JPH0762112B2 - Disazo compound and dyeing method of substrate using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a disazo compound and a method for dyeing a substrate using the same.

BACKGROUND ART Many dyes are used for dyeing and printing fiber materials, leather, paper or pulp, but the dyeing characteristics (dyeing speed,
There are not so many satisfactory dyeing rates.
Particularly, known dyes used for dyeing paper and pulp in red have a problem that the dyeing speed and dyeing rate are small, and in addition, there is a problem that the water fastness of the dyed product is not sufficient. is there.

Problems to be Solved by the Invention More and more streamlining processes in the dyeing industry are demanded, and especially from the viewpoint of shortening the dyeing time and environmental protection, the dyeing speed and the first-arrival rate are high, and the dyeing wastewater is close to colorless. so,
Moreover, development of a dye having good water fastness of the dyed product is desired.

Means for Solving the Problems In carrying out dyeing and printing of substrates such as textile materials, leather, wood, pulp and paper, the present inventors have excellent color value (dyeing density) and dyeing speed. Further, as a result of earnest research to find a red dye having a high dyeing rate and excellent waterfastness, 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 (1), R and R ₁ represent hydrogen, chlorine, methyl or methoxy, and R ₂ and R ₃ represent hydrogen, methyl or methoxy, respectively. ] The disazo compound represented by these, and the dyeing method of the base material characterized by using the same are provided. The disazo compound represented by the formula (1) of the present invention can be produced, for example, as follows. That is, a monoazo compound represented by the following formula (2) in the form of a free acid [In the formula (2), R, R ₁ , R ₂ and R ₃ have the same meanings as described above. ] Is diazotized to give 6-acetylamino-1-naphthol-
By coupling with 3-sulfonic acid and then hydrolyzing the acetylamino group, a disazo compound represented by the following formula (3) is obtained in the form of a free acid.

[In the formula (3), R, R ₁ , R ₂ and R ₃ have the same meanings as described above. The disazo compound represented by the formula (1) of the present invention can be obtained by reacting this disazo compound (1 mole ratio) with cyanuric chloride (1 mole ratio) and diethylaminopropylamine (2 mole ratio) in any order.

Further, the monoazo compound represented by the formula (2) is diazotized and coupled in the form of a free acid with the naphtholsulfonic acid derivative represented by the following formula (4), [In the formula (4), R ₄ and R ₅ represent chloro or diethylaminopropylamino. Further, when one or both of R ₄ and R ₅ is chloro, the disazo compound represented by the formula (1) can be obtained by reacting with 1 mol or 2 mol ratio of diethylaminopropylamine.

The respective diazotization and coupling can be performed by known methods. For example, diazotization is carried out in mineral acid at 0-30 ° C with sodium nitrite, and coupling is 0-30 ° C.
The pH value is 5-9. Condensation with cyanuric chloride is generally carried out at 0-20 ° C for the replacement of the first chloro atom, at 30-60 ° C for the replacement of the second chloro atom, and at 80-100 ° C for the replacement of the third chloro atom. To be done. The product can be isolated by a generally known method and, if necessary, purified.

The disazo compound of the formula (1) used in the present invention has a basic group (2) and a sulfonic acid group (2), but is easily soluble in water and has a good solubility particularly in the range of pH 2 to 11. is doing.

That is, for example, sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, and sodium hydrogencarbonate can be used as an inorganic base when it is dissolved in an alkaline state, and an inorganic acid or an organic acid can be used when it is acidified. , Hydrochloric acid, sulfuric acid, phosphoric acid, formic acid,
It can be easily dissolved in water by treating with acetic acid, lactic acid, citric acid, glycolic acid and methanesulfonic acid.

The disazo compound represented by the formula (1) can be used for dyeing a substrate in the form of a concentrated aqueous solution, but processing into a concentrated solution which is stable in storage can be carried out by a known method (for example, JP-B-39-39).
4879 and JP-A-57-65757). That is, it is prepared by adding a water-soluble organic solvent, if necessary, to the aqueous solution of the disazo compound of the formula (1) and the aforementioned inorganic base or inorganic acid, preferably organic acid. In this case, if desired, auxiliary agents (eg ureas,
Surfactants, quaternized alkylamines, and aliphatic amines such as ethanolamine, diethanolamine, triethanolamine, 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, propylene glycol monomethyl ether, butyl polyglycol, phenyl glycol , Hexylene glycol, thioglycol, glycerin, tetrahydrofuran, dioxane, butyrolactone, N-methyl-2-pyrrolidone, formamide, dimethylformamide, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol and the like. These water-soluble organic solvents may be used alone or in combination of two or more.

In order to facilitate the liquefaction, the reaction solution containing the disazo compound represented by the formula (1) is treated with an ultrafiltration membrane or a reverse osmosis membrane (eg, cellulose acetate membrane, polymer membrane, etc.) to remove the inorganic salt. It is also possible to remove and concentrate the solution and use it for processing into a concentrated solution. A concentrated solution is particularly preferable for dyeing paper, pulp, etc., but if necessary, a reaction solution containing the disazo compound represented by the formula (1) can be salted out and dried to obtain a powder. Is.

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

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, etc., and a reddish color for preparing a color ink used for printing those substrates. Although it has excellent suitability as a dye material, a substrate 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, 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, that is, natural cellulose fibers typified by cotton. , Recycled cellulose fiber, polyvinyl alcohol fiber, and further glass fiber. The 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 11 and a dyeing temperature of 60 to 130 ° C. or spray coating with an aqueous ink. , Batching 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 disazo compound of the formula (1), red dyeing or printing with extremely high color value can be obtained, and these dyeing or printing have extremely high dyeing rate and excellent water fastness. Show.

Furthermore, the most preferred use of the disazo compound 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 disazo compound of the formula (1) shows a large dyeing speed and a high dyeing ratio 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 the dyeing wastewater close to colorless in the absorption dyeing method, which is a great advantage from the viewpoint of wastewater regulation and environmental protection. The dyeing of these pulps and papers is carried out at pH values of 3 to 11, especially 4 to 10, at dyeing temperatures of 10 to 50 ° C, preferably 15 to 30 ° C. The obtained dyed product of pulp or paper exhibits a red color with a high color value and exhibits excellent water fastness. With respect to this excellent water fastness, for example, even if a dyed paper and a wet white paper are brought into contact with each other under pressure 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, it is very suitable for application fields of red paper such as napkins, table cloths and sanitary papers where "color bleeding" is particularly concerned.

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

The disazo compound of the formula (1) can also be applied to dyeing leather and wood (absorption, spraying, brush coating, printing, etc.). For example, the absorption dyeing method for leather is 15 at a temperature of 30 to 70 ° C. and a pH value of 3 to 10 in a dyeing bath containing the disazo compound of the formula (1).
After dyeing for ~ 60 minutes and then greasing in the usual way,
Wash with water and dry. PH value 3-10, temperature 20 for absorption dyeing of wood
It is carried out by immersing the wood in a water bath at ~ 130 ° C for a certain period of time, then taking it out, washing it with water and drying it.

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. 4-Amino-1,1'-azobenzene-4'-sulfonic acid 13.9 parts was added to 400 parts of water at 65 ° C. with sodium hydroxide to obtain a pH value of 1
It was made 0.0 and dissolved. To this, 0.1 parts of Liponox NA (Lion oil, anionic active material) and 3.6 parts of sodium nitrite were added, and this solution was added to an aqueous solution consisting of 11 parts of 35% hydrochloric acid and 35 parts of water by adding ice to 12 to 17 It took 30 minutes to add while maintaining the temperature at ℃. The diazotization was completed by stirring for 1 hour. The excess nitrous acid was then destroyed with sulfamic acid.

6-Acetylamino-1-naphthol-3-sulfonic acid
14.1 parts were dissolved in 100 parts of water with sodium hydroxide to a pH value of 8.0, and 10 parts of sodium hydrogen carbonate was added. To this solution, add the above diazotized solution to pH 8.0-8.5 with sodium carbonate.
The temperature was maintained at 8 to 13 ° C over 30 minutes, and the mixture was stirred for 2 hours. Next, 80 parts of 47% sodium hydroxide was added to this solution, and the mixture was stirred at 95 ° C for 3 hours. Then add 35% hydrochloric acid to this solution.
80 parts was added and the pH value was adjusted to 7.0. Further, 150 parts of sodium chloride was added to precipitate the product, and the product was dried. 22.9 parts of the disazo compound represented by the formula (5) was obtained.

Dissolve 10.5 parts of the disazo compound of formula (5) in 200 parts of water at 60 ° C. to a pH value of 9 to 10 with sodium hydroxide, and dissolve 40 parts of water,
Liponox NA 0.1 part and cyanuric chloride 3.8 parts are added to a water-cooled stirring dispersion liquid while maintaining the temperature at 10 ° C. The solution was stirred with sodium carbonate solution for 3 hours while maintaining the pH value at 7.0.

Furthermore, 7.8 parts of diethylaminopropylamine was added, and 9
The mixture was stirred at 5 ° C for 3 hours. Then pH with sodium hydroxide
The value was adjusted to 11-12 and 80 parts of sodium chloride was added to precipitate the product, which was dried. After adding this dried product to a mixture of 100 parts of water and 20 parts of urea, it was heated to 90 ° C. and pH value was 9.5.
It was dissolved in. A concentrated solution containing 15.5 parts of the disazo compound represented by the formula (6) with good stability, excluding insoluble matter 150
I got a part.

λmax 508nm (40% acetone, 10% acetic acid water) Example 2. 5.6 parts of the disazo compound represented by the formula (7) prepared in the same manner as in Example 1 was added to 100 parts of water at 60 ° C. with sodium hydroxide.
Dissolve at pH value 9-10 20 parts water, 0.1 parts liponox NA and cyanuric chloride
Add to 1.9 parts of water-cooled stirred dispersion while maintaining 10 ° C. The solution was stirred with sodium carbonate solution for 3 hours while maintaining the pH value at 7.0. Further diethylaminopropylamine
3.9 parts was added, and the mixture was stirred at 95 ° C for 3 hours. After that, the pH value was adjusted to 11 to 12 with sodium hydroxide, 35 parts of sodium chloride was added, the product was precipitated, and the crystals were separated. The crystals were added to a mixture of 40 parts of water, 10 parts of urea and 10 parts of ethylene glycol, heated to 90 ° C. and dissolved at a pH value of 9.5. The disazo compound represented by the formula (8), excluding insoluble components, 8.
As a result, 85 parts of a concentrated solution containing 0 part and having good stability was obtained. λmax516n
m (40% acetone, 10% acetic acid water) Example 3. 5.5 parts of 4-amino-1.1'-azobenzene-3'-sulfonic acid was added to 100 parts of water at 65 ° C with sodium hydroxide to obtain a pH value of 9.
It became 5 and melt | dissolved. To this, 1.5 parts of sodium nitrite was added, and this solution was added over 20 minutes while maintaining 12 to 17 ° C. by adding ice to an aqueous solution containing 6 parts of 35% hydrochloric acid and 15 parts of water. The diazotization was completed by stirring for 1 hour. Excess nitrous acid was destroyed with sulfamic acid.

12.1 parts of 2- (5'-hydroxy-7'-sulfonaphthylamino-2 ')-4.6-bis (3 "-N, N-diethylaminopropylamino) -1.3.5-triazine was added to 10 parts of water.
It was dissolved in 0 part at a pH value of 6.0, and 4 parts of sodium hydrogen carbonate was added thereto. The above diazotized solution was added to this solution with sodium carbonate while keeping the pH value at 7.5 at 8 to 13 ° C. over 30 minutes, and stirred for 4 hours. Then use lithium hydroxide to adjust the pH value to 11-12.
After adjusting to, the mixture was heated to 90 ° C., 54 parts of sodium chloride was added, the product was precipitated, and crystals were separated. This crystal in water
After being added to a mixture of 95 parts, 15 parts of urea and 15 parts of diethylene glycol, the mixture was heated to 90 ° C. and dissolved at a pH value of 9.0. Then, the insoluble component is removed and the disazo compound represented by the formula (9) is expressed.
160 parts of a concentrated solution containing 15.1 parts and having good stability were obtained. λmax
510nm (40% acetone, 10% acetic acid water) In this example, instead of 2- (5'-hydroxy-7'-sulfonaphthylamino-2 ')-4,6-bis (3 "-N, N-diethylaminopropylamino) -1.3.5-triazine 2- (5'-hydroxy-7'-sulfonaphthylamino-2 ')-4- (3 "-N, N-diethylaminopropylamino) -6-chlor-1.3.5-triazine 10.1 parts After completion of the coupling, 3.9 parts of diethylaminopropylamine was added and the reaction was carried out at 95 ° C. for 3 hours, whereby the same disazo compound as in the formula (9) could be produced.

Example 4. 2500 parts of water was added to 70 parts of bleached sulfite pulp obtained from birch wood and 30 parts of bleached sulfite pulp obtained from pine wood,
30 ° SR Freeness in the Beater (Schopper-
Rilgler Freeness). In this pulp liquid, 20 parts of light calcium having an average particle size of 3μ, 0.3 part of a polyacrylic amide-based retention aid, and a synthetic polymeric cation sizing agent.
0.2 part and 6.8 parts of the concentrated solution prepared in Example 1 (containing 0.7 part of the compound of formula (6)) are added. The mixture was well stirred for 5 minutes, adjusted to pH value of 8.0 to 8.5 with sodium carbonate, and 90,000 parts of water was added to prepare a paper by a conventional method. Almost no coloring was observed in the papermaking wastewater, and the obtained dyed paper showed a red color with a color value, and showed excellent water fastness.

Example 5. 6.4 parts of the concentrated solution prepared in Example 2 (compound of formula (8)
0.6 part) was dissolved in 93.6 parts of water, 2 parts of anionic surface sizing agent was added, and then a colored size press coating solution having a solution pH value adjusted to 8 to 9 was prepared. The obtained liquid was coated with a size press, and the obtained colored weak size paper having a Steckigt size degree of 7 seconds showed a red color with good leveling property and good water fastness.

Example 6. 13.8 parts of the concentrated solution prepared in Example 3 (compound of formula (9)
Containing 1.3 parts) diethylene glycol 20 parts and water 66.2
Part of the mixture and adjusted to a pH value of 9 with potassium hydroxide.
It was adjusted to -10 to obtain a water-based ink. The water-based ink was printed on a strongly acid-sized paper by using a felt pen or an ink jet printer. The obtained print showed red color with a color value in spite of the strongly acidic sizing paper, and the ink penetration and water fastness were also good.

Example 7. 15.5 parts by weight of a dried product of the disazo compound represented by the formula (6) obtained in Example 1, 100 parts of water and 3-chloro-2-hydroxypropyltrimethylammonium chloride 5.
25 parts of lactic acid was added to 6 parts of the mixture and heated to 90 ° C. to be dissolved to obtain 160 parts of a concentrated solution. λmax 508 nm (40% acetone, 10% acetic acid in water).

A dry material consisting of 50 parts of bleached sulphite pulp obtained from pine wood and 50 parts of bleached sulphite pulp obtained from birch wood was beaten with a beater in 5,000 parts of water to a 30 ° SR freeness. To this pulp liquor was added 8.3 parts of the above concentrated solution (containing 0.8 part of the compound of formula (6)). 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, add 95,000 parts of water to this and dilute it.
paper was made on a heater) by a conventional method. Almost no coloring of the papermaking wastewater was observed, and the obtained dyed paper showed red color with color value, and showed excellent water fastness.

Example 8 Dried product of the disazo compound of formula (6) obtained in Example 1
20 parts of acetic acid was added to a mixture of 15.5 parts, 100 parts of water and 5.6 parts of 3-chloro-2-hydroxypropyltrimethylammonium chloride, and heated to 90 ° C. to dissolve to obtain 155 parts of a concentrated solution. λmax 508 nm (40% acetone, 10% acetic acid in water).

Unbleached Sulfite Pulp Dry Material Obtained from Ezo Pine Wood 10
0 part and 3300 parts of water were beaten to 35 ° C SR freeness in a beater. To this pulp liquid was added 10 parts of the above concentrated solution (containing 1.0 part of the compound of the formula (6)) 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.
Almost no dye coloring was observed in the papermaking wastewater. The resulting dyed paper showed a red color with a high color value and showed excellent water fastness.

Example 9. 7.2 parts of the concentrated solution prepared in Example 7 (compound of formula (6)
0.7 parts), starch 0.5 parts and water 92.3 parts
2 to 3 for paper that has not been subjected to sizing treatment at 20 to 30 ° C
Soaked for a second. Excess aqueous solution was squeezed through two rollers and then dried at 60-80 ° C. The obtained dyed paper showed red color with a high color value, almost no dye bleeding due to wetting was observed, and the water fastness was also good.

Example 10. 8.8 parts of the disazo compound represented by the formula (10) added up according to Example 3 was added to a mixture of 46.2 parts of water, 15 parts of formic acid and 15 parts of diethylene glycol monobutyl ether, and 90 It was heated to 0 ° C. and dissolved to obtain 85 parts of a concentrated solution. λmax513
nm (40% acetone, 10% acetic acid in water).

100 parts of pig leather tanned with vegetable tannins is placed in a dyeing bath consisting of 250 parts of water at 50 ° C. and 3.9 parts of the above concentrated solution (containing 0.4 parts of the compound of formula (10)) and stirred for 30 minutes, then the same bath Was treated with 10 parts of anionic fats and oils containing sulfonated whale oil as a main component for 60 minutes.

Next, this leather was dried to obtain red dyed leather having a high color value. This dyed leather had very good wash fastness.

Example 11. 1.0 part of the concentrated solution described in Example 10 (compound 0.1 of formula (10)
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, and the cotton broad was dyed red with a color value. The dyeing has a good water fastness. Similarly, the viscose rayon woven fabric and the cupro woven fabric were dyed in red with a color value and showed good water fastness.

Examples 12 to 28. A disazo compound of formula (1) was prepared according to Examples 1 to 3. The following table shows the disazo compound represented by the formula (1) in the form of the free acid, and the λmax of the compound (40% acetone, 10%
Acetic acid water) and the hue when the paper was dyed with it were shown.

Effect of the Invention The disazo compound of the present invention has an extremely high dyeing speed, a first-arriving rate and a first-arriving concentration with respect to a substrate, and the obtained dyed or colored substrate has good water fastness.

Claims (2)

[Claims] 1. A formula (1) in the form of a free acid. [In the formula (1), R and R ₁ represent hydrogen, chlorine, methyl or methoxy, and R ₂ and R ₃ represent hydrogen, methyl or methoxy, respectively. ] The disazo compound represented by these. 2. The formula (1) in the form of the free acid. [In the formula (1), R and R ₁ represent hydrogen, chlorine, methyl or methoxy, and R ₂ and R ₃ represent hydrogen, methyl or methoxy, respectively. ] The dyeing method of the base material characterized by using the disazo compound represented by these.