JPS6059263B2 - How to make dye insoluble in solvents - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for making dyes insoluble in solvents.

The present inventor conducted repeated studies to find a method for sufficiently rendering water-soluble pigments water-insoluble, and first, a condensation product of benzaldehydes and a polyhydric alcohol of 5 or more valences, a surfactant, water, and a water-soluble pigment were prepared. Mix the dyes, separate the resulting float,
We have found a method for making water-soluble dyes water-insoluble by drying the separated float. The water-insoluble dye obtained by this method is useful as a coloring material for general water-based paints and certain types of emulsion paints.

However, many general paints, such as paints, gravure inks, and offset inks, use solvents and oils, and even plastic colors that are mixed in need to be used in a heated state. be. . Therefore, solvent resistance is required for these uses, and if the solvent resistance is insufficient, so-called bleeding or migration will occur. The above-mentioned water-insoluble dyes developed by the present inventors are slightly soluble in solvents, so they are not sufficient for these purposes. Therefore, the inventors of the present invention further conducted extensive studies to make this dye insoluble in solvents, and as a result, they arrived at the present invention.

That is, the present invention mixes a condensation product of benzaldehydes and a polyhydric alcohol having a valence of 5 or more, a surfactant, water, and a water-soluble dye, and separates the resulting one-color float,
The separated float is then mixed with a polar solvent and an amino resin, the mixture is heated in the presence of a curing catalyst, and then
A method for insolubilizing a dye in a solvent, which is characterized by dispersing a reaction product in water and separating the resulting adhered float.

The present invention will be explained in detail below.

Benzaldehydes used in the present invention include benzaldehyde and its derivatives, and the derivatives include:
Methyl, ethyl, propyl, isopropyl or te
It may be a benzaldehyde having one or more substituents on the aromatic nucleus, such as an alkyl group such as rt-butyl, an alkoxyl group such as methoxy or ethoxy, a hydroxyl group, or a halogen atom, and specifically, for example, tolualdehyde, cinnamaldehyde, Cuminaldehyde, methoxybenzaldehyde, piperonal, chlorbenzaldehyde, p-
Oxymetamethoxybenzaldehyde and the like can be mentioned.

Preferably, sugar alcohols such as pentate, hexylate, etc. are used as alcohols having a valence of 5 or more, and specifically, xyrite, arabite, adonite, sorbitol, etc.
Examples include mannitol, idisite, and talitz, but generally, xylitol and sorbitol are most preferably used because of their ease of availability. Further, among these derivatives, those having a substituent that does not cause a problem in the condensation reaction with aldehydes can also be used. In the reaction of benzaldehydes and polyhydric alcohols, various known methods used for conventional condensation reactions of aldehydes and alcohols may be applied, and the reaction is usually carried out as follows.

Benzaldehyde and a polyhydric alcohol are mixed in the presence or absence of a solvent using an inorganic acid such as sulfuric acid, hydrochloric acid, or phosphoric acid or an organic acid such as benzenesulfonic acid or valatoluenesulfonic acid as a catalyst, preferably under dehydration conditions. It is done by heating. The higher the reaction temperature, the higher the reaction rate tends to be, but there is no particular restriction on the reaction temperature, and it may be selected depending on each case. Usually, it is sufficient to select from the range of 100 to 250°C. The molar ratio of benzaldehyde and polyhydric alcohol can be varied as long as one does not become excessively large, but generally a ratio of about 2:1 gives the best results. The condensation reaction product is treated with an organic solvent such as methanol and/or
Alternatively, by treatment with hot water, unreacted products, water, and acid catalyst are removed and isolated, and obtained as a solid or powder. The condensation product used in the present invention is preferably in the form of fine powder from the viewpoint of dispersibility in water.

In addition, some of the polyhydric alcohols with a valence of 5 or more are glucose,
Substantially similar results can be obtained even when sugars such as galactose, mannose, fructose, maltose, lactose, sucrose, and dextrin are used in combination.

Ionic surfactants are mainly used in the present invention.

Nonionic materials can be used in combination with ionic materials, for example, when dispersion and emulsification are poor when using ionic materials alone. The ionic surfactant is preferably selected in accordance with the type of aqueous dye solution to be treated. More specifically, as an anionic activator, polyoxyethylene ether obtained by adding ethylene oxide to sodium alkyl sulfate, sodium amide sulfate, higher alcohol, alkylphenol, or alkylolamide, etc. is esterified with sulfuric acid, and then Glycol ether type sulfates obtained by neutralization, sodium alkyl sulfonates, sodium alkylaryl sulfonates, sodium amidosulfonates, etc. can be mentioned, and examples of cationic activators include higher alkyl sulfates such as dodecyl and hexadecyl. trimethylammonium chloride having a group or a higher alkenyl group such as octadecenyl or octadecadienyl, dimethylammonium chloride having two of the above groups,
Examples include quaternary ammonium chloride in which any one of the above long carbon chain substituents is partially substituted with a glycol ether bond, or an acetate amine salt type such as substituted imidazoline acetate; Examples of surfactants include various types having amine groups, quaternary ammonium groups, etc. as cationic active groups, and salts of carboxylic acids, sulfonic acids, sulfuric esters, etc. as anionic active groups as partial structures. It will be done. Furthermore, the water used together with the above-mentioned condensation product and surfactant in the present invention may also contain a small amount of a hydrophilic solvent, such as an alcohol.

On the other hand, the dye to be insolubilized may be various water-soluble dyes such as food dyes, natural dyes, and synthetic dyes. For example, the following food colors are allowed: Red No. 2 (Amaranth), Red No. 3 (Erythrosine), Yellow No. 4 (Tartrazine), Green No. 3 (Fast Green FCF), Blue No. 1 (Brilliant Blue FCF), and β-1. Examples include carotene, water-soluble annatto, iron chlorophyllin salts, copper chlorophyll, copper chlorophyllin salts, and the like. Other natural pigments include various carotenes, lycopenes, crocetins,
Examples include chlorophylls and plant component flavone glycosides. Furthermore, synthetic dyes include water-soluble ones such as direct dyes, acid dyes, basic dyes, cationic dyes, mordant dyes, acidic/mordant dyes, and reactive dyes.
For example, various water-soluble azos can be mentioned.

Copper complex azo dyes, water-soluble anthraquinone dyes or phthalocyanine dyes, diphenylmethane or triphenylmethane dyes, thiazine dyes, etc. are used.
These may be used singly or in mixed colors, and are usually used in powder form. The above condensation product, surfactant, water and water-soluble dye are mixed, for example, as follows.

The condensation product, surfactant and water-soluble dye are mixed and water is added.

The mixing of these four components is preferably carried out by heating and holding approximately 5 to 3 powders while stirring.

The temperature for heating is usually selected from about 40 to 100°C, preferably 60 to 8°C. The amounts of these four components used vary depending on the case, but usually the weight ratio of condensate: surfactant: water: water-soluble dye is 5 to 50:15.
Selected from the range of 50:15 to 50:0.1 to 50. In this way, by mixing the four components, an aqueous dispersion of colored float is obtained, which is further mixed with 0.
By leaving the mixture to mature for about 5 to 30 hours, the colored dregs can be easily separated. The colored scum is then separated from house to house, and usually thoroughly washed with hot or cold water.

Drying can be performed by a conventional method, if necessary. The resulting colored float is then mixed with a polar solvent and an amino resin.

Examples of polar solvents include dimethylformamide, N-alkylamides such as N-methylpyrrolidone, nitriles such as acetonitrile, dimethylsulfoxide,
Dulfoxides such as sulfolane, ethyl cellosolve, methyl cellosol. Specific examples include cellosolves such as alcohol, alcohols such as methanol, ethanol, isopropanol, and butanol, and ketones such as acetone. It may take shape.

Examples of the amino resin include melamine resin, area resin, benziguanamine resin, aniline resin, and co-condensed resins thereof.

The amount of these three components used is usually a weight ratio of colored float: polar solvent: amino resin (solid content) of 0.1 to 5:
5 to 100: selected from the range of 0.5 to about 100 ml. The mixture is heated and dissolved together with the catalyst to form a colored solution, which is subjected to the reaction while being shaken or stirred.

As the catalyst, those commonly used as curing agents for amino resins are preferably used.

Examples include various ammonium salts such as ammonium chloride, ammonium phosphate, ammonium thiocyanate, ammonium oxalate, and sulfonic acid amides. Furthermore, the present invention can be advantageously achieved by using an alkyl titanate, alkyl aluminum, or the like as a cocatalyst together with the above catalyst.

In this case, the above-mentioned catalyst and co-catalyst can be used at the same time, but it is preferable to first conduct the reaction in the presence of the catalyst for a predetermined period of time, then add the co-catalyst and continue the reaction. .

The amount of the catalyst used is about 0.5 to 30 W't%, preferably 5 to 15 Wt%, based on the dye, while the amount of the co-catalyst used is preferably 1 to 30%, based on the catalyst. 5-1
It is about 5wt%.

The heating temperature is usually about 60 to 100°C, preferably 70°C.
The temperature is selected from about 80°C.

Moreover, the reaction time is usually selected from about 1 hour to about 1 hour. The reaction product is then poured into water and stirred. In this case, the amount of water is usually 10-5% of the reaction product.
diameter, preferably selected from 15 to 25 f8. As a result, the colored dregs are dispersed in water, and then the dregs are separated by filtration, centrifugation, or the like. The obtained dregs are thoroughly washed with hot and cold water and then dried by a conventional method, but it is preferable to dry with hot air at about 80 to 120° C. for 1 to 3 hours.

Although the dried dregs may be used as it is depending on the case, it is usually preferable to crush it and use it in the form of powder. The solvent-insolubilized pigment bodies thus obtained can be used for a variety of purposes including coloring, such as printing inks, copier toners, paints, plastic colorants, etc., as is commonly known as the use of pigments. Various conventional methods may be used.

As detailed above, according to the present invention, it is possible to easily obtain solvent-insolubilized pigments from water-soluble pigments, and it is possible to easily obtain solvent-insolubilized pigments from water-soluble pigments. By applying the present invention, stable solvent-insolubilized plastids can be obtained with simple operations without any alteration, and the color density of the plastids can be changed by adjusting the amount of the dye. Furthermore, by mixing a plurality of pigments, the hue or saturation of the pigment body can be relatively freely changed and adjusted, which is extremely advantageous.

Further, since the specific gravity is approximately constant, the bulk of the produced insolubilized product is constant, which is extremely advantageous in terms of workability and packaging. Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited by the following Examples unless it exceeds the gist thereof.

In addition, in the examples.

Parts indicate parts by weight. Example 1 was thoroughly mixed, and further a cationic activator 0 Arcard C5O Shunbu (manufactured by Nippon Oil & Fats Co., Ltd.) was added, and then (1) part of warm water was added and mixed.

The temperature was gradually raised to a slight boil at about 80°C, held for 5 minutes, and then left for 1 hour. Next, the colored dregs were separated, washed with water, and dried to obtain a red water-insoluble powder.

1 part of water-insolubilized erythrosin thus obtained,
(manufactured by Nihon Kagaku Kogyo Co., Ltd.) is placed in a round flask equipped with a reflux condenser and heated.

After about 3 puffs at a temperature of about 60-70C, the mixture is completely dissolved. The color solution is maintained at a temperature of 70-80° C. with occasional stirring for about 20 minutes. Next, alkyl titanate (manufactured by Nippon Soda Co., Ltd.) “Alkyl titanate B-
0.01 part of r゛) was added, and the mixture was further reacted with one powder.

Claims (1)

[Claims] 1. Mix the condensation product of benzaldehydes and a polyhydric alcohol with a valence of 5 or more, a surfactant, water, and a water-soluble dye, separate the resulting colored float, and then separate the separated float. Solvent-insolubilizing the dye by mixing it with a polar solvent and an amino resin, heating the mixture in the presence of a curing catalyst, dispersing the reaction product in water, and separating the resulting colored float. Method.