JPS62215660A - Azo compound and method for dyeing material using same - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I {R is H, Cl, methyl or methoxy; n is 2 or 3; D is group shown by formula II (R1 is methoxy or ethoxy; X is H, Cl or sulfonamide) or group shown by formula III [R2 is Cl, methyl, methoxy or ethoxy; R3 is H or methyl; Y is acetyl or (Cl- or methyl-substituted) benzenesulfonyl]}. EXAMPLE:A compound shown by formula IV. USE:Dye for dyeing fibrous materials, leather, paper, pulp, etc., in clear yellow in improved dyeing concentration, dyeing rate and degree of exhaustion. PREPARATION:For example, an amino compound shown by formula V is diazotized to give a diazonium salt, which is coupled with an acetoacetylamino compound shown by formula VI in a molar ratio of 1:1 preferably at 0-30 deg.C at 4-8.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to an azo compound and a method for dyeing a substrate using the azo compound.

Conventional technology Many dyes are used for dyeing (printing) base materials such as textile materials, leather, paper, and pulp, but few are satisfactory in terms of dyeing properties (dying speed, dyeing rate, etc.) . In order to obtain bright yellow dyed materials such as paper and pulp, conventional dyes have problems in terms of dyeing efficiency due to their slow dyeing speed and dyeing rate. Gives no results.

Problems to be Solved by the Invention From the viewpoint of shortening the dyeing time and preserving the environment, a dye that has a high dyeing speed and dyeing rate, makes dyeing waste water nearly colorless, and has good water fastness of dyed products. development is desired.

Means for solving the problem Dyeing of substrates such as textile materials, leather, pulp and paper (
The aim of the present invention is to find a bright yellow dye that is suitable for textile printing, has an excellent color value (dye yield), has a high dyeing speed and dyeing rate, and has high water fastness. This is what we have come to.

That is, the present invention provides formula (1) [wherein R is hydrogen, chloro, methyl or methoxy, n is 2 or 3, D is R1 (R1 is methoxy or ethoxy, and X is hydrogen, chlor or sulfonamide] ) or R (R2 represents hydrogen, chloro, methyl, methoxy or ethoxy, R3 represents hydrogen or methyl, Y represents benzenecarbonyl or benzenecarbonyl which may be substituted with acetyl, chlor, or methyl.) represents. The present invention provides an azo compound represented by the following formula and a method for dyeing a substrate using the azo compound.

The azo compound represented by the formula (]) of the present invention can be produced, for example, as follows.

[In formula (2), R and n represent the same meanings as in the above formula (1). ] D NHCOCH2C0C)h (31 [Formula (
In 3), D has the same meaning as in formula (1) above. That is, a diazinium salt prepared by diazotizing 1 mole of the amine compound of formula (2) by a known method is coupled with 1 mole of the acetoacetylamino compound of formula (3). The diazotization here is advantageously carried out with a nitrite salt, such as sodium nitrite, in an aqueous mineral acid solution at a temperature below 5°C, and the coupling is carried out in an aqueous medium at 0-50°C, preferably at a pH of 0-30°C. 2 to 9, preferably 4 to 8. The products can be isolated as crystals and, if necessary, purified by generally known methods. Further, since the obtained compound has two diethylaminoalkylamino groups, a stoichiometric amount or more of an inorganic acid such as hydrochloric acid, phosphoric acid, sulfuric acid, or preferably an organic acid such as formic acid, acetic acid, lactic acid, citric acid, By treating with glycolic acid, methanesulfonic acid, etc., it is possible to dissolve the water-soluble compound of formula (]) as an acid addition salt. Further, if desired, the solution containing the acid addition salt can be dried up to obtain the nucleic acid addition salt as a solid substance. Here, the amine compound of formula (2) can be obtained, for example, by a method similar to that shown in German Patent Publication No. 2915323. That is, it can be produced by reacting (condensing) 1 mole of nitroaniline with 1 mole of sheamer chloride and 2 molar ratios of 3-diethylaminopropylamine or 2-diethylaminoethylamine in any order, and further reducing the nitro group. . Specific examples of the nitroanilines used include 4-nitroaniline, 3-nitroaniline, 7.4-nitro-2-methoxyaniline, 4-nitroaniline, 4-nitroaniline, 3-nitroaniline,
-nitro-2-methylaniline, 4-nitro-2-10
Luaniline, 5-nitro-2-methoxyaniline, 5-
Nitro-2-methylaniline, 5-nitro-2-chloroaniline, 4-nitro-3-methoxyaniline, 4-nitro-3-methylaniline, 4-nitro-3-chloroaniline, 4-methoxy-3-nitro Examples include 1,4-methyl-3-nitroaniline, 4-chloro-3-nitroaniline, and the like.

Furthermore, when a corresponding acetylaminoaniline is used instead of the nitroaniline, the amino compound of formula (2) is produced by condensation in the same manner as described above and then hydrolysis.

The acetoacetylamino compound represented by formula (3) can be obtained by reacting a corresponding aniline with diketene, methyl acetoacetate or ethyl acetoacetate using a known method, and the following are specific examples thereof: can be mentioned.

The novel azo compound represented by formula (1) is dried as a crystal in the form of a powder or granules, or preferably, is converted into a salt of the above-mentioned organic or inorganic acid of the compound of formula (]), and then dried in the form of a powder or granules. The concentrated solution can be prepared by a known method (for example, Japanese Patent Publication No. 39-4879). That is, the azo compound of formula () is dissolved in an aqueous solution of the above-mentioned inorganic acid, preferably an organic acid, by adding a water-soluble organic solvent as necessary, and further adjuvants (for example, activators, ureas, etc.) are added as desired. By adding, a concentrated solution is prepared. Suitable water-soluble organic solvents used as necessary at this time include, for example, ethylene glycol, diethylene glycol, triedalene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, methylse, Rosolve, calpitol, and methylcarpitol. , ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, butyl polyglycol, phenyl glycol, glycerin, dioxane, butyrolactone, formamide, dimethylformamide, and the like.

Next, a method for dyeing a substrate using the azo compound of formula (1) of the present invention will be described. The new azo compounds can be used as dyes for the dyeing of textile materials, leather, pulp, leather and paper, and as pigmentary materials for the preparation of color inks used in the printing of these substrates, as well as for the preparation of glass or transparent synthetic materials. It can also be used to dye (color) thin films of natural proteins such as gelatin and casein or nitrogen-containing photocurable resins provided on resin films, and they are useful as color filters.

Examples of fiber materials to which the azo compound of formula (1) of the present invention can be applied include materials that can be dyed with cationic dyes, such as acrylonitrile homopolymers and mixed polymers, and natural nitrogen-containing fibers such as acidified polyester and polyamide. , materials containing cellulose such as cotton, recycled cellulose fibers, polyvinyl alcohol fibers, and even glass fibers.

The dyeing of these fiber materials with the azo compound of the present invention is carried out by conventional methods, preferably by absorption dyeing in a neutral to acidic aqueous medium under normal pressure or pressure, or by continuous methods such as spray coating with water-based inks, padding, and printing. It is carried out by staining. At this time, the form of the fibrous material may be a single fiber, yarn, cloth, knitted fabric, or finished product. By using the azo compound of the present invention, it is possible to obtain a dyed product (printed product) with high color variability, bright yellow color, and a clear yellow color. It has the same fastness as a candy can, and exhibits an extremely high dyeing rate (exhaustion rate) and excellent water fastness.

A further preferred use of the azo compounds of the present invention is the dyeing of various pulps and papers, bleached or unbleached, unsized or sized. The azo compound of the present invention exhibits a very high dyeing rate and a very high dyeing rate even on unsized pulp and paper (napkins, tablecloths, sanitary paper, etc.), and this high dyeing is due to its high dyeing rate. This makes the dyeing wastewater nearly colorless, which is a huge advantage in terms of wastewater regulations and environmental conservation.

The dyeing of these papers or pulps has a pH value of 4 to 8, especially 5 to 7.
, the dyeing temperature is 10-50°C, preferably 15-30°C. The resulting paper or pulp dyed product (printed product) exhibits a bright yellow color with a high color density, and exhibits excellent dye fastness under room temperature. There is almost no transfer (bleeding) of the dye onto the white paper, and it shows excellent fastness to myopan, alkali, acid, and alcohol. Such high fastness properties are highly suitable for application areas where color bleeding is a particular concern, such as napkins, napkins, and sanitary paper. Furthermore, the azo compound of the present invention has an extremely high affinity for paper and a fast dyeing speed, so it can be applied to continuous paper dyeing and jet printer ink, and it can also be used for leather dyeing (exhaustion method, spray method). , brush painting method, etc.). For example, exhaust dyeing of leather requires a temperature of 30 to 70°C.
Dyeing is carried out by dyeing in an aqueous dye bath at a pH value of 3 to 8 for 15 to 60 minutes, followed by fatliquor treatment in a conventional manner, followed by washing with water and drying.

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples. In the examples, parts represent parts by weight, and % represents weight %.

Example 1 8.9 parts of 4-[2',4'-bis(3-N,N-diethylaminopropylamino)-8-toIJazin-6-ylamino]aniline in 100 parts of water and 8.3 parts No. 3
Dissolved in a solution consisting of 5% hydrochloric acid and 10% nitrous acid) IJ
Diazotization was carried out at 0 to 5° C. for 30 minutes using 14 parts of an aqueous solution of aluminum. Excess nitrous acid was then destroyed by addition of sulfamic acid. A solution obtained by dissolving 5.0 parts of 2.5-dimethoxyacetoacetanilide in 200 parts of water at 60°C to a pn value of 11 with sodium hydroxide was added to the diazonium salt solution at 5 to 10°C. Thereafter, 5 parts of sodium hydrogen carbonate was added to adjust the pH value to 6.0, and the mixture was stirred for 12 hours. Subsequently add sodium hydroxide solution to adjust the pH.
The value was adjusted to 10-11 and the product was precipitated, filtered and dried. This powder was added to a mixture of 20 parts of water, 8 parts of acetic acid, and 18 parts of diethylene glycol, heated to 90°C to dissolve, and filtered. Compound 12.4 represented by formula (4)
0 parts max 405 nm (50% acetone water) was able to obtain 79 parts of a highly stable concentrated solution containing 0 parts, and a similar concentrated solution could be obtained even if a corresponding amount of lactic acid was used in place of the acetic acid. was completed.

Example 2 8.9 parts of 4-C2',4'-bis(3-N,N-diethylaminopropylamino)-8-triazin-6'-ylumino]aniline and 100 parts of water and 8.3 parts of
1 part of 35% hydrochloric acid, and diazotization was performed using 14 parts of 10% sodium nitrite aqueous solution. Excess nitrous acid was then destroyed by addition of sulfamic acid.

5.0 parts of 2.4-dimethoxyacetoacetanilide was dissolved in 200 parts of water at 60°C at a pH value of 20% with sodium hydroxide, and then 7 parts of sodium acetate was added to the resulting solution, and the diazonium salt was added to the resulting solution. 1 at 5-10℃
Added in 5 minutes. Then add sodium carbonate solution to pH
The value was adjusted to 6.0 and stirred for 12 hours. Subsequently, a sodium hydroxide solution was added to adjust the pH (t!!) to 0.0, and the product was precipitated and isolated.
5 parts of ethylene glycol and 20 parts of ethylene glycol;
The mixture was heated to 0°C to dissolve and filtered. A solution containing 12.2 parts of the compound represented by formula (5)] 5 parts was obtained.
λmax 409 nm (50% acetone water) Even if a corresponding amount of diethylene glycol was used in place of the ethylene glycol, a similar one-thick bath could be obtained.

Example 3 8.9 parts of 4-[2+'-bis(3''-N,N-diethylaminopropylamino)-8-triazin-6'-ylumino]aniline in 100 parts of water and 8.3 parts of 35
% hydrochloric acid, 10% sodium nitrite dissolved in water 1 [1
Diazotization was carried out using 4 parts. Excess nitrous acid was then destroyed by addition of sulfamic acid. 60℃ water 20
5.7 parts of 2,5-dimethoxy-4-chloro-acetoacedoanilide is hydroxylated to 0 parts).
The solution obtained by polymerization in step 1 was added to the solution containing the diazonium salt at 5 to 10°C. Then, 10 parts of sodium acetate was added, and then a sodium carbonate solution was added, and p
The H value was adjusted to 6.0, and the mixture was stirred for 12 hours. The pH value was then adjusted to 10.0 by adding sodium hydroxide solution and the product was precipitated and isolated. Add this to 30 parts of water, 25 parts of acetic acid, 5 parts of urea, and 3 parts of ethylene glycol motubutyl ether.
0 parts of the mixture, heated to 90°C to dissolve and filter. Compound 13 represented by formula (6), 117 parts of a concentrated solution containing 0 λmax 407 nm was obtained.
(50% acetone water) Example 4 8.9 parts of 4-C2',4'-bis(3"-N,N-diethylaminopropylamino)-8-triazin-6'-ylumino]anii The mixture was dissolved in 1 part of water and 8.3 parts of 35% hydrochloric acid, and diazotized using 14 parts of a 10% aqueous sodium nitrite solution at 0 to 5°C for 30 minutes.

Thereafter, excess nitrous acid was decomposed by adding sulfamino acid. Add 5.0 parts of 4-acetylaminoacetoacedoanilide to 200 parts of water at 45°C and adjust the pH with sodium hydroxide.
A solution obtained by dissolving the solution to a value of 11 was added to the solution containing the diazonium salt at 5 to 10°C. Thereafter, 5 parts of sodium hydrogen carbonate was added to adjust the pH value to 6.0, and the mixture was stirred for 2 hours. Then gradually add sodium hydroxide solution.
The H value was adjusted to 10.0 and the product was precipitated and isolated.

This was added to a mixture of 15 parts of water, 18 parts of acetic acid, and 18 parts of diethylene glycol, heated to 80°C to dissolve, and filtered. It was possible to obtain 84 parts of a highly stable concentrated solution containing 12.3 parts of the compound represented by formula (7). λmax 404 nm (
50% acetone water). A similar concentrated solution could be obtained by replacing the diethylene glycol with a corresponding amount of diethylene glycol mobutyl ether.

Example 5 9.5 parts of 4-(2',4'-bis(3"-N,N-diethylaminopropylamino)-s-triazin-6'-yl-aminoco-2-methoxyaniline and 100 parts of water) of water and 8.3 parts of 35% hydrochloric acid, and diazotization was carried out using 14 parts of a 10% aqueous solution of sodium nitrite at 0 to 5"C for 30 minutes. Excess nitrous acid was then removed by addition of sulfamic acid. A solution obtained by dissolving 5.0 parts of 3-acetylaminoacetoacedoanilide in 200 parts of water at 45°C and adjusting the pH value to 11 with sodium hydroxide was added to the solution containing the diazonium salt at a concentration of 5 to 10 parts. ℃. Then, 5 parts of sodium hydrogen carbonate was added to adjust the pH value to 6.0, and the mixture was stirred for 12 hours. Subsequently, hydroxide solution was added gradually, and the pH value was adjusted to 10.0. The product was precipitated and isolated. 12.9 parts of the compound represented by formula (8) could be obtained.

λmax 4 ] Onm (50% acetone water, acetic acid) Example 6 Dry material consisting of 50% unbleached sulfite valve and 50% mechanical valve was heated to 40° SR Freeness with water in a beater. ), adjust the valve content to 30% with 5 water and add 0 acetic acid.
．． 02 parts were added to obtain a mixture. The mixture was stirred for about 5 minutes, then 0.03 parts of rosin size and 0.06 parts of crystalline aluminum sulfate were added, followed by stirring for 5 minutes. Furthermore, 1400 parts of water was added to this prepared solution to dilute it, and this was made into paper using a conventional method on a sheeter (5 heater). Almost no coloration of papermaking wastewater was observed, and the colored paper obtained showed a clear yellow color with good color value, good light exposure, and excellent water fastness.

Example 7゜Bleach sulfite valve] Dry material consisting of 00%
The product was beaten at 35°SR freeness using water and adjusted to a valve concentration of 3%. To 100 parts of this prepared solution, 0.28 parts of the concentrated solution obtained in Example 2 (0.0 parts of the compound of formula (5)
3 parts) was added. Stir this well for 5 minutes, then add 1
After diluting by adding 400 parts, paper was made by a conventional method. In this case, almost no dye coloring was observed in the papermaking wastewater, and the paper obtained showed a bright yellow color with a high color value, and good light and water fastness.

Example 8 4.47 parts of the compound 1 thick solution obtained in Example 3 (containing 0.5 part of the compound of formula (6)), 0.5 part of starch, and 99% of water were mixed with paper that had not been subjected to sizing treatment. It was immersed in a mixed solution consisting of .0 part at 20 to 30°C for 2 to 3 seconds.

After squeezing out excess water through two rollers, 6
Dry at 0-80°C. The obtained dyed paper exhibited a bright yellow color with a high color value, excellent fastness to light and water, and almost no dye bleeding due to wetness was observed.

Example 9 100 parts of ragweed rubbed with vegetable tannins were mixed with 2 parts of water at 50°C.
50 parts and 2.73 parts of the concentrated solution obtained in Example 4 (containing 0.4 parts of the compound of the formula
Stir for 1 minute and then treat in the same bath for 60 minutes with 10 parts of anionic fat and oil based on sulfonated whale oil. The leather was then dried to obtain yellow uniformly dyed leather. This dyed leather had very good washing fastness.

Example 10 Into 100 parts of a water bath containing 0.64 parts of the concentrated solution found in Example 1 (containing 0.1 part of the compound of formula (4)), 5 parts of scoured and bleached cotton broadcloth were added, While stirring the dye bath and the article to be dyed, the temperature was raised to 100° C. over 40 minutes, and the temperature was maintained for 20 minutes. The azo compound in the dyebath was completely exhausted by the cotton broadcloth, and the bright yellow dyed product obtained showed good light exposure and excellent water fastness.

Similarly, viscose rayon fabrics and cupro fabrics were also dyed in bright yellow, exhibiting good light absorption and excellent water fastness.

Example 11 An aqueous dye solution containing 0.5% of the compound of formula (5) prepared from the concentrated solution obtained in Example 2 was sprayed in an amount of 50% based on the weight of unsized paper, and ~70
It was dried at ℃ for 10 minutes. The dyed paper exhibited a bright yellow color with a high color value and good light and water fastness.

Example 12-48° According to Example 1, an azo compound of formula (1) was produced.

The following table shows the amine compounds represented by the above formula (2), the above formula (
The λmax (50% acetone water) of the acetoacetylamino compound and azo compound (acetate solution) represented by 3) and the hue when paper was dyed using the acetate salt of these azo compounds are shown.

Effects of the Invention The novel azo compound obtained by the present invention has extremely high dyeing speed, dyeing rate, and dyeing density on a substrate, and the resulting dyed or colored substrate has good water fastness.

Claims (1)

[Claims] 1. Formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) [In the formula, R is hydrogen, chloro, methyl or methoxy, n is 2 or 3, D is ▲ Mathematical formula , chemical formulas, tables, etc. ▼ (R_1 represents methoxy or ethoxy, X represents hydrogen, chloro, or sulfonamide) or ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (R_2 represents hydrogen, chlor, methyl, methoxy, or ethoxy, R_3 represents hydrogen or methyl, and Y represents acetyl, or benzenecarbonyl, which may be substituted with chloro or methyl, or benzenesulfonyl). ] Azo compound 2, formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) [In the formula, R is hydrogen, chloro, methyl or methoxy, n is 2 or 3, D is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R_1 represents methoxy or ethoxy, X represents hydrogen, chloro, or sulfonamide) or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R_2 represents hydrogen, chlor, methyl, methoxy or ethoxy, R_3 represents hydrogen or methyl, and Y represents benzenecarbonyl or benzenesulfonyl which may be substituted with acetyl, chloro, or methyl. ] A dyeing method for a base material characterized by using an azo compound represented by the following.