JPS6058263B2 - Disazo dye solution composition - Google Patents

Description

[Detailed description of the invention] Enni.

1 (TEL shi～～■.R.

(In the formula, R,,R.

and R. each independently represents hydrogen or a hydroxyalkyl group having 2 to 3 carbon atoms
ι≧0 (I) The present invention relates to stable concentrated aqueous solution compositions of novel blue disazo dyes.

The blue disazo dye in the present invention has the general formula (I) □□2
〉------[nie:jtraI:;T nee ni ni ni 4.

To. (I) It is expressed as

Heretofore, the blue disazo dye of the general formula (■) has been commercially available and put to practical use in the form of a finely ground sodium salt and, in some cases, in the form of a blend with suitable diluents and auxiliaries.

However, it is well known that these dye powders have many disadvantages in terms of public health, work efficiency, and quality control of dyed products. For this reason, it is desired to develop a highly concentrated and highly stable aqueous solution composition for a bright blue direct dye, which is in high demand in the paper manufacturing industry and other industries. However, due to its properties and manufacturing method, it is difficult to prepare a solution composition of this type of blue direct dye that has a satisfactory concentration and is stable for storage. It has not been put into practical use, and no solution has yet been found. The dye solution composition of the present invention is a highly concentrated fluid liquid that is completely stable on storage, completely overcoming the drawbacks mentioned above.

This allows the dye to be measured by volume and can be diluted with cold water at any ratio, making it possible to avoid complicated operations during use. Moreover, the dye does not scatter at all, and furthermore, the dye is already in a completely solution state.
When using the compositions of the invention, the risk of incomplete dyeing due to undissolved dye stains is avoided. Thus, the present invention has realized an ideal dye solution composition that is completely different from the conventional dye solution composition. According to the research of the present invention, by converting two or more of the acid groups constituting the blue disazo dye of the general formula (■) into an amine salt as shown in the general formula (1), other dyes can be dyed. It is uniquely hydrophilic and easily soluble compared to metal salts such as sodium and potassium salts alone. It has been found that the properties and stability can be increased.

According to the present invention, an ideal pure dye component 1 that is completely different from the conventional one
Very stable blue disazo dye aqueous solutions can be obtained at high concentrations containing 0-40%. Examples of aminonaphthol disulfonic acids that can be used as a force/coupling component for producing the blue disazo dye of the present invention include 1-amino-8-naphthol-3,6-disulfonic acid (H acid), 1
-Amino-8-naphthol-2,4-disulfonic acid (S
S acid) etc.

Examples of hydroxyalkylamines having 2 to 3 carbon atoms include monoethanolamine, diethanolamine, triethanolamine, 3-propanolamine, 2-propanol aamine, dipropanolamine, and tripropanolamine. The blue disazo dye used as dye component in the novel concentrated aqueous solutions of the invention can be prepared using methods known per se.

For example, basically and advantageously 1 mol of dianisidine is tetrazotized and then 2 mol of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (H acid) of a hydroxyalkylamine salt, especially a triethanolamine salt, or 2 mol of a triethanolamine salt or A desired hydroxyalkylamine salt is produced by coupling with a hydroxyalkylamine salt of 1-amino-8-hydroxynaphthalene-2,4-disulfonic acid (SS acid) and a mixture of the above compounds, and this is directly used to form a dye solution composition. It can be a thing.

Alternatively, the blue disazo dyes described above can be prepared by dissolving the corresponding sodium salt in water, precipitating with hydrochloric acid or sulfuric acid, and adding the appropriate hydroxyalkylamine to the resulting wet cake of free acid to obtain the desired hydroxyalkylamine. It can also be obtained by making it with salt. The novel hydroxyalkylamines thus obtained exhibit markedly increased water solubility compared to known sodium, lithium or potassium salts, and have high concentrations of blue disazo dyes ranging from 10 to 4% by weight. It is possible to obtain stable aqueous solutions containing.

The dye solution composition according to the present invention may further contain various additives known to those skilled in the art, if necessary, such as glycols such as ethylene glycol and diethylene glycol, alcohols such as isopropyl alcohol, dioxane, Water-soluble organic solvents such as dimethyl sulfoxide, formamide, tetrahydrofuran, glycol monoalkyl ethers, acid amide compounds such as urea, alkylurea, E-calactam, diethylamine, triethylamine, diethanolamine, triethanolamine, propanolamine, ethyldiethanolamine and other aliphatic amines, various surfactants, antifoaming agents, etc. Such supplementary additives will be appropriately selected by those skilled in the art depending on the end use. The blue disazo dye concentrated stable solution composition according to the present invention not only dyes various natural or synthetic celluloses, such as paper, cotton, etc., but also dyes natural or synthetic polyamide materials such as silk, wool, polyamide fibers, leather, etc. in bright blue color. Can be used to dye
It can also be used as felt-tip pen ink.

The present invention will be specifically explained with reference to the following examples.

In the description, parts indicate parts by weight. Example 1 4,4′-diamino-3,3-dimethoxydiphenyl (
Anisidine) 24.4 parts (0.10rr101e) were thoroughly stirred with 50 parts of water and 45.2 parts of hydrochloric acid (d=1.18), and then 30% NaNO
Tetrazotization was gradually carried out using 46 parts of 2 solution.

The mixture was stirred for about 2 hours, optionally clarified by removing small amounts of impurities, and excess nitrous acid removed using sulfamic acid. Then 1-amino8
-Hydroxynaphthalene-3,6-disulfonic acid monosodium salt (H acid) 681 parts (a). 2rr101e)
To a solution consisting of 100 parts of water and 10 parts of triethanolamine were added 10 parts of urea and 100 parts of water to bring the temperature to below 0°C, and the tetrazonium salt solution obtained above was added dropwise at 0 to 5°C.

After stirring this mixture at 15° C. or below until the reaction is completed, water is added to bring the total amount to 8 (1) parts. A concentrated liquid composition can be obtained by removing a small amount of undissolved matter. This composition has a dye content of the formula: 15. Contains 100% slag weight.

This dye can be diluted with cold water at any ratio, and no deterioration was observed even after storage for 6 months (in contrast, conventional sodium salt dyes have a 1.0
% by weight, and even at 80° C. it dissolves only 4% by weight). The above composition is diluted with water and used as a stock solution to continuously dye bulbs to obtain a bright blue paper product. Additionally, 1-amino-8-hydroxynaphthalene-2.4 was used instead of the 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (H acid) used above.
Even if disulfonic acid (SS acid) is used in an equimolar amount, a highly concentrated and stable dye solution composition similar to the above can be produced, and when a bulb is dyed in the same manner as above, it produces a clear blue color with a slight greenish hue. paper products were obtained.

It also has good level dyeing properties. Example of Use 1 Add 0.3 of the dye solution obtained in Example 1 into 3 (9) parts of the bulb solution of LBKP3Of/e with freshness of 25 sR (7).
After stirring thoroughly for 10 minutes, add 0.1 part of a sizing agent, add 0.3 part of anhydrous aluminum sulfate after one powder, and continue stirring for one powder to dye.

When this is made into paper, a paper with a clear blue color and excellent level dyeing properties is obtained. Use example 2 5 parts of viscose rayon thread was introduced into a solution prepared by diluting 0" part of the dye solution obtained in Example 1 with 250 cc of water.
The temperature is raised to 85°C, and anhydrous sodium sulfate is added after 1 coat to dye 4 coats.

When the dyed thread is washed with water, a blue dyed product with excellent level dyeing properties is obtained. Example 2 A concentrated liquid composition containing the diethanolamine salt of the direct dye represented by Example 2 is prepared as follows.

The sodium salt of the direct dye of the above formula prepared by known methods is dissolved in water and sulfuric acid is added to give PHL. 5, and when the precipitate was washed with water, the free acid form of the dye was 95%.
190 parts of a wet cake are obtained containing 50%. After adding 31.5 parts of diethanolamine and 7 parts of ethylene glycol, water was added to bring the total amount to 3 (1) parts, stirring was continued at room temperature for 1 hour, and undissolved portions of horseradish were removed. Dye of the above formula 40. A thick liquid composition is obtained containing % vol. As a result of testing in the same manner as Example 1,
It could be diluted with cold water at any ratio, and no deterioration was observed even after storage for 6 months. When this dye solution composition is used as a raw material for ink for ballpoint pens and felt-tip pens, it produces a stable bright blue ink with a density not found in other inks.

Example 3 A concentrated liquid composition containing the monoethanolamine salt of the direct dye represented by Example 3 is prepared as follows.

The sodium salt of the direct dye of the above formula prepared by known methods is dissolved in water and hydrochloric acid is added to give PHL. 5 and washing the precipitate with water gives 185 parts of a wet cake containing 95 parts of the dye in the free acid form.

After adding 20.0 parts of monoethanolamine, 3 parts of urea, and 15 parts of E-caprolactam, water was added to bring the total volume to 300 W), stirring was continued at room temperature for 1 hour, and insoluble components of horseradish were removed. do. 38. Dye of the above formula. A thick liquid composition is obtained containing 10% slag. As a result of testing in the same manner as in Example 1, it was found that the product could be diluted with cold water at any desired ratio, and no deterioration was observed even after storage for 6 months.

Usage example 3 After washing the chrome-rolled leather with water and reducing the squeezing rate to 100% with a mangrora, the 20W) of it was mixed with 1 part of water in a drum.
00m and 0.4 parts of sodium bicarbonate for 5 minutes.

After rinsing with water for 2 minutes, 1 (1) part of water and 0.1 part of the dye solution composition obtained in Example 3 were added, and 45 to 50
Stain three times at ℃.

Claims (1)

[Claims] 1 General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1, R_2 and R_3 each independently represent hydrogen or a hydroxyalkyl group having 2 to 3 carbon atoms) A concentrated aqueous solution of a blue disazo dye.