JPS6041095B2 - Method for making water-soluble dyes insoluble in solvents - Google Patents

Description

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

The present inventors have conducted repeated studies to find a method for sufficiently rendering water-soluble pigments water-soluble.
Condensation products with polyhydric alcohols with higher valences, surfactants,
By adding an emulsion breaker to a colored liquid in which a mixed solution of a polar solvent and a water-soluble dye is dispersed in water, separating the colored birch particles that are produced, and drying the separated floating particles. We have discovered a method to make water-soluble dyes water-insoluble.

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 common paints, such as paints, gravure inks, and offset inks, use oil as a solvent, and even plastic colors must be used in a heated state. 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 present inventor further aimed to make this water-soluble dye insoluble in a solvent.
As a result of extensive research, we have arrived at the present invention.

That is, in the present invention, an emulsion breaker is added to a colored liquid in which a mixed solution of a condensation product of benzaldehydes and a polyhydric alcohol having a valence of 5 or more, a surfactant, a polar solvent, and a water-soluble dye is dispersed in water. The colored floats formed are then separated, the separated floats are mixed with a polar solvent and an amino resin, the mixture is heated in the presence of a curing catalyst, and the reaction product is then dissolved in water. A method for making a water-soluble dye insolubilized in a solvent, the method comprising dispersing the dye in a solvent and separating the resulting colored float.

The present invention will be explained in detail below.

Penzaldehydes used in the present invention include benzaldehyde and its derivatives, and the derivatives include:
Methyl, ethyl, propyl, isopropyl or
It can be a penzaldehyde having one or more substituents on the aromatic nucleus, such as an alkyl group such as t-butyl, an alkoxyl group such as methoxy or ethoxy, a hydroxyl group, or a halogen atom, and specifically, for example, tolualdehyde, cinnamaldehyde. , cuminaldehyde, methoxybenzaldehyde, piveronal, chlorbenzaldehyde, P-
Oxymethane methoxy. Examples include sibenzaldehyde and the like.

Further, as the alcohol having a valence of 5 or more, bran alcohols such as benzite and hexite are preferably used, and specifically, xyrite, arabite, adonite, sorbitol,
Examples include mannitol, digit, and talit, 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 any hindrance to the condensation reaction with aldehydes can also be used. In the reaction of penzaldehydes 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.

Preferably, penzaldehyde and a polyhydric alcohol are dehydrated 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 paratoluenesulfonic acid as a catalyst. This is done by heating under certain conditions. 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 squares. The molar ratio of penzaldehyde and polyhydric alcohol can be varied as long as one is not 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. In addition, some of the polyhydric alcohols with a valence of 5 or more include glucose, galactose, mannose, fructose,
Almost the same results can be obtained even if maltose, lactose, lactose, etc., and bran such as 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, examples of anionic activators include polyoxyethylene ether obtained by adding ethylene oxide to sodium alkyl sulfate, sodium amide sulfate, higher alcohol, alkylphenol or alkylolamide, etc. Examples of the cationic activator include glycol ether type sulfates obtained by esterification with sulfuric acid and subsequent neutralization, sodium alkylsulfonates, sodium alkylarylsulfonates, and sodium amidosulfonates. , trimethylammonium chloride having a higher alkyl group such as dodecyl or hexadecyl or a higher alkenyl group such as octadecenyl or octadecagenyl;
Dimethylammonium chloride having two of the above-mentioned groups, quaternary ammonium chloride in which any one of the above-mentioned long carbon chain substituents is partially substituted with a glycol ether bond, or substituted imidazoline acetate, etc. Examples of amphoteric surfactants include amino groups, quaternary ammonium groups, etc. as ionic active groups, and carboxylic acids, sulfonic acids, and sulfuric acid esters as anionic active groups. There are various types of salts having salts such as these as a partial structure. Next, as polar solvents, dimethylformamide, N-alkylamides such as N-methylpyrrolidone, nitriles such as acetonitrile, sulfoxides such as dimethyl sulfoxide and sulfolane, cellosolves such as ethyl cellosolve and methyl cellosolve, Specific examples include alcohols such as methanol, ethanol, isopropanol, and butanol, and ketones such as acetone, and may also be in the form of a hydration liquid containing a small amount of water. . On the other hand, the pigment to be insolubilized in the present invention can be a variety of water-soluble pigments such as food pigments, natural pigments, and synthetic dyes, but especially natural pigments and food pigments that easily change quality and discolor during processes such as concentration and powderization. The advantages of the present invention are more clearly exhibited in the treatment of.

For example, Red No. 2 (amaranth), Red No. 3 (erythrosin), Red No. 102 (
Newcoxin), Red No. 103 (Eosin), Red 1
No. 04 (Phloxin), Red No. 105 (Rose Bengal), Red No. 106 (Acid Red), Yellow No. 4 (Tartrazine), Yellow No. 5 (Sunset Yellow FCF), Green No. 3 (Fast Green FCF), Blue 1 No. (Brilliant Blue FCF), Blue No. 2 (Indigo Carmine)
, Purple No. 1 (acid violet group), 3-carotene, water-soluble phanato-, iron chlorophyllin salt, copper chlorophyll, copper chlorophyllin salt, etc., but various dyes other than those permitted, such as acidic The pigments are Ponceau 3R, Ponceau SX, Ponceau R,
Orange 1, Naphtolo Yellow S', Guinea Green B
, Light Green SF Yellow □, Azur Blue-VX, Azorubin, Acid Fast Red, Ponsot-Kai, Orange Lo, etc., and basic pigments include Rhodamine R, Auramine, Malachite Green, Methyl Violet,
Diamond green, methylene flue, crystal violet, etc. are preferably used, and as the direct dye, direct deep black etc. are preferably used. Other natural pigments include various carotenes, lycopenes, crocetins,
Examples include chlorophylls and plant component flavone glycosides. These may be used singly or in a mixture of several types to match the color, and are usually used in their unpowdered state.

The above condensation product, surfactant, sacrificial solvent, and water port dye are mixed, for example, as follows.

A polar solvent and a surfactant are mixed, and a condensation product and a water-soluble dye are added.

Next, in order to form a mixed solution, it is preferable to heat the mixture, bringing it to a slight boil and holding it for about 5 to 10 minutes, and then gradually dispersing it in hot water.

After a while, the viscosity increases and a stringable colored liquid is formed. This is carried out for about 5 to 30 hours, preferably 10 to 30 hours.
Leave to mature for 24 hours. Thereafter, when an emulsion breaker is added as described below, the colored particles are immediately separated and can be separated from a colorless and transparent liquid layer. This will be explained in more detail below.

Since the condensation product is difficult to dissolve even in a magnetic solvent at room temperature, it is desirable to heat the mixture containing the four components described above.

During this heating, not only is the condensate dissolved, but even after the condensate has been dissolved to obtain a homogeneous solution containing the four components,
It is preferable to continue heating. The temperature during the heating is usually selected from the range of 40 qo to the boiling point of the polar solvent, more preferably 50 to 150 oo, most preferably 80 to 120 oo. The amounts of these four components used vary depending on the case, but the weight ratio of condensate: surfactant: polar solvent: water-repellent dye is usually 5 to 50:15 to 50:15.
50: It is sufficient to select from the range of 0.1 to 50.

Water-soluble dyes can be made immovable to the same extent as condensates, but
Since the solubility of water-soluble dyes in polar solvents differs, undissolved fine powder dyes are adsorbed as they are and become insolubilized, resulting in a blackish color. Therefore, in order to obtain a vivid color, the dye must be compared to the condensation product. 5-20%
is the most preferred.

Next, the mixed solution thus obtained is dispersed in water to obtain a colored liquid.

A mixed solution of four components usually has the ability to gel a large amount of water in a small amount, so when dispersing this solution into water, it is necessary to stabilize the system, and the power required for the rope is There is a tendency that the lower the temperature of the water serving as the dispersion medium, the larger the value becomes.

Therefore, the water used as the dispersion medium is preferably at least warm water at room temperature or higher, and industrially it is most preferable to use warm water with a temperature of about 60 to 8,000. 4 above into the water like this
Since the water will at least partially gel when a mixed solution containing the components is supplied, a strong rope is required to uniformly disperse the solution, preferably a key having the ability to crush solids. Azusa: A homogenizer, now known as an emulsifying machine, performs a strong rope attack, or a high-speed slurry that causes cavitation. Specifically, 20 enemies. p.
m. Above, preferably 300 to 1000. p. m. A rotation speed within the range of is selected. Also, the loss frame using ultrasonic irradiation is extremely effective. The amount of the four components in the colored liquid is usually about 0.01 to 1.5% by weight, more preferably 0.1 to 10%, most preferably 1 to 7% in terms of solid content. selected from the range. Below the lower limit of the widest range, the colored liquid may become an emulsion that no longer exhibits stringiness or a solution state, and when the upper limit is exceeded,
It is impractical because it puts too much stress on the process of uniformly dispersing the ingredients into water. Thus, although the details of the colored liquid in which the above four components are uniformly dispersed in water are still unknown, it is a type of colored hydrosol in which the condensate is colored with a water-soluble dye and is an extremely fine colloid. It is believed that there is a liquid, which is characterized by a viscous colored liquid, and when this composition is divided into two parts, for example, after penetrating the tip of a rod into this composition,
When lifted upwards, it has an extremely strong threading ability, pulling a strong thread of 20 skins or more and resisting splitting.

An emulsion breaking agent is then added to the colored liquid to further break up the hydrosol and separate the colored condensate.

As the emulsion breaking agent to be added, so-called emulsion breaking agents such as alcohols, ionic activators, acids, alkalis, and salts can be used.

For example, examples of the alcohol include lower alcohols such as methyl alcohol, ethyl alcohol, and inpropyl alcohol. Further, when a cationic surfactant is used as the surfactant, anionic surfactants, calcium hydroxide, aqueous ammonia, casein-ammonia, casein-shelf sand, etc. may be mentioned.

Furthermore, when an anionic activator is used as an activator, examples thereof include cationic activators, dilute sulfuric acid, dilute hydrochloric acid, calcium chloride, and the like. When the emulsion breaker is added, the colored liquid separates into two layers.

That is, colored floating birch substances separate into the upper layer, and the lower layer becomes a colorless to light-colored transparent water layer. The colored floats in the upper layer are separated by a furnace or the like, and usually washed thoroughly 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. As the polar solvent, the same polar solvent as described above is used.

Further, examples of the amino resin include melamine resin, urea resin, benziguanamine resin, aniline resin, and co-condensed resins thereof.

The amount of these three components used is usually 0.1 to 5:5 as a weight ratio of colored float: polar solvent: amino resin (solid content).
~100: Selected from the range of 0.5 to 19 degrees. 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 condensed.

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 tate, 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 catalyst and the co-catalyst can be used simultaneously, but it is preferable to first conduct the reaction for a predetermined period of time in the presence of the catalyst, then add the co-catalyst and continue the reaction.

The amount of catalyst used is about 0.5 to 3 skin t% based on the pigment.
Preferably, it is 5 to 15 wt%, and on the other hand, the amount of co-catalyst used is 1 to 3%, preferably 5 to 15 M%, based on the catalyst.
That's about it.

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

Moreover, the reaction time is usually selected from about 15 minutes to 1 hour. The reaction product is then poured into water and poured into water. In this case, the amount of water is usually 10 to 10% of the reaction product.
It is selected from 50 times, preferably 15 to 25 times. By this, the colored floats are dispersed in the water and then heated
The lewd matter is separated by centrifugation or the like. The resulting floating material is thoroughly washed with hot and cold water and then dried by a conventional method, including hot air drying at 80-120 pm.
It is preferable to carry out the treatment for 3 hours.

The dried floating birch material may be used as it is depending on the case, but it is usually preferable to crush it and use it in powder form. When using the thus obtained solvent-insolubilized pigment, it can be used for various purposes such as coloring, for example, in printing inks, copying machine toners, paints, etc., using various conventional methods known for the use of pigments. It is good to adopt.

As detailed above, according to the present invention, it is possible to easily obtain solvent-insolubilized pigments from water lacquer pigments, which have particularly poor resistance and are prone to deterioration and discoloration during various processing steps. By applying the present invention to pigments, stable solvent-infusible pigments can be obtained with simple operations without any alteration, and the color of the pigment can be changed by adjusting the amount of pigment. By mixing a plurality of pigments, it is possible to relatively freely change and adjust the hue or saturation of the pigment, which is extremely advantageous.

Furthermore, since the specific gravity is approximately constant, the bulk of the formed solids is constant, which is extremely advantageous in terms of workability and packaging. EXAMPLES 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 Dimethylformamide 42 parts Cationic activator "Alucard C501 (manufactured by NOF Co., Ltd.)
24. Mix well.

Next, dibenzylidene mannitol 22.5
As a auxiliary agent (stabilizer), 9.0" of tartaric acid and 6.0" of food color red No. 3 (erythrosin) were weighed and added to the mixture of the solvent and the activator, and the mixture was overflowed and melted.

Gradually raise the temperature to 120-1300 and bring to a slight boil.
The mixture was held for a minute and then poured into 2500 cc of warm water to obtain a colored hydrosol.

When this was left to cool for 5 hours, it matured and became a beautiful viscous liquid with extremely strong stringiness. When 100 tons of methyl alcohol was added to the mixture, the hydrosol was destroyed and colored particles were separated into an upper layer.

This was washed with water, separated in an oven, and dried to obtain a red water-insoluble powder. 1 part of water-insolubilized erythrosine thus obtained, 9 parts of methanol, 0.3 parts of aqueous butylated melamine solution (30%), curing solvent "Kittanit A" (manufactured by Nihon Kagaku Kogyo ■)
0.01 part of the mixture was placed in a round flask equipped with a reflux condenser and heated.

After about 30 minutes at a temperature of about 60-70 qo, the mixture is completely dissolved. The coloring solution is maintained at a temperature of 70-80°C for about 20 minutes with occasional stirring. Next, 0.01 part of alkyl titanate (manufactured by Nippon Soda Co., Ltd., "Alkyl Titanate B-1") was added, and the mixture was reacted for an additional 10 minutes.

Claims (1)

[Claims] 1. Adding an emulsion breaker to a colored liquid in which a mixed solution of a condensation product of benzaldehydes and a polyhydric alcohol having a valence of 5 or more, a surfactant, a polar medium, and a water-soluble dye is dispersed in water, separating the resulting colored float, then mixing the separated float with a polar solvent and an amino resin, heating the mixture in the presence of a curing catalyst, and dispersing the reaction product in water; A method for insolubilizing a water-soluble dye in a solvent, the method comprising separating the colored dregs obtained.