of sulfamic acid to destroy excess nitrous acid. A decomposed solution of 2.9 parts of 2-amino-3-nitrothiophene, 20 parts of DMF, and 20 parts of methanol is added dropwise to the diazotization solution at 0 to 5°C over about 20 minutes. At this time, a 16.5% sodium acetate solution was added dropwise at the same time to maintain the pH at 3-4. After stirring for about 3 hours, the precipitated crystals are separated, washed with water and dried. 4.3 parts of an amino-azo dye of the following formula (a) are obtained. 30 parts of acetic acid-propionic acid (4:1), 15 parts of concentrated sulfuric acid
2.1 parts of the pre-test amino-azo dye was added to the mixed solution of 1 part under stirring at 10°C or below, and stirred for 1 hour until it was almost dissolved. −
Cool to 5°C, add 2.8 parts of 44% nitrosyl sulfuric acid, and stir for 1 hour at -5±2°C to diazotize. This diazotized solution containing 2 parts of 3-[N,N-bis-(β-methoxyethyl)-amino]-acetanilide
Pour into 200 parts of 1.5% hydrochloric acid solution at 0-5°C. Separately, the crystals that precipitate after stirring for 1 hour are washed with water. Pour the cake into 800 parts of 2% soda ash at 50-60℃.
After stirring for 1 hour, separate and wash with water. 2 more cakes
Pour into 800 parts of % hydrochloric acid, stir at 60±5°C for 1 hour, wash separately with water, and dry. In this way, 2.3 parts of a disazo dye of the following formula (b) is obtained. Example 2 3.8 parts of 3-chloro-aniline, 10 parts of 35% hydrochloric acid,
Dissolve 200 parts of water with stirring, add 2.3 parts of sodium nitrite at 0±2°C, stir for 1 hour, and diazotize.
Excess nitrous acid is decomposed by adding 0.3 parts of sulfamic acid, and to this 6.3 parts of 2-amino-3-cyano-4-ethoxycarbonylmethyl-thiophene is added to DMF20.
30 parts, a suspension of 30 parts of acetone at 0 to 5°C.
It takes several minutes to drip. During this time, 16.5% sodium acetate solution was added dropwise to maintain the pH at 3 to 5. After stirring for 2 hours, the precipitated crystals were washed separately with water and dried to obtain 9.2 parts of an amino-azo compound of the following formula (c). 30 parts of acetic acid-propionic acid (4:1) mixture;
Add 2.7 parts of the above amino-azo compound to a mixed solution of 15 parts of concentrated sulfuric acid at 10°C or lower with stirring, and almost dissolve. -5℃
Add 3.5 parts of 44% nitrosyl sulfuric acid at ±2°C and stir for 1 hour to diazotize. This diazotized solution was poured into a solution of 1.8 parts of N-ethyl-N-cyanoethyl-meta-toluidine and 200 parts of 2% HCl at a temperature below 5 DEG C. for coupling. After 1 hour, wash separately with water. Pour the cake into 800 parts of a 2% aqueous soda ash solution, stir at 60±5°C for 1 hour, and wash separately with water. Further, this cake was poured into 800 parts of 2% hydrochloric acid, stirred at 60±5°C for 1 hour, and washed separately with water. When dried, disazo dye 3.0 of the following formula (d)
part is obtained. Example 3 To an aqueous solution of 3.8 parts of aniline, 13 parts of 35% hydrochloric acid, and 200 parts of water, 3.0 parts of sodium nitrite was added at 0±2°C with stirring and maintained for 1 hour to diazotize. Add 0.3 parts of sulfamic acid to destroy excess nitrous acid. Add 8.4 parts of 2-amino-3-cyano-4-ethoxycarbonylmethyl-thiophene to this solution and 50 parts of DMF.
A suspension of 50 parts of acetone and 50 parts of acetone is added dropwise at a temperature below 5°C. At the same time, add 16.5% sodium acetate solution dropwise to pH 3~
Hold at 5. After stirring for 2 hours, the precipitated crystals are collected, washed with water, and dried to obtain 12 parts of an amino-azo compound of the following formula (e). 40 parts of acetic acid-propionic acid (4:1) mixture;
Add 3.1 parts of the above amino-azo compound to a mixed solution of 15 parts of concentrated sulfuric acid at 10°C or less while stirring, and dissolve almost. -5
4.3 parts of 44% nitrosyl sulfuric acid was added at ±2°C and stirred for 1 hour to diazotize. This diazotized solution was mixed with 2.0% of N-ethyl-N-cyanoethyl-aniline.
Pour the mixture into a solution of 200 parts of 2% hydrochloric acid at 5°±2°C with stirring and couple. After 1 hour, the cake is washed with water separately, and the cake is placed in 800 parts of a 2% aqueous soda ash solution, stirred for 1 hour at 60-65°C, and washed with water separately. Pour the cake into 800 parts of a 2% aqueous hydrochloric acid solution and stir at 60-65°C for 1 hour.
Disazo dye of the following formula (f), separated, washed with water and dried 2.3
part is obtained. Examples 4 to 50 As described in Examples 1 to 3, the amine of formula () is diazotized and coupled to the amino-thiophene of formula (), and further diazotized and coupled to formula (), resulting in the formula () shown in the following table. The compound is obtained.

【table】

[Table] Example 51 30 parts of disazo dye described in Example 1, Demol N
(manufactured by Kao Atlas, anionic dispersant) 40 parts, Demol C (manufactured by Kao Atlas, anionic dispersant) 30 parts by adding a small amount of water to make a slurry, thoroughly wet-pulverized in a sand mill to a finely dispersed state, and sprayed. Dry with a hair dryer. A dye composition is obtained which is well dispersed in water. Add 3,000 parts of water to 4 parts of the above dye composition to prepare a dispersion, and then adjust the pH to 5 with acetic acid. 100 parts of processed polyester yarn fabric is soaked and dyed at 130° under pressure for 1 hour at the same temperature. Next, the dyed fabric is thoroughly soaped, washed with water, and dried to obtain a uniform green dyed fabric. Excellent light fastness, sublimation fastness, and wet fastness after resin processing. Example 52 Dye composition described in Example 51 4 parts Motoko (thickening (gum type) 301EX-RF12%)
Water 88% 60 parts Tartaric acid 0.2 parts Sodium chlorite 0.5 parts Water 35.5 parts Total 100 parts Mix the mixture with the above composition in a homomixer to prepare a printing lake. Printed on polyester fiber with this printing lake, 80±
Dry for 5°30 minutes. Next, steam for 30 minutes at 130°C to develop the color. Wash thoroughly with water, rinse with hot water to remove the water, and perform reduction washing to obtain a solid green color. Example 53 Stannous chloride 10 parts Sunsolt 7000 (aromatic carrier) 10 parts Locust bean gum 12% 60 parts Water 20 parts Total 100 parts Mix the above in a homomixer to prepare a discharge dyeing lake,
Print on the green cloth described in Example 51. After intermediate drying, steam at 130℃ for 20 minutes. Then wash with water,
After hot water washing and reduction washing, a green cloth with excellent whiteness in the discharge printing area can be obtained. Example 54 23 parts of the disazo dye described in Example 28, 4.6 parts of a block copolymer of polyethylene oxide/polypropylene oxide, 1,3 parts of 3-methylpantane,
A mixture of 20 parts of 5-triol and 52 parts of water is micronized using a sand mill for 4 hours to produce a liquid dye with good dispersibility in water. Liquid dye 5 parts Water 22.6 parts Citric acid 0.2 parts Improver 880 (printability improver manufactured by Yokohama Polymer Co., Ltd.) 2 parts Sodium dotecylbenzenesulfonate 0.2 parts Motoko (Faingum MC-8:4 Sorbitose C
-5:6) 70 parts Total 100 parts The above mixture was thoroughly mixed to form a color lake, which was printed on a polyester processed fabric using a hand screen. Dry at 80° for 10 minutes, then steam at 170°C for 8 minutes to fix. A beautiful blue cloth can be obtained by washing with water and reduction washing.

Claims (1)

[Claims] 1 formula (In the formula, Y represents nitro, cyano, or lower alkoxycarbonyl, and X represents hydrogen, methyl, ethyl, or lower alkoxycarbonylmethyl. However, when Y is nitro, X represents hydrogen, methyl, ethyl, or lower alkoxycarbonylmethyl. and when Y is cyano or lower alkoxycarbonyl,
X represents lower alkoxycarbonylmethyl.
A, B, and C are hydrogen, chloro, bromo, nitro, cyano, lower alkoxycarbonyl, lower alkylsulfonyl, NN-lower alkylsulfonyl,
It represents lower alkyl, lower alkoxy, or lower acylamino, and D and E represent hydrogen, methyl, chloro, lower alkoxy, or lower acylamino. R ¹ and R ² represent hydrogen, lower alkyl, lower alkoxyalkyl, cyanoethyl, hydroxy lower alkyl, lower acyloxyalkyl or lower alkoxycarbonylalkyl. However, "lower" means one having 1 to 4 carbon atoms. ) A disazo compound represented by 2 formula () (In the formula, Y represents nitro, cyano, or lower alkoxycarbonyl, and X represents hydrogen, methyl, ethyl, or lower alkoxycarbonylmethyl. However, when Y is nitro, X represents hydrogen, methyl, ethyl, or lower alkoxycarbonylmethyl. and when Y is cyano or lower alkoxycarbonyl,
X represents lower alkoxycarbonylmethyl.
A, B, and C are hydrogen, chromium, bromine, nitro, cyano, lower alkoxycarbonyl, lower alkylsulfonyl, NN-lower alkylsulfonyl,
It represents lower alkyl, lower alkoxy, or lower acylamino, and D and E represent hydrogen, methyl, chloro, lower alkoxy, or lower acylamino. R ¹ and R ² represent hydrogen, lower alkyl, lower alkoxyalkyl, cyanoethyl, hydroxy, lower alkyl, lower acyloxyalkyl or lower alkoxycarbonylalkyl. However, “low grade”
means one having 1 to 4 carbon atoms. ) A method for dyeing or printing hydrophobic fibers using a disazo compound shown in