JPH0784712B2 - Substrate dyeing method using heterocyclic compounds - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for dyeing a substrate using a heterocyclic compound.

BACKGROUND ART Many dyes are used for dyeing and printing fiber materials, leather, paper or pulp, but the dyeing characteristics (dyeing speed,
There are few things that can be satisfied in terms of dyeing rate etc. In particular, known dyes used for dyeing paper and pulp in a clear yellow color have a problem that their dyeing speed and dyeing rate are small, and in addition, they are also satisfactory in water fastness of the dyed product. There are few at the right level.

Problems to be Solved by the Invention In recent years, there has been an increasing demand for streamlining of the dyeing industry, but especially in terms of shortening dyeing time and environmental protection, the dyeing speed and dyeing rate are high, and the dyeing wastewater is colorless. There is a demand for the development of a dye that is close to the above and has good water fastness of the dyed product.

Means for Solving the Problems In carrying out dyeing and printing of substrates such as textile materials, leather, pulp and paper, the present inventors have an excellent color value (dyeing density), dyeing speed and dyeing speed. The present invention has been achieved as a result of intensive research to find a clear yellow dye having a high rate of deposition and excellent waterfastness.

That is, the present invention uses the formula (1) [Wherein R is hydrogen, chloro, methyl or methoxy, n is 2 or 3 and D is (R ₁ represents hydrogen, chloro or methyl.) Or (R ₂ and R ₃ are hydrogen, chloro, bromo, methyl, methoxy,
Represents ethoxy, acetylamino, sulfonamide, thiocyano, methylsulfonyl, methoxycarbonyl or ethoxycarbonyl. ), Respectively. ] A method for dyeing a substrate, which comprises using a heterocyclic compound represented by The heterocyclic compound represented by the formula (1) can be produced, for example, as follows.

[In the formula (2), R and n have the same meanings as described above. ] D in D-NHCOCH ₂ COCH ₃ (3) [Equation (3) are as defined above. That is, 1 mol of the amino compound of the formula (2) is diazotized,
Coupling with 1 molar ratio of acetoacetylamino compound of formula (3). The diazotization and coupling can be performed by known methods. For example, the diazotization is carried out in mineral acid at temperatures below 10 ° C. with sodium nitrite and the coupling is advantageously in aqueous medium from 0 to 50 ° C., preferably 0 to 30 ° C., pH values of 2 to 9 preferably. 4-8. The product can be isolated by a generally known method (for example, salting out, alkali precipitation, etc.) and, if necessary, purified.

Since the heterocyclic compound of the formula (1) used in the present invention has a basic group (2), at least a theoretical amount of an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid or preferably an organic acid such as formic acid, By treatment with acetic acid, lactic acid, citric acid, glycolic acid, methanesulfonic acid, etc., the compound can be easily dissolved as a water-soluble acid addition salt form of the heterocyclic compound of the formula (1). This solution may be used as it is for dyeing a substrate or the like, or if desired, the solution may be dried up to obtain the acid addition salt in the form of powder.

The amino compound of the above formula (2) can be obtained, for example, by the same method as shown in German Patent Publication No. 2915323. That is, it can be produced by condensing 1 mol of nitroanilines with 1 mol of cyanuric chloride and 2 mol ratio of 3-diethylaminopropylamine or 2-diethylaminoethylamine in any order, and further reducing the nitro group. Specific examples of the nitroanilines used here include the following.

4-nitroaniline, 3-nitroaniline, 4-nitro-2-methoxyaniline, 4-nitro-2-methylaniline, 4-nitro-2-chloroaniline, 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-nitroaniline, 4-methyl-3-nitroaniline, 4-chloro-3-nitroaniline and the like.

When a corresponding acetylaminoaniline is used instead of nitroaniline, the amino compound of formula (2) is produced by condensing as described above and then performing hydrolysis instead of reduction.

The acetoacetylamino compound represented by the formula (3) can be obtained by reacting the corresponding amino compound with diketene, acetoacetic acid methyl ester or acetoacetic acid ethyl ester by a known method. It can, but is not limited to.

Etc.

The heterocyclic compound represented by the formula (1) is dried in the form of an acid addition salt in the form of powder or granules, or preferably without drying, in the form of a concentrated solution containing the above-mentioned organic acid or inorganic acid. It can be used for dyeing materials.

Processing into an appropriate concentrated solution is known in the art (eg, Japanese Patent Publication No.
The method described in No. 39-4879) can be used. That is, it is prepared by adding the heterocyclic compound of formula (1) to an aqueous solution of the aforementioned inorganic acid, preferably an organic acid, if necessary together with a water-soluble organic solvent. , Urea, etc.) can also be added. Examples of the water-soluble organic solvent used at this time include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, methyl cellosolve, carbitol, methyl carbitol, ethylene. Glycol dimethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, triethylene glycol monomethyl ether, butyl polyglycol, phenyl glycol, glycerin, tetrahydrofuran, dioxane, butyrolactone, N-methyl-2-pyrrolidone, formamide, Examples thereof include dimethylformamide. These water-soluble organic solvents may be used alone or in combination of two or more.

Next, a method of dyeing the substrate with the heterocyclic compound of formula (1) will be described.

The heterocyclic compound of the formula (1) can be used as a dye for dyeing fiber materials, leather, pulp, paper and the like, and as a dye material for preparing a color ink for printing those substrates.

The fiber material to which the heterocyclic compound of the formula (1) can be applied is a material that can be dyed with a cationic dye, for example, homopolymers and mixed polymers of acrylonitrile, acid-modified polyester and silk, and natural materials such as animal hair. Materials including nitrogen fibers and cellulose, for example, natural cellulose fibers typified by cotton, regenerated cellulose fibers, polyvinyl alcohol fibers, and further glass fibers are available.

The dyeing of these fibrous materials with the heterocyclic compound of formula (1) is carried out by an ordinary method, for example, an absorption dyeing method from a water bath under the conditions of pH 3 to 8 and temperature of 60 to 130 ° C. or spray coating with an aqueous ink, padding and It is carried out by continuous dyeing such as printing. The form of the fibrous material in this case can be monofilaments, yarns, cloths, knits and finished products. By using the heterocyclic compound of the formula (1) for these substrates, a clear yellow dyeing or printing with high color value can be obtained, and these dyeing or printing have excellent dyeability. In particular, it is characterized by an extremely high dyeing rate and excellent water fastness. A further preferred use of the heterocyclic compounds of formula (1) is in the dyeing of various bleached or unbleached, unsized or sized pulp and paper.

The heterocyclic compound of the formula (1) shows a very high dyeing speed and a very high dyeing rate even on pulp and paper (napkin, table cloth, sanitary paper, etc.) which has not been subjected to the sizing treatment. This high dyeing property makes the dyeing wastewater almost colorless, which can be said to be a great advantage in terms of wastewater regulation and environmental protection.

The dyeing of these papers and pulps is carried out at a pH value of 4 to 8, especially 5 to 7, and a dyeing temperature of 10 to 50 ° C, preferably 15 to 30 ° C. The obtained dyed product exhibits a clear yellow color with high color value,
Shows excellent dyeing fastness. In particular, with respect to water fastness, even if, for example, a dyed paper and a wet white paper are brought into contact with each other under pressure at room temperature, the dyed paper hardly shows a white transfer (bleeding). In addition, alum, alkali, acid,
Since it shows excellent robustness against alcohol,
It is highly suitable for paper applications where color bleeding is particularly concerned, such as napkins, tablecloths and sanitary paper. Even if two kinds of the heterocyclic compound of the formula (1) are mixed and used, the same effect as when used alone can be obtained. Further, the heterocyclic compound of the formula (1) has an extremely high affinity for paper and a high dyeing speed, and therefore can be applied to continuous dyeing of paper and ink for jet printers. The heterocyclic compound of formula (1) can also be applied to dyeing leather (exhaustion, spraying, brushing, etc.).
For example, exhaust dyeing of leather is carried out by dyeing in a dyebath containing a compound of heterocyclic (1) at a temperature of 30 to 70 ° C. and a pH value of 3 to 15 for 15 to 60 minutes, and then greasing treatment by a conventional method, It is performed by washing with water and drying.

EXAMPLES The present invention will be described in more detail by way of examples.

In the examples, parts are parts by weight and% is% by weight.

Preparation Example 1. 4- [2 ', 4'-bis (3 "-N, N-diethylaminopropylamino) -S-triazin-6'-yl-amino] aniline 8.9 parts of 100 parts of water and 8.3 parts of It was dissolved in 35% hydrochloric acid and diazotized with 1.4 parts of sodium nitrite (3.5 parts in 40% solution) for 30 minutes at 0 to 5 ° C. After that, excess nitrous acid was decomposed by addition of sulfamic acid. 60 ° C
A solution obtained by dissolving 4.9 parts of 5-acetoacetylaminobenzimidazolone in 200 parts of water with sodium hydroxide at a pH value of 11.0 was added to the above diazonium salt solution at 5 to 10 ° C. Then, add 4 parts of sodium hydrogen carbonate to adjust the pH value to 6.
The mixture was adjusted to 0 and stirred for 12 hours. Further adjust the pH value to 10.5 by adding sodium hydroxide solution, to precipitate the product,
After drying, 12.3 parts of the heterocyclic compound of formula (4) was obtained. This dried product was added to a mixture of 30 parts of water, 18 parts of acetic acid, and 18 parts of ethylene glycol, and heated to 90 ° C. to dissolve. Formula (4) Concentrated solution with good stability containing 12.3 parts of compound 8
You can get 0.0 copies. Even if λmax 405 nm (50% acetone water), a considerable amount of lactic acid or diethylene glycol was used instead of the acetic acid or ethylene glycol, a concentrated solution containing the compound of the formula (4) could be obtained in the same manner as above.

Also, dry powder of 12.3 parts of the compound of formula (4) was added with 10 parts of acetic acid and
It was possible to obtain a dried product of the acetic acid addition salt of the compound of formula (4) by dissolving in 130 parts of water at 85 ° C. and drying up the resulting solution. (14.4 parts) Production Example 2. 4- [2 ', 4'-bis (3 "-N, N-diethylaminopropylamino) -S-triazin-6'-yl-amino] aniline 8.9 parts 100 parts water And dissolved in 8.3 parts of 35% hydrochloric acid and 3.5 parts of 40% sodium nitrite for 0-5
Diazotization was performed at 30 ° C. for 30 minutes. After that, excess nitrous acid was decomposed by adding sulfamic acid. In 150 parts of water at 70 ° C., 5.8 parts of 2-acetoacetylamide-6-ethoxybenzothiazole was dispersed for 20 minutes by adjusting the pH value to 11.0 with sodium hydroxide. This solution was added to the above solution of the diazonium salt at 5-10 ° C. Then add 10 parts of sodium acetate and further sodium carbonate solution to adjust the pH value to 7.5.
The mixture was stirred for 12 hours while maintaining the H value. Then sodium hydroxide solution was added to adjust the pH value to 11.0, the product was precipitated and the crystals were separated. The obtained crystals are 10 parts of water and 20 parts of acetic acid.
Parts, 5 parts of urea and 18 parts of diethylene glycol were added, heated to 90 ° C. to dissolve and filtered. It was possible to obtain 85 parts of a concentrated solution containing 13.1 parts of the compound represented by the formula (5) (almost no insoluble matter). λmax 415nm (50% acetone water) Preparation Example 3. 4- [2 ', 4'-bis (3 "-N, N-diethylaminopropylamino) -S-triazin-6'-yl-amino] aniline 8.9 parts of 100 parts of water and 8.3 parts of Dissolve in 35% hydrochloric acid and add 0 to 5 with 3.5 parts of 40% sodium nitrite.
Diazotization was performed at 30 ° C. for 30 minutes. After that, excess nitrous acid was decomposed by adding sulfamic acid. To 150 parts of water at 70 ° C., 5.6 parts of 2-acetoacetylamide-6-methoxybenzothiazole was sufficiently dispersed for 30 minutes by adjusting the pH value to 11.0 with sodium hydroxide. This solution was added to the above solution of the diazonium salt while maintaining the temperature at 5 to 10 ° C. Thereafter, 4.5 parts of sodium hydrogen carbonate and further sodium carbonate solution were added to adjust the pH value to 7.5, and the mixture was stirred for 12 hours while maintaining the pH value. Then sodium hydroxide solution was added to adjust the pH value to 11.0, the product was precipitated and the crystals were isolated. The obtained crystals were added to a mixture of 10 parts of water, 24 parts of acetic acid, 5 parts of urea and 23 parts of ethylene glycol, heated to 90 ° C. to dissolve, and then filtered (with almost no insoluble matter) to give the formula ( Compound represented by 6) It was possible to obtain 102 parts of a concentrated solution containing 12.9 parts. λmax 41
A concentrated solution containing the compound of the formula (6) could be obtained in the same manner as above, even if a considerable amount of diethylene glycol was used in place of the ethylene glycol at 5 nm (50% acetone water).

Production Example 4. 9.5 parts of 4- [2 ', 4'-bis (3 "-N, N-diethylaminopropylamino) -S-triazin-6'-yl-amino] -2-methoxyaniline was added to 100 parts of water and 100 parts of water. It was dissolved in 8.3 parts of 35% hydrochloric acid and subjected to diazotization with 3.5 parts of 40% sodium nitrite for 30 minutes at 0 to 5 ° C. After that, excess nitrous acid was decomposed by addition of sulfamic acid.
To 200 parts of water at ℃, 4.9 parts of 5-acetoacetylaminobenzimidazolone was dissolved in a sodium hydroxide solution at a pH value of 11.0, and the solution was dissolved in the solution of the diazonium salt at 5 to 10 ℃.
Added while keeping. Thereafter, 4.5 parts of sodium hydrogen carbonate was added to adjust the pH value to 6.0, and the mixture was stirred for 12 hours. , Gradually add sodium hydroxide solution to adjust the pH value to 11.0,
The product was precipitated and isolated. 10 parts of the obtained precipitate with water,
Acetic acid 18 parts and ethylene glycol monobutyl ether 18
Part of the mixture was added, heated to 90 ° C. to dissolve and filtered. It was possible to obtain 85 parts of a concentrated solution containing the compound 12.9 represented by the formula (7) (insoluble matter was hardly seen). λmax 410 nm (50% acetone water) A concentrated solution could be obtained even if a considerable amount of formic acid was used in place of the acetic acid.

Example 1 A dry material consisting of 50% unbleached sulphite pulp and 50% mechanical pulp was beaten to 40 ° SR Freeness with water in a Beater with a pulp content of 3%. I adjusted it with water. This preparation
To 100 parts of water, 0.20 part of a concentrated solution of the compound of the formula (4) prepared in Production Example 1 prepared with water, acetic acid and ethylene glycol (containing 0.03 part of the compound of the formula (4)) and 0.02 part of acetic acid were added. The mixture is stirred for about 5 minutes and rosin size 0.
03 parts and 0.06 parts of crystalline aluminum sulfate were added, and the mixture was further stirred for 5 minutes. Then, 1400 parts of water was added to the mixture to dilute it, and this was paper-made on a Sheeter by a conventional method. Almost no coloring of the papermaking wastewater was observed, and the obtained colored paper showed a vivid yellow with color value, good light fastness and excellent water fastness.

Example 2 A dry material consisting of 100% bleached sulfite pulp was beaten to 35 ° SR freeness with water in a beater to give a pulp concentration of 3
Adjusted to%. 0.19 parts of a concentrated solution of the compound represented by the formula (5) described in Production Example 2 prepared by using 100 parts of this preparation solution with water, acetic acid, urea and diethylene glycol (containing 0.03 part of the compound of the formula (5)) Was added, and the mixture was stirred well for 5 minutes, diluted with 1400 parts of water, and then paper was made by a conventional method. In this case, the papermaking wastewater was scarcely colored by the dye. The resulting paper had a bright yellow color with high color value and good waterfastness.

Example 3. 4.0 parts concentrated solution of a compound of formula (6) as described in Preparative Example 3 prepared using unsized paper with water, acetic acid, urea and ethylene glycol (compound of formula (6) 0.5 parts), starch (0.5 parts) and water (95.5 parts) at 20-30 ° C for 2-3 seconds. Excess aqueous solution was squeezed through two rollers and then dried at 60-80 ° C. The dyed paper obtained had a bright yellow color with a high color value, was particularly excellent in water fastness, and almost no dye bleeding due to wetting was observed.

Example 4. Concentration of 100 parts of pig leather tanned with vegetable tannins using 250 parts of water at 50 ° C. and water, acetic acid, ethylene glycol monobutyl ether A solution containing 2.64 parts (containing 0.4 parts of the compound of formula (7)) was placed in a container containing the solution and stirred for 30 minutes, and then 10 parts of anionic oil containing sulfonated whale oil as the main component was added to 60 parts.
Processed for a minute. Next, this leather was subjected to a drying treatment to obtain a yellow uniform dyed leather. This dyed leather had very good wash fastness.

Example 5. Concentrated solution of a compound of formula (5) according to Preparation 2 prepared using water, acetic acid, urea and diethylene glycol.
Water bath 100 containing 65 parts (containing 0.10 part of compound of formula (5))
5 parts of cotton bleached by scouring and bleaching were added to the parts, and the temperature was raised to 100 ° C. in 40 minutes while stirring the dyebath and the material to be dyed, and the same temperature was maintained for 20 minutes. The compounds in the dyebath were completely exhausted to the cotton broad, and the cotton broad was dyed in a bright yellow color.
The water fastness of this dyed product was very good. Similarly, the viscose rayon woven fabric and the cupro woven fabric were dyed in a vivid yellow color and showed excellent water fastness.

Example 6. Production Example 1 prepared with water, acetic acid, and ethylene glycol
An aqueous solution consisting of 3.3 parts of a concentrated solution of the compound of formula (4) (containing 0.5 parts of the compound of formula (4)) and 96.7 parts of water is uniformly sprayed in an amount of 50% on the weight of the unsized paper. And dried at 60-70 ° C for 10 minutes. The dyed paper obtained had a yellow color with a high color value and showed good light resistance and water fastness.

Examples 7 to 42. Using the compounds shown in the table as the compounds of formula (3) and formula (2), heterocyclic compounds of formula (1) were produced according to Production Examples 1 to 4. In the following table, the acetoacetylamino compound represented by the formula (3), the amino compound represented by the formula (2), and λmax (5 of the obtained acetic acid addition salt of the compound of the formula (1)
(0% acetone water) and the hue when the paper was dyed with it were shown.

Effects of the Invention The specific heterocyclic compound used in the present invention has an extremely high dyeing speed, dyeing rate and dyeing concentration on a substrate,
And the waterfastness of the obtained dyed or colored substrate is good.

Claims (1)

[Claims] 1. A formula (1) [Wherein R is hydrogen, chloro, methyl or methoxy, n is 2 or 3 and D is (R ₁ represents hydrogen, chloro or methyl.) Or (R ₂ and R ₃ are hydrogen, chloro, bromo, methyl, methoxy,
Represents ethoxy, acetylamino, sulfonamide, thiocyano, methylsulfonyl, methoxycarbonyl or ethoxycarbonyl. ), Respectively. ] The dyeing method of the base material characterized by using the heterocyclic compound represented by these.