JPS59187061A - Production of disazo dye - Google Patents

Abstract

PURPOSE:An amino-azo compound is diazotized and allowed to couple with a specific amine to give a disazo dye which dyes polyester fibers purple to blue fast to light, heat and moisture. CONSTITUTION:An amino-azo compound of formula I (A is H, Cl, Br, nitro, methylsulfonyl, ethylsulfonyl; X, Y are cyano, nitro) is diazotized, then allowed to couple with an amine of formula II (B is H, Cl, methyl, methoxy, ethoxy, acetylamino; C is H, Cl, methoxy, ethoxy; R1, R2 are H, 1-4C alkyl, allyl, 3- 6C alkoxyalkyl, cyanoethyl, 2-4C hydroxyalkyl) such as 3-N,N-diethylamino- acetanilide to give the objective disazo dye of formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing disazo dyes for fast dyeing polyester fibers in synthetic carpets.

More specifically, formula (1) (In formula (1), A represents a hydrogen atom, a chlorine atom, a bromine atom, a nitro group, a methylsulfonyl group, or an ethylnulfonyl group, and Y represents a cyano group or a nitro group, respectively.

] The amino-azo compound represented by the formula (I
f) [In formula (II), B represents a hydrogen atom, a chlorine atom, a methyl group, a methoxy group, an ethoxy group or an acetylamino group,
C represents a hydrogen atom, a chlorine atom, a methoxy group or an ethoxy group, respectively. R1 and R2 are hydrogen atoms, 01-4 alkyl groups, allyl groups, C5-6 alkoxyalkyl groups, cyanethyl groups, C2-4 hydroxyalkyl groups, 04-6 acyloxyalkyl groups, or C3+7 alkoxy groups. Represents a carbonyl group. ] Formula (fil) characterized by coupling to an amine represented by [Formula (lit), A, B, C, X, Y,
R1 and R2 have the same meanings as above. ] It is related with the manufacturing method of the disazo dye represented by these.

Conventionally, various dyes have been studied as disazo dyes for dyeing synthetic fibers purple to blue, but these dyes have poor fastness, particularly light fastness, or various manufacturing difficulties, so they have not been put to practical use. There are few things offered.

For example, in the following formulas (IV) and (V), in JP-A-50-13227, formula (IV) (1)
:4-No2-,'EG: CH30-,F
K knee H, R3R4 knee C, 2H5).

In JP-A-55-23195, formula (IV) (D: 4
-NO2-.

E: -CH3, G: CH30-, FK
j-H, R6R4nee cH5).

Japanese Unexamined Patent Publication No. 55-40790 (N) (D24-NO
2-.

G E: CH30-, F: -H, K
: -CH3+ R31-C2H5.

R4: C2H40COCH3) JP-A-54-295
In No. 55, formula (V) (Eng.: 4-NO2-,, T +
-NHCOCH3,R5R6nee CH2-CH=CH2
) and the like are exemplified as dyes that dye purple to blue, but these dyes have poor light fastness and are not suitable for practical use.

Moreover, in Special Publication No. 45-20995, formula (IV) (D:
4-cI (3-, E: -H, F: -CN, G
: CH30-, Knee NHCOCH3, R6R4nee C2H51D E: -H, F: -CN.

G i -C1, K: -NHCOCJ, R3R
4: -C2Hs'+DI: -H, FG: -
CN, K: -NHCOCH3,R3R4:~C2
Disazo dyes such as H3) are listed, but the production method for these dyes is to add dimethylformamide and N-methyl-pyrrolidone to the corresponding dye of formula (IV) (FG: halogen atom) (halogen disazo dye fm). This method involves reacting cuprous cyanide in an organic solvent such as chloride to substitute a cyano group for a rogene atom. The production efficiency is low because the raw material is azo dye with a relatively large molecular weight, and the reaction is carried out in a large amount of expensive organic solvent, and a large amount of cost is required to remove harmful heavy metals such as metal cyanide. However, in the present invention, since the disazo dye represented by the formula (Ill)K is produced by a conventional diazotization coupling method, it is free from the above-mentioned drawbacks and is industrially extremely advantageous.

The disazo dye according to the present invention has a purple to blue color tone and has good dyeing properties on polyester fibers, and has excellent light fastness, heat fastness (sublimation fastness), and wet fastness of ing.

The amino-azo compound of formula (1) used in the present invention includes 4-phenylazo-2,6-disi7/-7=
7,4-(4'-nitrophenyl)azo-2,6-dicyazouaniline, 4-(3'-nitrophenyl)azo-2,6-cycyanoaniline, 4-(3'- Chlorphenyl)azo-2,6-dicyano-7=lJ 7. 4
-(4'-methylsulfonylphenyl)azo-2,6-
dicya2aniline, 4-(phenyl)azo-2-cyano-6-nitro-7=lJ, 4(4'-nitrophenyl)azo-2-cyano-6-nitro-aniline, 4(4
'-bromphenyl)azo-2-cyano-6-nitro-
Aniline, 4-(4'-ethersulfonyl-phenyl)
Examples include azo-2-Schiff/-6-nitro-aniline, 4-phenylazo-2,6-sinitroaniline, 4-(4'-methylsulfonylphenyl)azo-2,6-sinitroaniline, etc. These amino-azo compounds are synthesized by various methods.

Example, t 4-phenylaso 2,6-difluoroaniline, 4-(4'-nitrophenyl)azo-2-pOA
-6-= Drawaniline etc. are reacted with dimethylformamide and phosphorus oxychloride to form an amidine derivative, and then bromine at the ortho position of the amidine group is prepared using cuprous cyanide in an organic solvent such as dimethylformamide or N-methylpyrrolidone. is subjected to cyanide substitution and finally treated in an acidic medium. Also, 4-(4'-chlorophenyl)azo 2
- Nitroanisole, 4-(4'-methylsulfonylphenyl)azo-2-nitroanisole, etc. are nitrated with a mixed acid in sulfuric acid, and then treated with concentrated aqueous ammonia to convert the methoxy group to an amine group. Obtained by converting.

The amine represented by the formula (I'l) used in the present invention is used as a coupler for ordinary dispersion dyeing t1, but the specifics of B, C, R,, R2 in 2 (1) Examples include:

That is, C: hydrogen atom, chlorine atom, methoxy group, ethoxy group R1, R2: methyl group, ethyl group, butyl group, methoxy ether group, butoxy ether group, sia/ : r-f
group, β-hydroxyethyl group.

β-hydroxy-r-methoxypropyl group, β-acetyloxyethyl group, β-calphomethoxyethyl group, β-
These include a carboethoxyethyl group, a β-carbobutoxyethyl group, an allyl group, and the like.

The amino-azo compound of formula (It) is dissolved or dispersed in sulfuric acid, phosphoric acid, acetic acid, propionic acid, or a mixture thereof by a conventional method, and a diazotizing agent such as nitrosyl sulfate, etc. is added at a low temperature, preferably below 5°C. It is diazotized by adding sodium nitrite, etc. Then, this diazotized solution is mixed with a weakly acidic solution of the amine of formula (II) at 10° C. or lower for coupling. At this time, if necessary, sodium acetate, soda ash, etc. are added to adjust the pH and promote coupling.

The precipitated disazo dye is taken up and washed with water.

The disazo dyes according to the invention are used as dispersions for dyeing polyester fibers. That is, the disazo dye a is a formalin condensate of naphthalene sulfonic acid, an anionic dispersant such as sulfated creosote oil, lignin sulfonic acid, a block copolymer of ethylene oxide and propylene oxide, a non-containing material such as an ethylene oxide adduct of alkylphenol, etc. The dye composition is prepared by pulverizing with a ball mill, sand mill, etc. in the presence or absence of an ionic activator and a small amount of water, or by spray-drying as necessary when pulverizing in the presence of water. Use it as a body.

Using this dye composition, conventional high temperature dyeing, carrier dyeing, thermosol dyeing, etc. are carried out.

In addition, when printing is carried out, natural sizing agents, synthetic sizing agents, pH adjusters, etc. are used in combination. Discharge dyeing can also be performed by printing a paste containing a discharge dye such as tin chloride, overprinting a color paste containing a dye according to the method of the present invention, and steaming.

Next, examples will be given to explain the present invention in detail.
"" indicates "1 part by weight" and "O.1 part by weight".

Example 1 7.5 parts of 2,6-zineara-4-thenylazoaniline was added to 80 parts of acetic acid-pyrobionic acid (3:1), and the mixture was heated at 5°C.
While stirring, add 9.0 parts of 44% nitrosyl sulfuric acid. 5℃
Diazotization is carried out by stirring for 1 hour.

3 N,N-diethylamino-acetanilide 6.3
The above diazotized solution is added dropwise to a 1.5% diluted hydrochloric acid solution containing 1.5 parts at a temperature below 10°C. Add ice water to dilute to BOD and stir to complete coupling.

The precipitated dye is separated from each other, washed with water, and then dried. The following dye 9.5
part is obtained.

Max. (85% acetone aqueous solution) 59Dnrn
Dyeing hue of polyester fiber Blue 2.6-Zineara-4-Thenylazoaniline is synthesized as follows.

2,6-dipromu4 in 100 parts of dimethylformamide
-Dissolve 17.7 parts of phenylazo-aniline at 10°C.
8 parts of phosphorus oxychloride are then added dropwise. then 2[]-2
The mixture was stirred at 5°C for 6 hours and poured into 500 parts of ice water. The precipitate was washed with water and dried to obtain 18.8 parts of the amidine derivative. 517 parts of this amidine derivative were added and dissolved in 35 parts of dimethylformamide, 5 parts of cupric cyanide were added, the temperature was gradually raised, and the mixture was stirred at 130 to 135°C for 10 hours. After cooling, add 29 parts to 150 parts of ice water and 50 parts of ammonia water.
After adding 50% of the total amount of water and stirring, the mixture is taken from house to house. Refill the cake with 100 parts of water and 2
I) I!
After stirring, wash separately with water.

The cake was poured into a solution consisting of 50 parts of methanol and 20 parts of 35% hydrochloric acid, and stirred at 70±2°C for 2 hours.

Dilute with 500 parts of water, remove precipitate, wash with water and dry.

2.6-dicyano-4-phenylazo-aniline 3.0
part was obtained. (MP255-263°C) Example 2 75.5 parts of 2-cyano-6-nitro-4-(4'-methelsulfonylphenylnoazoanili) was added to 60 parts of acetic acid-pyropion 9 (3:1) and dissolved.

At 5°C or lower, add 5.0 parts of 44% nitrosyl sulfuric acid and stir for 1 hour to diazotize. The above diazotized solution is poured into a 1.5% hydrochloric acid solution containing 2.1 parts of 3-N,N-diethylamino-acetanilide at a temperature below 10°C. Add ice water to dilute to about 600 parts and stir for 1 hour to complete the coupling. When the precipitated dye is separated from each other, washed with water and dried, 3.7 parts of the following dye is obtained.

λmax (85% acetone aqueous solution) 6o, sn
Dyeing hue of polyester fiber Green-blue 2-cyano-6-nito T:14 (41-methylsulfonylphenyl)azo-aniline was synthesized as follows.

13.9 parts of ortho-nitrophenol was mixed with 2 parts of caustic soda.
Dissolve or disperse in 400 parts of water containing 0 parts of soda ash and 5 parts of soda ash. Also 4-methylsulfonyl-aniline 17.1
1 part dissolved in 300 parts of water containing 50 parts of 35% salt and heated at 5°C.
Below, 7.2 parts of sodium nitrite is added and stirred for 1 hour to diazotize. After adding sulfamino acid to decompose excess nitrous acid, the diazotized solution is added dropwise to the above-mentioned oronnitrophenol solution at an eVc of 1o° C. or less over about 1 hour.

2 while adjusting the pH to 4-7 by adding dilute soda ash solution.
Stir for an hour to complete the coupling.

The precipitated crystals are separated from each other and washed with water. Add the cake to 40 [1
4.0 parts of caustic soda was added to the mixture and stirred for 15 hours.

12.6 parts of dimethyl sulfate is added dropwise at 80-90°C over a period of about 1 hour. After further stirring at 90±5° C. for 1 hour, the mixture was cooled to room temperature, and the precipitate was separated, washed with water, and then dried.

2-nitro-4-(4'-methylsulfonylphenyl)
25.0 parts of asodianisole are obtained.

2-nitro 4-(4'-#frsulfonylphenyl)
20 parts of Azo-Ayuzol and 200 g of ethanol 29%
140± in an autoclave with 80 parts of ammonia water
゛Heat and stir at 2°C for 7 hours. After cooling, add 600 parts of water to dilute, and add vJA hydrochloric acid to neutralize to pH=5.

Separate the precipitated crystals in a furnace, wash with water, and dry! = 16.7 parts of 2-nitro-4-(a'-methylsulfonylphenyl)azo-aniline were obtained.

This amino-monoazo compound and 8 parts of anhydrous vinegar and soda were added to 1 part of vinegar.
A solution of 100 parts of acetic acid containing 16 parts of bromine was added dropwise at 15-20°C over 3 hours, and the mixture was further stirred at 40±5°C for 3 hours to form bromination. . Dilute with 700 parts of water and separate the precipitated crystals, wash with water and dry.

16.0 parts of 2-nitro-6-promo-4-(4'-methylsulfonylphenyl)azo-ayu 9F were obtained. 2-nitro-6-bromo in 70 parts of dimethylformamide
8.9 parts of 4-(4'-methylsulfonylphenyl)azo-aniline is dissolved, and 3.7 parts of phosphorus oxychloride is added dropwise to the solution under stirring at 10 DEG C. or below.

After stirring 20 parts at 2°C for 1 hour and 40 parts at 5°C for 1 hour, add 5 parts to ice water.
00 parts and neutralized to pH=7 by adding a caustic soda water bath solution. The precipitated crystals are separated, washed with water and dried to obtain 9 parts of amidine rust conductor. 8.5 parts of this amidine derivative were added and dissolved in 80 parts of dimethylformamide, 6.6 parts of cupric cyanide were added, and 130 parts were heated and stirred at 2 DEG C. for 10 hours. After cooling, dilute with 150 parts of ice water, add 80 parts of aqueous ammonia of Section 29, stir, and wash separately with water. The cake was again stirred in a mixture of 150 parts of water and 70 parts of 29% aqueous ammonia, and washed separately with water. The cake was refluxed for 1 hour in a mixture of 75 parts of methanol and 25 parts of concentrated hydrochloric acid. After cooling, the mixture is diluted with 300 parts of water, and the precipitated crystals are separated from each other and washed with water and dried. 5.0 parts of 2-nitro-6-diatu 4-(4'-methylsulfonylphenyl)azo-aniline are obtained. This product is recrystallized from acetone]11. p
, 262-266°C.

Example 5 2,6-sinitro 4-('4'-methylsulfonylphenyl) in 30 parts of acetic acid-propionic acid (3:1)
Dissolve 5.6 parts of azo-aniline. Stir at 5℃ or below 1
3 parts of 44% nitrosyl sulfuric acid was added to the mixture and stirred at the same temperature for 1 hour to diazotize the mixture. This diazotized solution was mixed with 4-acetylamino-2-N,N-di(propiene-2-)amino-
200% dilute salt solution containing 2.6 parts of Ayuzol:
The solution is gradually added to the solution at a temperature below 5°C.

Dilute with 600 parts of ice water to make approximately 50% of 30% sodium acetate solution.
to complete the coupling. The precipitate was separated, washed with water, and dried to obtain 3.5 parts of a disazo dye having the following structure.

λmax (85 thiacetone aqueous solution) 573 parts m Polyester N, T& dyeing hue Blue Color 2.6
-Sinitro 4-(4'-methylsulfonylphenyl)
Ann-aniline is synthesized as follows.

2-nitro-4-(4'-methylsulfonylphenyl)azo-ayuzole as described in Example 26. F part 100'
% Sulfur # (Monohthard) with stirring at 10° C. or lower. -5 parts of mixed acid (sulfuric acid; nitric acid 1:1) 2.6 parts
The mixture is added dropwise at a temperature of -1°C for about 30 minutes. After stirring at the same temperature for 1 hour, the mixture was poured into 700 parts of ice water, and the precipitated nitride was separated from the furnace and washed with water.

Add the cake to 120 parts of ethanol and 40 parts of 29% ammonia water.
of the mixture and heated in an autoclave at 150±5° C. for 3 hours with stirring. After cooling, dilute with 500 parts of water and neutralize to pH=5 by adding concentrated hydrochloric acid. The precipitate was separated, washed with water, and then dried to obtain 76.0 parts of 2,6-sinitro-4-('4'-methylsulfonylphenyl)asoanili. m
, p, 180-183°C Examples 4 to 38 In the same manner as in Examples 1 to 3, the aminoazo compound of formula (1) is diazotized and coupled to the amine of formula (I[), resulting in a disazo dye of formula (fl). is produced and dyes polyester fibers a strong purple to greenish-blue color.

(1) (II) (]■)

Claims (1)

[Claims] (1) Formula (1) [In formula (1), A represents a hydrogen atom, a chlorine atom, a bromine atom, a nitro group, a methylsulfonyl group or a ethylsulfonyl group, and Y represents a cyano group or a nitro group, respectively. ] The amino-azo compound represented by the formula (H
) [In formula (n), B represents a hydrogen atom, a chlorine atom, a methyl group, a methoxy group, an ethoxy group, or an acetylamino group;
represents a hydrogen atom, a chlorine atom, a methoxy group or an ethoxy group, respectively. R1 and R2 are hydrogen atoms, 01-4 alkyl groups, allyl groups, C5-6 alkoxyalkyl groups, cyanoethyl groups, C2-4 hydroxyalkyl groups.
It represents a C4-6 acyloxyalkyl group or a 05-7 alkoxycarbonylalkyl group. ] The formula ([+1) is characterized by coupling to the amine represented by [Formula ([[l], A, B, C, X, Y,
R1 and R2 have the same meaning as above. ] A method for producing a disazo dye represented by