JPH0696827B2 - Substrate dyeing method using disazo compound - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for dyeing a substrate in black. More specifically, it relates to a method for dyeing a base material such as a fiber material or paper using a specific disazo compound.

2. Description of the Related Art Many dyes are used for dyeing and printing various fiber materials, leather, paper or pulp, but few are satisfactory in dyeing properties (dyeing speed, dyeing rate, etc.). In particular, the conventional dyes used for dyeing paper and pulp in black are difficult to obtain a deep black color due to the problem that the dyeing speed and the dyeing rate are small, and in addition, in the water fastness of the dyed product. There are few that are at a satisfactory level.

Problems to be Solved by the Invention Recently, the rationalization of the dyeing process has been increasingly required, but the dyeing speed and dyeing rate are high and the dyeing wastewater is almost colorless from the viewpoint of shortening the dyeing time and environmental protection. It has been desired to develop such dyes having good water fastness to the dyed products. In particular, in obtaining a black dyed product, the use concentration of the black dye reaches several times the amount of dyes of other hues, so that the dyeing speed and dyeing rate are excellent, and the water fastness of the black dye is excellent. The development of a method for giving a dyed product has long been desired.

Means for Solving the Problems The present inventors have found that various base materials (for example, textile materials, leather,
To find a method that gives a hard black dyeing product with high dyeing speed and dyeing rate, excellent color value (dyeing density) and water fastness when dyeing and printing wood, pulp, paper, etc.) As a result of intensive studies, the present invention has been achieved.

That is, the present invention provides a compound of formula (1) in the form of a free acid. [In the formula, R ₁ and R ₂ each independently represent an alkyl or hydrogen having 1 to 3 carbon atoms which may be substituted by alkoxy having 1 to 4 carbon atoms, phenyl, phenoxy, hydroxyl or cyano, and R ₃ is hydrogen. , Chloro, methyl, methoxy or ethoxy, R ₄ is acetylamino, propionylamino or ureido, R ₅ is hydrogen, chloro, methyl or methoxy, and n is 2 or 3, respectively.] The present invention provides a black dyeing method for a substrate, which is characterized by being used.

The dyeing method of the present invention using the disazo compound of formula (1) will be described below.

The disazo compound of the formula (1) used in the present invention is used as a dye for dyeing various fiber materials, leather, wood, pulp, paper and the like, and for preparing a color ink used for printing those substrates. A substrate which exhibits excellent suitability as a black dye material but to which the disazo compound of the formula (1) can be applied and a dyeing method thereof will be specifically described. First, as the fiber material, various materials that can be dyed with a cationic dye, for example, homopolymers and mixed polymers of acrylonitrile, acid-modified polyester and silk, natural nitrogen-containing fibers such as animal hair, various materials including cellulose such as cotton. And natural cellulose fibers, regenerated cellulose fibers, polyvinyl alcohol fibers, and glass fibers. Dyeing of these fiber materials using the disazo compound of the formula (1) is carried out by a conventional method, preferably an absorption dyeing method in a water bath having a pH value of 3 to 8 and a dyeing temperature of 60 to 130 ° C. or spray coating with an aqueous ink. , Batch and continuous dyeing such as padding and printing. The form of the fibrous material in this case may be any form of monofilament, yarn, cloth, knit and finished product. By using the disazone compound of the above formula (1), a deep black dyeing or printing product having an extremely high color value can be obtained, and these dyeing or printing products have an extremely high dyeing rate and excellent waterfastness. And shows good light fastness.

Furthermore, the most preferred use of the disazo compounds of formula (1) is dyeing pulp and paper. That is, absorption method (internal addition method) of various types of bleached or unbleached unsized or sized pulp and paper, surface dyeing method (addition to coat or size press liquid), padding method, printing method and spraying method. It is a dyeing method such as a batch method and a continuous method. The disazozone compound of the formula (1) shows a very high dyeing speed and a very high dyeing rate even on pulp and paper which are not subjected to the sizing treatment (such as napkin, table cloth and sanitary paper). This high dyeing property makes dyeing wastewater close to colorless in absorption dyeing, which is a great advantage from the viewpoint of wastewater regulation and environmental protection. The dyeing of these pulps and papers has a pH value of 4 to
8, especially 5 to 7, dyeing temperature 10 to 50 ° C, preferably 15 to 30
It is carried out at ° C. The resulting dyed product of paper or pulp exhibits a deep black color with a high color value and exhibits excellent light fastness and water fastness. In particular, with regard to water fastness, even if, for example, a dyed paper and a wet white paper are brought into pressure contact with each other at room temperature, there is almost no transfer (bleeding) from the dyed paper to the white paper. Furthermore, since it shows excellent fastness to alum, alkali, acid, alcohol, napkin,
It is very suitable for the application fields of dark black paper such as table cloth and sanitary paper, where "color bleeding" is a particular concern.

Furthermore, since the disazo compound of the formula (1) has an extremely high affinity for paper and has a fast dyeing speed, it is intended for ink jet recording ink and stationery ink (feet pen, felt-tip pen) intended for recording on paper. Etc.) can also be applied by a conventional method.

Further, the disazo compound of the formula (1) is also applied to dyeing of leather and wood (absorption, spraying, brush coating, printing etc.). For example, the absorption dyeing method for leather is dyeing in a dyeing bath containing the compound of formula (1) at a temperature of 30 to 70 ° C. and a pH value of 3 to 8 for 15 to 60 minutes,
Then, after greasing treatment by a conventional method, it is washed with water and dried.
Absorption dyeing of wood is carried out by immersing the wood in a water bath having a pH value of 3 to 8 and a temperature of 20 to 130 ° C. for a certain period of time, then taking out the wood, washing with water and drying.

The disazo compound represented by the formula (1) is produced, for example, as follows. That is, the amino compound of the following formula (2) [In the formula (2), R ₅ and n have the same meanings as described above. ] Is diazotized and coupled to an anilino compound of the following formula (3) [In the formula (3), R ₃ and R ₄ have the same meanings as described above. By doing so, a monoazo compound represented by the following formula (4) is obtained. The monoazo compound is further disazo-ized,
Coupling with naphthol sulfonic acids of formula (5) below.

[In the formula (4), R ₃ , R ₄ , R ₅ and n have the same meanings as described above. ] [In the formula (5), R ₁ and R ₂ have the same meanings as described above. Each diazotization and coupling can be performed by a known method. For example, diazotization is carried out in mineral acid at 0 to 25 ° C. with sodium nitrite, and coupling is 0 to 30 ° C.
C., pH value is 2-9. The product can be isolated by a generally known method and, if necessary, purified.

Since the disazo 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, acetic acid is used. It can be easily dissolved as a water-soluble acid addition salt form of the disazo compound of the formula (1) by treating with lactic acid, citric acid, glycolic acid and methanesulfonic acid. This solution may be used as it is for dyeing a substrate or the like, or if desired, the solution may be driven up to obtain the acid addition salt of the disazo compound in the form of powder.

The amino compound of the formula (2) is prepared by condensing 1 mol of acetylaminoanilines with 1 mol of cyanuric chloride and 2-diethylaminopropylamine or 2-diethylaminoethylamine 2 mol ratio in any order, and further hydrolyzing the acetylamino group. It can be manufactured by disassembling. The following can be mentioned as specific examples of the acetylaminoanilines used here.

4-acetylaminoaniline, 3-acetylaminoaniline, 4-acetylamino-3-methoxyaniline, 4
-Acetylamino-3-methylaniline, 4-acetylamino-3-chloroaniline, 4-methoxy-3-acetylaminoaniline, 4-methyl-3-acetylaminoaniline, 4-chloro-3-acetylaminoaniline,
4-acetylamino-2-methoxyaniline, 4-acetylamino-2-methylaniline, 4-acetylamino-2-chloroaniline, 5-acetylamino-2-methoxyaniline, 5-acetylamino-2-methylaniline, 5-acetylamino-2-chloroaniline and the like.

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

The following can be mentioned as specific examples of the aniline compound represented by the formula (3).

Examples are 5-acetylamino-2-methoxyaniline, 5-acetylamino-2-ethoxyaniline, 5-acetylamino-2-chloroaniline, 3-acetylaminoaniline, 3-propionylaminoaniline and 3-ureidoaniline. The following can be mentioned as specific examples of the naphtholsulfonic acids represented by the formula (5), but the naphtholsulfonic acids are not limited to these. (Both are shown as liberation) Etc.

The disazo compound represented by the formula (1) is dried in the form of an acid addition salt, as described above, in the form of powder or granules, or preferably without drying, in a concentrated bath solution containing the above-mentioned organic acid or inorganic acid. Although it can be used for dyeing the substrate in the form, it can be processed into a suitable concentrated solution by a known method (for example, the method described in JP-B-39-4879). That is, the disazo compound of the formula (1) is prepared by adding a water-soluble organic solvent, if necessary, to an aqueous solution of the aforementioned inorganic acid, preferably an organic acid. In this case, if desired, an auxiliary agent (for example, activator, urea, etc.) can 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, hexylene glycol, thioglycol, glycerin, tetrahydrofuran, dioxane, butyrolactone, N-methyl- 2-pyrrolidone, formamide, dimethy Formamide, it may be mentioned methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol and the like. These water-soluble organic solvents may be used alone, and 2
More than one species may be used in combination.

EXAMPLES The present invention will be described in more detail by way of examples. The middle part of the examples is part by weight, and% is% by weight. The sulfonic acid group in the examples is represented as a free acid.

Example 1. Formula (6) 17 parts of the disazo compound represented by the formula (3) was added to a mixture of 70 parts of water, 25 parts of lactic acid and 20 parts of urea, and heated at 80 ° C. to dissolve, to obtain 132 parts of a concentrated solution having good stability. λmax 597nm (50
% Acetone water), bleached sulfite pulp obtained from pine wood 50
Parts and 50 parts of bleached sulphite pulp obtained from birch wood were used to dry 30% SR in 5000 parts of water using a beater (Schopper-Riegler Freeness)
Beaten to become. Add 11.6 of the above concentrated solution to this pulp liquid.
Parts (containing 1.5 parts of the compound of formula (6)) were added. The mixture was stirred for about 5 minutes, 1 part rosin size and 2 parts crystalline aluminum sulfate were added and stirred for a further 5 minutes. Next, 95,000 parts of water was added to the mixture to dilute it, and this was paper-made on a Sheater by a conventional method. Almost no coloring of the papermaking wastewater was observed, and the obtained dyed paper showed a deep black color with a color value, good light fastness and excellent water fastness.

The disazo compound of the above formula (6) was produced as follows.

4- [2 ', 4'-bis (3 "-N, N-diethylaminopropylamino) -S-triazin-6'-yl-amino] aniline 9.7 parts to 110 parts water and 9.1 parts 35% hydrochloric acid. It was dissolved and diazotized with 1.5 parts of sodium sulfite (3.8 parts in 40% solution) for 30 minutes at 0 to 5 ° C. Powder of 5-acetylamino-2-methoxyaniline 4.0 was added to this solution.
Parts were added at 5-10 ° C over 15 minutes and stirred for 2 hours. After that, add sodium carbonate solution to adjust the pH value to 3.0.
The mixture was stirred at 0 ° C for 10 hours. To this solution was added 3 parts of 35% hydrochloric acid, and the mixture was subjected to diazotization with 1.6 parts of sodium sulfite (4.0 parts of 40% solution) at 5 to 10 ° C for 1 hour. After that, excess nitrous acid was decomposed by adding sulfamic acid. 60 ° C water
130 parts to 7-N-methylamino-1-naphthol-3-
While dissolving 5.5 parts of sulfonic acid in sodium hydroxide to a pH value of 10.0, the above diazonium salt solution was maintained at a pH value of 8.0 with sodium carbonate solution, while maintaining a pH value of 15 at 5 to 10 ° C.
It was added over a period of 1 minute, and the mixture was further stirred for 2 hours. Then, a sodium hydroxide solution was gradually added to adjust the pH value to 11.0, the product was precipitated, isolated and dried to obtain 17 parts of a disazo compound represented by the formula (6).

Example 2. Formula (7) 17.6 parts of the disazo compound represented by the above was added to a mixture of 74.4 parts of water, 25 parts of acetic acid and 15 parts of urea, and heated to 80 ° C. to be dissolved to obtain 132 parts of a concentrated solution having good stability. λmax 598 (5
0% acetone water). 100 parts of dry material of unbleached sulfite pulp obtained from pine wood and 3300 parts of water at 35 ° S in a beater
I beat R Freeness. Add this concentrated solution 1 to this pulp liquid.
5 parts (containing 2 parts of the compound of formula (7)) were added and well stirred for 5 minutes. To this, 96700 parts of water was added and diluted, and then paper was made by a conventional method. In this case, almost no dye coloring was observed in the papermaking wastewater. The dyed paper obtained showed a deep black color with a high color value, and showed excellent water fastness and good light fastness.

The disazo compound represented by the above formula (7) is 7-in Example 1.
It was synthesized according to Example 1 except that 6.2 parts of 7- (β-hydroxylethylamino) -1-naphthol-3-sulfonic acid was used instead of N-methylamino-1-naphthol-3-sulfonic acid.

Example 3. 3.1 parts of the concentrated solution described in Example 1 (compound 0.4 of formula (6)
5 parts of a cotton bleached by scouring and bleaching were put into 100 parts of a water bath containing 100 parts), and the temperature was raised to 100 ° C. in 20 minutes while stirring the dyeing bath and the material to be dyed, and the same temperature was maintained for 40 minutes. The compounds in the dyebath were almost completely exhausted to the cotton broad cloth, which was dyed a deep black color. The dyeings show good fastness to light and fastness to water. Similarly, the viscose rayon woven fabric and the cupro woven fabric were dyed in a deep black color and showed good light fastness and water fastness.

Examples 4 to 19 The compounds shown in the table were synthesized by the same method as in Example 1, and the paper was dyed according to the method described in Examples 1 and 2. Good light resistance and water resistance were obtained as described above. A high-color-value, dark-black dyed paper with fastness is given. The following table shows the diazo compound represented by the formula (1), λmax (50% acetone water) of the lactic acid addition salt of the compound, and the hue when paper is dyed with the same.

EFFECTS OF THE INVENTION By using the disazo compound represented by the formula (1), a substrate can be dyed in a dark black color at a high dyeing speed and a high dyeing density, and the resulting dyed substrate has light fastness and water fastness. Is very good.

Claims (1)

[Claims] 1. A formula (1) in the form of a free acid. [Wherein R ₁ and R ₂ each independently represent an alkyl or hydrogen having 1 to 3 carbon atoms which may be substituted with alkoxy having 1 to 4 carbon atoms, phenyl, phenoxy, hydroxyl or cyano, and R ₃ represents hydrogen. , Chloro, methyl, methoxy or ethoxy, R ₄ is acetylamino, propionylamino or ureido, R ₅ is hydrogen, chloro, methyl or methoxy, and n is 2 or 3, respectively.] Black dyeing method for substrates characterized by using