JPS6128555A - Monoazo compound and dyeing of hydrophobic fiber by using it - Google Patents

Abstract

PURPOSE:A monoazo compound which has excellent dyeing properties and fastness properties, can dye hydrophobic fibers in red color, and has a specified constitution consisting of 2-amino-5-nitrothiazole as diazo component. CONSTITUTION:A monoazo compound of the formula (where X is a 1-6C alkoxy, phenoxy, phenyl, chlorophenyl, a 1-6C carboalkoxy, cyano, tetrahydrofuryl, etc.; Y is a 1-6C alkyl, aryl, benzyl, chlorobenzyl, cyanoethyl, a 1-6C alkoxy, etc.; n is 1 or 2). This compound is suitable for dyeing, printing, discharge printing, and reserve printing of hydrophobic fibers such as polyester or acetate fibers, gives a dyed material in red color with excellent fastness, light- fastness, etc., especially very good wet color fastness after post-treatment or heat setting.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a monoazo compound and a method for dyeing hydrophobic fibers using the same.

"Prior art" Disperse dyes containing 2-amino-5-nitrothiazole as a diazo component are disclosed in, for example, Japanese Patent Publication No. 46-33227 and Japanese Unexamined Patent Publication No. 1983-1989.
-40493 and the like, many ≠≠ are known.

Most of them are dyes that give purple to greenish-blue dyed products, and generally have excellent dyeing properties and build-up properties, and are suitable for discharge printing and
Since they are suitable as resist dyes, many of them are put to practical use as disperse dyes for resist discharge printing. However, all of them are dyes for fruits and vegetables, and among red dyes, there are dyes that have good dyeability (color burr), build-up properties, resistance to discharge printing (resistance and discharge properties), and fastness. It has not been discovered yet.

"Problems to be solved by the invention" Development of a red dye that takes advantage of the dyeing properties and fastness properties of 2-amino-5-nitrothiazole disperse dyes, such as color coverage, build-up properties, and discharge resistance. is desired.

``Means for solving problems'' We worked hard to find a dye that would be practical as a red disperse dye without impairing the dyeing properties and fastness properties that are the characteristics of 2-amino-5-nitrothiazole disperse dyes. As a result of research, the present invention was arrived at. That is, the present invention is based on the formula (Il (in formula (11), X is alkoxy (C1-6), alkoxy (C8-6) ethoxy, phenoxy, allyloxy, phenyl, chlorophenyl, nitrophenyl, carbalkoxy (C1-6) cyano, ethynyl or tetrahydrofuryl, Y is alkyl (C1-6) allyl, benzyl, chlorobenzyl, nitrobenzyl, cyanoethyl, cyanmethyl or alkoxy (C1-6) carbonylalkyl (C0-3), n is 1 or 2. (Represents an integer.)
The purpose is to produce a monoazo compound represented by the formula and use it to dye hydrophobic fibers.

The compound represented by the formula (I) can be obtained by diazotizing 2-amino-5-nitrothiazole by a known method to form the compound represented by the formula (2) (wherein, X, Y, and n have the same meanings as above). .

) can be obtained by coupling with the compound shown in

The compound of formula (2) used here as a coupler can be obtained as follows.

That is, (a) reacting anthranilic acid with Y-hal in the presence of a neutralizing agent or reacting with a compound having an active ethylene group in the presence of a catalyst to form a compound of formula (III); In the presence of a base, the compound represented by formula (IV) hal -(CHz)n-X (IV) (where h
al is obtained by reacting chlorine, bromine, an element, and n represents the above meaning), or (cl If Y is -(CHz)n acid methyl ester or anthranilic acid ethyl ester ≦=#=iptmilt
-Alcohol (CH2)n I can do it.

Specific examples of X in formula ■ include methoxy, ethoxy,
Butoxy, hexyloxy, methoxyethoxy, butoxyethoxy, hexoxyethoxy, phenoxyallyloxy, phenyl, chlorophenyl, p-chlorophenyl, o-chlorophenyl, 0-nitrophenyl, p-nitrophenyl, m-nitrophenyl, methoxycarbonyl, ethoxy Examples include carbonyl, butoxycarbonyl, hexyloxycarbonyl, cyanide, ethynyl, tetrahydrofurin, etc. Specific examples of Y include methyl,
Ethyl, butyl, hexyl, allyl, be/zyl, p-chlorobenzyl, 〇-chlorobenzyl, m-chlorobenzyl, p-nitrobenzyl, m~nitrobenzyl, o-nitrobenzyl, cyanoethyl, cyanomethylmethoxycarbonylmethyl, Ethoxycarbonylmethyl, butoxycarbonylmethyl, hexyloxycarbonylmethyl,
Methoxycarbonylethyl, butoxycarbonylethyl, ethoxycarbonylprobyl, etc.

The monoazo compound of formula (I) of the present invention is suitable for dyeing, printing, and discharge printing and resist printing of hydrophobic fibers such as polyester fibers and acetate fibers. They can be used in combination.

Next, the dyeing method will be explained.

The monoazo compound of formula (I) is a formalin condensate of naphthalene sulfonic acid, an anionic dispersant such as lignin sulfonic acid, or a nonionic dispersion such as an ethylene oxide adduct of an alkylamine or an ethylene oxide adduct of an alkaline phenol. The product is thoroughly ground in a crusher or sand mill with a small amount of water in the presence of an agent, and is used as a liquid or as a dried powder as required.

For the actual dyeing, for example, the following method known per se is employed.

do color.

(2) Carrier dyeing method Dyeing is carried out at 100°C in an aqueous medium in the presence of auxiliary agents such as methylnaphthalene and monochlorobenzene.

(3) Thermosol dyeing method (4) Printing method A printing paste consisting of pulverized dye and other chemicals is printed, followed by HT steaming (high temperature steaming) or HP steaming (high pressure steaming).

(5) Discharge printing method A discharge printing agent containing IJum, potassium carbonate, etc. is printed on the dyed fabric obtained in the above (11 or (2)) in a desired pattern, and then HT steaming or Perform HP steaming.

(6) Resist dyeing method A paste containing a resist dye such as stannous chloride or sodium carbonate or potassium carbonate is printed in advance in a desired pattern, and then a color paste containing a pulverized dye is printed. Perform HT steaming or HP steaming. Alternatively, a padded Tetron cloth containing crushed dye is immersed, and after intermediate drying, resist dyeing paste is printed in a desired pattern and HT steaming or HP steaming is performed.

These methods are the most typical examples, and the application of the present invention is not limited to these methods.

The dyed product obtained by the present invention has a red hue, and its fastness is excellent in sublimation fastness, light fastness, etc., and in particular, very good wet fastness after post-processing or heat setting.

[Example J] Next, the present invention will be specifically explained with reference to Examples. In the examples, "part" and "%" mean parts by weight and % by weight, respectively.

Example 1 2-Amino-5-
5.8 parts of nitro-thiazole was added at 5° C. or below, and diazotization was carried out by stirring at the same temperature for 1 hour.

A DMF solution containing 10.6 parts of cyanomethyl-2-(N-benzylamino)-benthia) was mixed with 60 parts of methanol.
1 part, 40 parts of acetic acid, and 50 parts of ice water, and the above diazo solution was gradually added at 0°C or lower. After further stirring at 5° C. or lower for 2 hours, the mixture was filtered, washed with water, and dried to obtain 11.8 parts of a monoazo compound represented by the following formula (■) as red crystals.

This product was recrystallized from dioxane and had a λmax of 519 nm (in 75% acetone). Moreover, the melting point was 190-191°C.

The coupler used in this example, cyanomethyl-
2-(N-benzylamino)-benzoate was obtained as follows.

27.4 parts of anthranilic acid was dissolved in a solution consisting of 250 parts of water and 8.3 parts of caustic soda at 70-80°C.
25.3 parts of pendyl chloride was added dropwise over a period of 1 hour, and the mixture was allowed to react at the same temperature for 4 hours.

Filtered, washed with hot water and dried to give N-benzyl-anthranilic acid 42.
．． 4 parts were obtained as white crystals.

11.4 parts of the above compound are dissolved in 15 parts of DMF, 4.0 parts of potassium carbonate are added, and 4.1 parts of chloroacetonitrile is added dropwise at 70 to 80°C over 30 minutes. Stir at the same temperature for 1 hour to complete the reaction.
DM containing 2-(N-benzylamino)-benzoate
A F solution was obtained. This DMF solution is used as it is as a Kaglar solution.

Example 2 Diazotization was carried out in the same manner as in Example 1 using 5.8 parts of 2-amino-5-nitro-thiazole. Compound 12 of formula (■).
A DMF solution containing 5 parts was dissolved in 60 parts of methanol, 40 parts of acetic acid, and 50 parts of ice water, and the above diazo solution was added and treated in the same manner as in Example 1. Obtained as crystals.

The λmaX (in 75% acetone) of this is 523n
It was m.

In addition, the solution of the compound of the formula (Mr.
In place of the chloroacetonitrile used in Example 1, chloroacetic acid ethyl ester was used, and the other conditions were as in Example 1.
obtained in the same way.

Example 3 Diazotization was carried out in the same manner as in Example 1 using 5.8 parts of 2-amino-5-nitro-thiazole. Compound 1 of formula (to)
A DMF solution containing the equivalent of 2.41 was mixed with 60 parts of methanol, 40 parts of acetic acid, and 50 parts of ice water.
The above diazo solution was added dropwise and treated in the same manner as in Example 1 to obtain 12.4 parts of a monoazo compound represented by the following formula (XID) as red crystals.

λmax (in 75% acetone) was 513 nm.

The compound of formula (XD) used in this example was obtained as follows.

While stirring 6.9 parts of anthranilic acid, 11.4 parts of potassium carbonate, 0.5 parts of potassium iodide, and 25 parts of DMF,
18.4 parts of ethyl acetate was added dropwise at 0 to 110° C. over 1 hour, and stirred at the same temperature for 3 hours to obtain a DMF solution containing the compound of formula (XI).

Examples 4-39° The fibers were dyed, and red dyed products were obtained in both cases.

Example X Y
λmax (nm) 4 Irregular H32-CH2COOC
2H55195-0C4H9〃
5196, -0C6H+3"
5197-OC21 (40C2H6〃
“520s, -()C2)mu0C
6HI3' “
5209-oQo
51810-OCI]2CH-CH
2〃〃51711, -@ ' , 1 #
51915-COOC4H9CHa
53216' C4H9
5331'7'' C6H+a
53318#,
7CHZCH=CH253019CN'
C4H9' 5292olI-CH2C
N-cH2526 21#' -CHzeCI 517
22 pI-cHt@517 ρ1 Example X n, Y
λmax (nm)23 CN' I C
H2■XN0251624'
rr 'C2H4CN 52425
〃 ＃CH2CN
50626' 〃-CH
2COOC2H551027tr #
-CH2COOC4H9'51028'
# C2H4COOCH35252
9'I-C2H4COOC4H9
52530-COOC41-I9# -CHω
52331 -CH=Cnyl # -CI-I2
COOC2)15 51734 -0CH32#
52835-OC2H40C2N(
5Lf〃52836 -0CzH40CH, + #
-CH2COOC2H652037-COOC4H
9a I CH2(◇ 52338 -CN
# -CH2COOC6I4+1+
51039 # # -C
3H6COOC2H5527 Example 40° 3 parts of the monoazo compound of formula (■) obtained in Example 1 was added to Demol (manufactured by Kao Atlas', dispersant) in 4 parts and Demol C (same) in 3 parts in a wet state. After extracting for 5 hours, the mixture was dried to obtain a finely divided dye. After dispersing 0.1 part of this micronized dye in 100 parts of water and adjusting the pH to 5 with acetic acid, 5 parts of polyester fiber cloth was added and kept at 130°C for 60 minutes, taken out and washed with water, then added to 1000 parts of water. 80° CI with 100 parts of a solution containing 2 parts of caustic soda, 2 parts of hydrosulfide, and 1 part of Monogen (manufactured by Dai-ni Kogyo Seiyaku).
After processing for 5 minutes and washing with water, a dried mushroom red dyed product was obtained.

This product had excellent sublimation fastness and light fastness, and especially excellent water fastness and heat fastness after antistatic treatment or heat setting.

Example 41゜The monoazo compound of formula (IX)- obtained in Example 2 was treated in the same manner as in Example 40 to obtain a finely divided dye.

Next, a color paste consisting of 3 parts of the above micronized dye, 20% carboxylic acid dimethylcellulose, 60 parts of sodium chlorate, 0.5 parts of tartaric acid, 0.2 parts of a leveling agent, 2 parts of hot water, and 34.3 parts of hot water was then added. Prepared. The color paste was printed on the colored polyester fiber, dried at 80°C, held in superheated steam at 170°C for 5 minutes, washed with water, reduced, washed with water, and dried.The colored paste was printed. A dyed product was obtained in which parts were colored red. This dyed product had excellent sublimation, light fastness, and post-processing resistance.

Example 42 Using the modiazo compound of the formula (X[D) obtained in Example 3, the same treatment as in Example 40 was carried out to obtain a fine particle dye.

In the pad tank, add the above micronized dye 20P/4 and sodium alginate IP/ as a migration inhibitor! ) was added to the radish solution, and a polyester/cotton blend fabric was radd at room temperature to reduce the weight increase rate to 65%. After performing intermediate drying, dry fixation is performed at 200°G for 90 seconds. Then, a red dyed product was obtained by reduction washing, washing with water, and drying. This dyed product had excellent sublimation, light fastness, and post-processing resistance.

Example 43゜10 parts of stannous chloride, 5 parts of polyethylene glycol, 60 parts of a 12% aqueous solution of locust bean gum (manufactured by Adachi paste),
A discharge paste consisting of 25 parts of water is printed on a polynisnal fiber cloth and dried at 100°C for 5 minutes.
0.5 parts sodium chlorate 0.
5 parts water
A colored paste having a composition of 36.0 parts was overprinted on this dried fabric. Next, after the drying process, steaming using superheated steam was performed at 170° C. for 5 minutes. Then, by washing with water and reduction washing, a red dyed product with remarkable white discoloration in the area where the discharge paste stamp was printed was obtained.

Example 44 Sodium carbonate 5 parts Glycerin 10 parts Fine Gum D-2514 20% glue 55 parts (No.
(manufactured by Kogyo Seiyaku) 30 parts of water Color paste was overprinted on the entire surface. 20 at 130℃ after intermediate drying
Steaming with saturated steam was performed for 1 minute. Next, it was washed with water, reduced and dried.

A red dyed product with excellent white discoloration in the area printed with the alkaline resistance dyeing paste was obtained.

Example 45゜J The red dyed cloth obtained in Example #0 was partially printed with an alkaline discharge printing paste of the following composition, and after intermediate drying, it was steamed with heated steam at 180°C for 8 minutes. . Then, it was washed with water, hot water, reduced washing, and dried. A dyed fabric with excellent white discoloration in the area printed with the alkaline discharge printing paste was obtained.

<Alkaline discharge paste> Sodium carbonate 3 parts Sodium hydroxide 2 parts Dicyandiamide
2 parts Fine gum D-2514 (manufactured by Dai-Kogyo Seiyaku) 20% and water.
70 parts Color Fine AD (manufactured by Dai-Kogyo Seiyaku)
Part 1 Dispaint PC (Nicca Chemical System)
5 parts water
8 parts Example 46゜Snow Algin 5SL (Fuji Chemical Exhibition) 1 part citric acid 2 parts Sakushitool C3-K (manufactured by Tohoku, Japan) 0.5 part water
A Tetron georgette cloth was soaked in a pad solution having a composition of 956.5 parts, and then mixed with a mangle.
After narrowing down to 0%, intermediate drying was performed at 8°C for 3 minutes. Next, an alkaline resist dyeing paste with the following composition was partially printed on this cloth, and after intermediate drying was performed again at 80°C for 3 minutes,
HT steaming was performed at 75°C for 7 minutes. Then, it was washed with water, hot water, reduced washing, water washed, and dried. A red dyed product with excellent white discoloration in the area printed with alkaline resist dyeing paste was produced.

<Alkaline resist dyeing paste> Base paste consisting of 20% Fine Gum D-2514 (manufactured by Dai-Kogyo Seiyaku) and water 55 parts Sodium carbonate 5 parts Color Fine AD (manufactured by Dai-Kogyo Seiyaku) 10 parts water
Part 30 "Effects of the Invention" By using 2-amino-5-nitrothiazole as a diazo component, it is possible to obtain red disperse dyes with excellent dyeing properties and fastness properties, and hydrophobic fiber dyed products using them.

Claims (2)

[Claims] (1) Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In formula (I), X is alkoxy (C_1_～_6),
Alkoxy (C_1_-_6) ethoxy, phenoxy,
Y is alkyl (C_
1_-_6), allyl, benzyl, chlorobenzyl, nitrobenzyl, cyanoethyl, cyanomethyl, or alkoxy (C_1_-_6) carbonylalkyl (C_1
_~_3), n represents an integer of 1 or 2. ) A monoazo compound represented by (2) Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In formula (I), X is alkoxy (C_1_～_6),
Alkoxy (C_1_-_6) ethoxy, phenoxy,
Y is alkyl (C_
1_-_6), allyl, benzyl, chlorobenzyl, nitrobenzyl, cyanoethyl, cyanomethyl or alkoxy (C_1_-_6) carbonylalkyl (C_1_
~_3), n represents an integer of 1 or 2. ) A dyeing method for hydrophobic fibers characterized by using a monoazo compound represented by