JP3020433B2 - Manufacturing method of yellow vat dye - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a process for producing an anthraquinone thiazole compound as a yellow vat dye from 2,6-diaminoanthraquinone.

[0002]

2. Description of the Related Art The compound of formula (1) (formula 2) which is the object compound of the present invention

[0003]

Embedded image Anthraquinone thiazole compound (2,8-diphenyl-anthra [2,1-d: 6,5-d '] bisthiazole-6,12-dione; CI Vat Yellow
w2; Mikethren Yellow GCN)
(Hereinafter abbreviated as GCN) is a compound well known as a yellow vat dye for a long time.

[0004] As a method of manufacturing this GCN,
A method of reacting 6-diaminoanthraquinone with benzoyl chloride and sodium bisulfide and converting the resulting reaction product to thiazole with sulfuric acid has been known for a long time, and is still a general production method.

As a specific method, as described in, for example, “Theoretical Production Dye Chemistry” by Yutaka Hosoda (Gihodo, 1968), after the thiazolation in 96% or 100% sulfuric acid, the reaction solution is water And GCN is precipitated by rapidly lowering the concentration of sulfuric acid and then filtered.

However, the GCN obtained by this prior art
Often contains impurities of unknown structure that cause dark red or dark blue, and there is no known purification method. I couldn't.

[0007]

SUMMARY OF THE INVENTION The present invention is a further improvement of the prior art, which provides a high-quality G without impairing the yield.
It provides a method for obtaining CN.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found an industrially extremely valuable method, and have completed the present invention.

That is, according to the present invention, 2,6-diaminoanthraquinone is reacted with benzoyl chloride and sodium hydrosulfide to obtain a compound of the formula (1)

[0010]

Embedded image A method for producing a yellow vat dye, the method comprising the step of heating and dissolving the compound produced after the reaction in an aqueous sulfuric acid solution, followed by cooling to precipitate crystals. .

Hereinafter, the present invention will be described in detail. A specific embodiment of the method of the invention is that the G
Dissolve CN in sulfuric acid and add water to adjust the ratio of sulfuric acid to water to 6
Prepare from 0:40 to 90:10. After further heating, the GCN is completely dissolved, and then slowly cooled to 40 ° C. or lower, and a crystal part is collected by filtration. Further, the crystal part may be stirred with an aqueous solution of sodium hypochlorite in order to clean the crystal part.

In the method of the present invention, there is no problem in using GCN in the sulfuric acid solution after the reaction as it is or using GCN extracted as a crystal. That is, the method of the present invention can also be used for GCNs isolated as dark red and dark blue.

In the method of the present invention, there is no problem with the concentration of sulfuric acid used as long as it can completely dissolve GCN.
Normally, the concentration may be 60% or more, though it depends on the amount used.

In the method of the present invention, the ratio of sulfuric acid to water after dissolving GCN is preferably adjusted in the range of 60:40 to 90:10, more preferably 80:20 to 90:10.

In the method of the present invention, the temperature for heating and dissolving GCN in sulfuric acid is usually 60 ° C. or higher, preferably 70 ° C. or higher.
° C or higher. Furthermore, at that temperature, the desired GCN
Is preferably not precipitated, but even if precipitated, it may be dissolved again by further raising the temperature.

The cooling temperature depends on the sulfuric acid concentration and the cooling start temperature, and there is no problem as long as GCN can be precipitated.

The cooling time varies depending on the cooling start temperature and is not uniquely determined, but is usually in the range of 1 to 24 hours.

[0018]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.

Example 1 600 g of 2,6-diaminoanthraquinone was suspended in 3600 g of o-chlorobenzene, and the temperature was raised to 40 ° C.
After dropping 920 g of benzoyl chloride, the temperature was raised to 150 ° C., and the reaction was carried out for 5 hours. Thereafter, the mixture is cooled to 30 ° C., 900 g of phosphorus trichloride is charged, and then 514 g of chlorine is blown in for 12 hours. After heating to 120 ° C and stirring for 2 hours, the mixture is cooled to 40 ° C. The crystal part is collected by filtration and washed with alcohol. To the crystals are added 2885 g of alcohol and 640 g of sodium hydrogen sulfide, and the mixture is stirred at 80 ° C. for 7 hours. 2000 g of water is added, and the crystal part is collected by filtration, washed with water, and dried. 973.8 g of the crystals of the thiazole precursor are dissolved in 4300 g of 98% sulfuric acid, and the mixture is stirred at 105 ° C. for 6 hours. By the above operation, the target compound can be synthesized.

658 g of water while maintaining the temperature at 80 ° C. or higher.
Is added dropwise to adjust the sulfuric acid concentration, and the temperature is raised to 130 ° C. to dissolve the target compound, followed by stirring for 30 minutes. Thereafter, it is cooled to 40 ° C. The precipitated crystals are collected by filtration, washed with water until neutral, and the filter cake is dried. This gives 550 g of a bright yellow GCN.

Example 2 30 g of red and dark GCN was added to 270 g of 98% sulfuric acid, and the mixture was heated to 105 ° C. and dissolved. Internal temperature 90 ~ 11
While maintaining the temperature at 0 ° C., 78 g of water is added dropwise to adjust the sulfuric acid concentration. After the temperature was raised to 130 ° C, the temperature was cooled to 40 ° C, and the precipitated crystals were collected by filtration. Washing with water until neutral and drying yields 25.5 g of bright yellow GCN.

Example 3 To 270 g of 98% sulfuric acid was added 30 g of dark red GCN, the temperature was raised to 105 ° C., and the mixture was stirred for 2 hours to dissolve. 9
After cooling to 0 ° C, water 4 was added to maintain the internal temperature at 90-110 ° C.
1 g is added dropwise. Thereafter, the temperature is raised to 130 ° C., and the mixture is dissolved with stirring for 30 minutes. After slowly cooling to 40 ° C., the crystal part is collected by filtration and washed with water until neutral.
This is suspended in 600 g of water, and the pH is adjusted to 11 to 12 with an aqueous NaOH solution while maintaining the temperature at 70 ° C. An aqueous solution of sodium hypochlorite is added until the potassium iodide starch paper turns purple. The temperature is raised to 95 ° C., stirred for 3 hours, and then cooled to 40 ° C. The crystal part is collected by filtration and washed with water until neutral. Drying gives 26 g of a bright yellow GCN.

Example 4 To 270 g of 98% sulfuric acid was added 30 g of bluish dark GCN, and the mixture was heated to 105 ° C. and stirred for 2 hours to dissolve. 9
After cooling to 0 ° C, water 7 was added to maintain the internal temperature at 90 to 110 ° C.
8 g are added dropwise. Otherwise, the same procedure as in Example 3 is carried out to obtain 22.5 g of bright yellow GCN.

Comparative Example 600 g of 2,6-diaminoanthraquinone was suspended in 3600 g of o-chlorobenzene, and the temperature was raised to 40.degree.
After dropping 920 g of benzoyl chloride, the temperature was raised to 150 ° C., and the reaction was carried out for 5 hours. Thereafter, the mixture is cooled to 30 ° C., 900 g of phosphorus trichloride is charged, and then 514 g of chlorine is blown in for 12 hours. After heating to 120 ° C and stirring for 2 hours, the mixture is cooled to 40 ° C. The crystal part is collected by filtration and washed with alcohol. To the crystals are added 2885 g of alcohol and 640 g of sodium hydrogen sulfide, and the mixture is stirred at 80 ° C. for 7 hours. Water 2
000 g is added, the crystal part is collected by filtration, washed with water, and dried. 973.8 g of the crystals of this thiazole precursor were added to 9
Dissolve in 4300 g of 8% sulfuric acid and stir at 105 ° C. for 6 hours. By the above operation, the target compound can be synthesized.

After cooling to 20 ° C. and washing with 2700 g of water while maintaining the temperature at 40 ° C. or lower, the precipitated crystals are collected by filtration. After washing with 2700 g of 49% sulfuric acid, 1000 g of water
Suspended in While maintaining the pH at 11 to 12, an aqueous sodium hypochlorite solution is added until the potassium iodide paper turns purple. After stirring at 95 ° C for 3 hours, it is cooled to 40 ° C. The crystal part is collected by filtration and washed with water until neutral. Drying gives 558 g of reddish dark GCN.

[0026]

According to the method of the present invention, anthraquinone thiazole compounds which are industrially extremely useful as yellow vat dyes can be obtained with high quality. That is, the present invention is an industrially efficient and extremely valuable method by which anthraquinone thiazole compounds can be obtained with high quality.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C09B 67/28 C09B 5/60

Claims (3)

(57) [Claims] 1. A method of reacting 2,6-diaminoanthraquinone with benzoyl chloride and sodium hydrosulfide to obtain a compound of the formula (1)
(Formula 1) A method for producing a yellow vat dye, comprising the steps of: dissolving the compound produced after the reaction in an aqueous sulfuric acid solution, followed by cooling to precipitate crystals. 2. The ratio of sulfuric acid to water after heat dissolution is 60: 4.
The method according to claim 1, wherein the ratio is 0 to 90:10. 3. The method according to claim 1, wherein the heat dissolution temperature is 60 ° C. or higher.