JPS6261623B2 - - Google Patents

Description

[Detailed Description of the Invention] The present invention is based on the formulas (), (), () and (). (In the formula, R represents H, CH ₃ or OCH _3. ) The present invention relates to a dye solution composition using a dye obtained by reacting one or a mixture of the dyes represented by with methylolsulfonic acid and/or monochloroacetic acid.

The present inventors achieved the present invention with the aim of obtaining a stable, highly concentrated solution of a black direct dye.

In general, liquid dye products are more expensive than powdered products.
Although it is already well known that this liquid product has various advantages in use, various difficulties are involved in obtaining this liquid product. In particular, the important conditions required in this case are that the dye content is high, that is, that it is sufficiently concentrated and that it remains stable and homogeneous over time, including changes in temperature, etc. Conventionally, various methods have been proposed for preparing liquid compositions of anionic dyes, but among anionic dyes, direct dyes, especially black dyes, generally have low water solubility, and without exception, these dyes are Because they contain amino groups in their molecular structures, when liquid compositions of these dyes are stored for long periods of time, they deteriorate due to oxidation, etc., leading to undesirable results such as increased viscosity, decreased concentration, and formation of precipitates. It is requested.

The present inventors attempted to improve the dyes represented by the formulas (), (), (), and (), which are frequently used as direct black dyes, by treating these dyes with methylolsulfonic acid and/or monochloroacetic acid. The dye obtained has amazing hydrophilicity and easy solubility that are not found in untreated raw material dyes, and it was discovered that the liquid form of the dye itself is stable for a long time, leading to the present invention. .

Next, the method of the present invention will be specifically explained. The dyes shown in the general formulas (), () and () are CI
Direct Black 19.CI35255, CIDirect Black17.
They are known as CI27700, CIDiret Black 22.CI35435, and their manufacturing methods are for example
It is described in detail in FP245557, FIAT, 764, etc. Also expression () (In the formula, R represents H, CH ₃ , OCH _3. ) Among the dyes shown, those with R = H are CIDirect
It is famous as Black 38.CI30235, and its manufacturing method is detailed in FIAT764, etc., and R=
CH ₃ and R=OCH ₃ can also be easily produced using the same method. When using these dyes to carry out the present invention, the commercially available products mentioned above may be used, but it is also possible to use pastes obtained in the dye manufacturing process or highly concentrated products obtained by spray drying or the like. The reaction between these dyes and methylolsulfonic acid or/and monochloroacetic acid is carried out by reacting methylolsulfonic acid (HOCH ₂ SO ₃ H ) or an aqueous solution of sodium methylolsulfonate or monochloroacetic acid (Cl.
This can be easily carried out by adding CH ₂ COOH).

The dye solution composition using the thus obtained dye according to the present invention can be prepared using a known method, that is, a concentrated dye solution obtained as described above, or a paste obtained by extracting and purifying the concentrated dye solution using a known method, or Water and/or an organic hydrophilic solvent as well as surfactants, antifoaming agents, etc. are added to the powder.
Namely, glycol, glycol monoalkyl ether, isopropyl alcohol,
Water-soluble organic solvents such as dioxane, dimethyl sulfoxide, dimethyl formamide, formamide, tetrahydrofuran, and dimethyl acetamide, polyamino or hydroxy compounds such as urea, alkylurea, dextrin, alkyl cellulose, and glycerin, various surfactants and antifoaming agents, and antifoaming agents. Agents, dyes, etc. may also be included.

The dye solution composition according to the present invention can be applied to paper, cotton, linen,
It is valuable for use in dyeing silk, leather, and other miscellaneous goods, and especially for ballpoint pen ink.

Next, the effects of the present invention will be illustrated by Examples, but the present invention is not limited to the Examples.

Example 1 Formula () 100 g of a commercially available dye (solubility in water about 2%) consisting of 42 g of the dye represented by and a diluent (mainly sodium chloride and anhydrous sodium sulfate) are added to 200 ml of water and heated to 50-55°C. Separately, 11g of sodium acid sulfite, 10g of 30% formalin aqueous solution
Add a sodium methylolsulfonate solution prepared by heating g and 50 ml of water at 60-65°C for 30 minutes, and stir at 50-55°C for 2-3 hours. A deep black aqueous solution is obtained. It can no longer be precipitated by salting out, is stable for more than 6 months, and is useful as a coloring agent for leather, pulp, etc.

Example 2 Commercial dye similar to that used in Example 1
Add 100g to 400ml of water and heat to 70-75°C. After adding 7 g of soda ash, gradually add 10 g of monochloroacetic acid and stir for 2 to 3 hours to make it alkaline. The obtained black concentrated liquid was concentrated and dried, and then purified by a known method to obtain 50 g of black dye powder.

A black solution obtained by mixing and dissolving 10 g of this black powder with 70 g of water and 30 g of ethylene glycol colors paper, has excellent water resistance, and is stable without increasing viscosity for more than 6 months.

In addition, ballpoint pen ink is prepared as follows.

Black powder 8g Glycerin 5g Ethylene glycol 5g Diethylene glycol 10g Prysurf A212E 0.5g (Daiichi Kogyo Seiyaku surfactant) Butyl paraoxybenzoate 0.1g Water 71.4g The ink prepared in this way is stable for more than 6 months. be. In the case of the ink using this formulation and the dye of formula () instead of the black powder, gelation occurred in 4 weeks.

Example 3 Formula () 100 g of a commercially available dye (solubility in water 1%) consisting of the dye represented by and a diluent are added to 400 ml of water and heated to 70-75°C. Add 100 g of an aqueous solution containing 27 g of sodium methylolsulfonate, and stir at the same temperature for 4 to 5 hours until the reaction solution is dissolved. This solution is stable for over 6 months and is suitable for leather,
Useful for coloring pulp, paper, etc.

Example 4 100 g of commercially available dye similar to that used in Example 3
Add to 400ml of water and heat to 70-75℃. After adding 14 g of soda ash, gradually add 20 g of monochloroacetic acid and stir for 2 to 3 hours to make it alkaline. The obtained black solution was salted out to remove the dye, and purified by a known method to obtain 60 g of black powder.

The ink obtained by mixing and dissolving 10 g of this black powder with 70 g of water and 30 g of ethylene glycol colors paper, has good water resistance, and is stable for more than 6 months.

In addition, ballpoint pen ink is prepared as follows.

Black powder 10g Water 62.5g Ethylene glycol 14g Thiodiglycol 13g Sodium pentachlorophenol 0.5g The ink thus prepared is stable for more than 6 months. In the case of the ink using this formulation and the dye of formula () instead of the black powder, gelation occurred in 4 weeks.

Example 5 Formula () 100g of spray-dried product containing 40g of the dye indicated by
Add to 300ml of water and heat to 50-55℃. Add 50 ml of an aqueous solution containing 6.8 g of sodium methylolsulfonate and stir at the same temperature for 5 to 6 hours. A concentrated dye solution is obtained. It is stable for more than 6 months and is useful for coloring leather, pulp, paper, etc.

Example 6 Formula () 200 g of spray-dried product containing 118 g of the dye indicated by
Add to 500 ml of water, heat to 50-55°C, add 100 g of an aqueous solution containing 27 g of sodium methylolsulfonate, and stir at the same temperature for 4-5 hours to dissolve. A thick black solution is obtained. Stable for more than 6 months,
Useful for coloring paper, cotton cloth, etc.

Example 7 Commercially available dye containing 42g of dye represented by formula ()
Add 100g of commercially available dye containing 48g of dye represented by formula () to 600ml of water, heat to 50-55℃, add 150g of an aqueous solution containing 40g of sodium methylolsulfonate, and stir at the same temperature for 4-5 hours. . The resulting black solution is stable for more than 6 months,
Useful for coloring paper, pulp, cotton, etc.

Example 8 Commercially available dye containing 42g of dye represented by formula ()
100 g of a commercially available dye containing 48 g of the dye of formula () are added to 800 ml of water and heated to 70-75°C. After adding 21g of soda ash, 30g of monochloroacetic acid was gradually added, and the alkaline solution was heated to the same temperature for 2 hours.
Stir for ~3 hours. After concentration and drying, it was purified by a known method to obtain about 110 g of black powder.

This is useful for coloring paper, pulp, etc., and especially for ballpoint pen inks.

Example 9 Formula () 100g of spray-dried product containing 40g of the dye indicated by
A stable thick black solution is obtained using a method similar to that shown in Example 5.

This is useful for coloring paper, pulp, miscellaneous goods, etc.

Claims (1)

[Claims] 1 Formula (), (), () and () (In the formula, R represents H, CH ₃ or OCH _3. ) A dye solution composition comprising a dye obtained by reacting one or a mixture of the dyes represented by with methylolsulfonic acid and/or monochloroacetic acid.