JPH10183008A - Method for purifying coloring matter, purified coloring matter, coloring agent comprising purified coloring matter, and colored article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain coloring matter which is excellent in color forming properties, solubility, and long-term shelf stability as a coloring agent and gives a colored article having high physical properties such as insulation properties, by using a charged mosaic membrane consisting of a cationic polymer component comprising an at least partly crosslinked particulate polymer and an anionic polymer component for purifying through desalting a salt-containing aqueous solution and/or aqueous dispersion of coloring matter. SOLUTION: The charged mosaic membrane known and herein used comprises the one which is made from a cationic polymer comprising an at least partly crosslinked particulate polymer and an anionic polymer, capable of readily forming a film, and enables desalting even when the concentration of salts to be dialyzed is at most a few hundred ppm. Examples of the coloring matter include water-soluble dyes comprising, e.g. a direct dye, an acid dye, a basic dye and a reactive dye, water- dispersible dyes comprising, e.g. an azo dye, an architectural dye, a disperse dye and an oil-soluble dye, and pigments (comprising, e.g. a phthalocyanine pigment, an insoluble azo pigment and a condensed azo pigment).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for desalting and purifying a salt-containing dye using a charged mosaic membrane, a purified dye, a coloring agent comprising the purified dye, and a colored article.

[0002]

2. Description of the Related Art Conventionally, water-soluble dyes, water-dispersible dyes and pigments often contain salts. In particular, water-soluble dyes such as direct dyes, acid dyes and reactive dyes have a high salt content due to the neutralization and salting-out steps in the synthesis step. When the content of the salt is high, the coloring properties and solubility of the coloring matter, long-term storage stability as a coloring agent, and the physical properties of the colored article, such as insulating properties, are often adversely affected.

In addition, in the case of ink for ink jet recording, if salt is present in the ink, the tip of the nozzle of the printer is clogged, precipitates are formed in the ink during long-term storage of the ink, There has been a problem that the ejection of ink becomes unstable and clear recording cannot be obtained. Further, in the case of a color filter, if a salt is present in the color filter ink, the salt in the formed color filter tends to cause a malfunction of the liquid crystal, which adversely affects a transistor arranged for each pixel. was there.

In the case of coloring electric and electronic materials such as electric wire coating and sealing materials, the presence of salts in the coloring material has an effect on the insulating properties of the coloring material. As described above, when using a dye, desalting and purification from the dye is performed for the purpose of enhancing the color developing property, solubility, long-term storage stability as a colorant, and physical properties of the colored article, for example, insulating properties. There is a need. As a method for solving such a problem, for example, an ion exchange resin method, a reverse osmosis method, a membrane filtration method, an electrodialysis method and the like are known.

[0005]

However, the desalting of the dye by the above-mentioned ion exchange resin method has a problem that the cost of regenerating the ion exchange resin is high, and the reverse osmosis method requires a pressure higher than the osmotic pressure of the dye solution. Therefore, energy costs are high and a large pressure-resistant device is required. In addition, the electrodialysis method requires a large-sized apparatus, has a high energy cost, and has problems such as deterioration of a target substance due to heat generation during dialysis and membrane contamination due to ion adsorption.

As a result of various studies on the above desalting and purification methods of the dye, the present inventors have found that the dye is desalted using a charged mosaic membrane in which cationic polymer domains and anionic polymer domains are alternately arranged. The inventors have found that salt purification is an effective means for solving the problems of the present invention, and have completed the present invention.

As a method for producing a charged mosaic film used for purifying a dye, there is a method using a block copolymer, but the film forming method is very difficult. However, the method using cationic and anionic polymer fine particles has an advantage that the film formation is very easy. Accordingly, an object of the present invention is to desalinate and purify an aqueous solution and / or aqueous dispersion of a salt-containing dye at a low energy cost using a charged mosaic membrane prepared from polymer fine particles with a simple apparatus. is there.

[0008]

The above object is achieved by the present invention described below. That is, the present invention provides an aqueous solution and / or an aqueous dispersion of a salt-containing dye, using a charged mosaic membrane composed of a cationic polymer component and an anionic polymer component, which are at least partially crosslinked granular polymers. And a coloring agent comprising the purified dye, and a colored article. Color development, solubility, by purifying the dye by the method of the present invention,
A pigment having high physical properties such as long-term storage stability as a coloring agent and physical properties of a colored article, for example, insulating properties, is provided, and an excellent coloring agent and a colored article are provided.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below in more detail with reference to preferred embodiments. The dye used in the present invention may be any dye conventionally known as a dye, for example, direct dyes, acid dyes, basic dyes,
Reactive dyes, water-soluble dyes such as food dyes, azo dyes, vat dyes, disperse dyes, water-dispersible dyes such as oil-soluble dyes, and phthalocyanine, insoluble azo, and condensed azo pigments System, soluble azo system, quinacridone system, dioxazine system, indigo-thioindigo system, perylene / perinone system, isoindolinone system, azomethine system, azomethine azo system, anthraquinone system, dye pigment system, titanium oxide system, iron oxide system, Pigments such as composite oxide pigments and carbon blacks are exemplified.

Particularly, direct dyes, acid dyes, reactive dyes and the like, which have a neutralization and salting-out step in the synthesis step, are preferably used because of their high salt content. The salt contained in such a dye is an inorganic salt generated by neutralization, salting out, or the like in the synthesis step, such as sodium chloride, potassium chloride, calcium chloride, magnesium chloride, ammonium chloride, sodium carbonate, sodium sulfate, sodium phosphate, and the like. Examples of the organic salt include sodium acetate and calcium acetate.

In the method of the present invention, since the salt concentration difference and the pressure difference between the dye stock solution side and the dialysis solution side are created and desalting and purification are performed, the concentration of the salt contained in the dye stock solution is not particularly limited. Excellent desalting and refining effects are exhibited not only when the concentration of the salt in the dye stock solution is high but also when the concentration is as low as 1% by weight or less.

The charged mosaic film used in the method of the present invention is a film that has already been proposed.
No. 430, Japanese Patent Application No. 4-279248, Japanese Patent Application No. 5-76435, Japanese Patent Application No. 6-198957, Japanese Patent Application No. 6-319513, Japanese Patent Application No. 7-1995.
Any of the charged mosaic films described in Japanese Patent Application No. 103193 and Japanese Patent Application No. 8-263747 can be used in the method of the present invention.

In particular, the mosaic charged membrane used in the present invention is:
It has a composition comprising a cationic polymerizable component and an anionic polymer component which are at least partially crosslinked granular polymer, can be easily formed into a membrane, and has a salt concentration of several hundred ppm or less when dialyzed. It has the characteristic that it can be dialyzed and desalted.

The method for purifying a dye of the present invention is characterized in that the above-described charged mosaic membrane is used as a dialysis membrane, and desalting and purification can be performed with a simple apparatus at low energy cost. The structure of the device is not particularly limited. FIG. 1 shows an example of the apparatus. A container 1 is filled with an aqueous solution and / or aqueous dispersion of a dye, a container 2 is filled with deionized water, and a charged mosaic membrane is sandwiched between the two containers.
When the mixture is stirred at normal pressure while maintaining the temperature at 0 ° C., only the water-soluble salt is transferred to the deionized water, and the salt concentration in the container 1 is reduced, whereby the dye is desalted and purified. Further, by using the charged mosaic membrane having pressure resistance used in Japanese Patent Application No. 7-103193, dialysis under pressure is possible, and the structure of the pressure device is not particularly limited.

FIG. 2 shows another example. This apparatus is capable of dialysis and desalting of an aqueous solution and / or aqueous dispersion of a dye under pressure, and a tank 7 for storing an aqueous solution and / or an aqueous dispersion of a dye is a pressure-resistant tank. A stirring motor 5 is sealed with a mechanical seal 6 and attached to the tank 7 so that dialysis can be performed under stirring.

The charged mosaic film 11 is supported by a filter backup 12 so as to withstand the applied pressure, and is hermetically attached to the tank 7 by a packing 10 on the flange bottom 9 of the tank 7. When the charged mosaic membrane is formed by the pressure at the time of dialysis desalting or using a pressure-resistant asymmetric porous body, the filter backup 12 may be omitted.

The dialysis and desalting of the aqueous solution and / or aqueous dispersion of the dye is performed at an optimum pressure according to the performance of the charged mosaic membrane, the type of the dialysate, and the like. The pressure in the tank is measured with a pressure gauge
3 is displayed. The valves N-1 to N-3 also serve as a valve for reducing the pressure of the tank, a valve for injecting the aqueous solution and / or aqueous dispersion of the dye, and a valve for increasing the pressure. In addition, this device
It is supported by a ring mount 16 fixed to a mount shaft 15 by a clamp 14.

In the present invention, the dye purified by using the charged mosaic film is used for coloring an electric material such as an ink for ink-jet recording, a color filter, an electric wire coating and a sealing material, an electronic material, and dyeing a fiber material. Or used for printing. For example, the dye purified by the method of the present invention is used in the same manner as the dye used for a conventionally known coloring agent for the above-mentioned application.

When the dye purified by the method of the present invention is used for an ink jet recording ink, the dye is used in the same configuration as a conventionally known ink jet ink.
The ink-jet ink comprises an aqueous solution containing a desalted and purified dye and a polyhydric alcohol, and may contain a preservative, a fungicide, and a surfactant for improving the surface tension, if necessary.

When the dye purified by the method of the present invention is used for a color filter, it is used in the same configuration as a conventionally known color filter ink.
The ink is desalted and purified dye, resin varnish, a solvent suitable for the resin varnish, an aqueous medium, if necessary conventionally known additives, such as a dispersing aid, a smoothing agent,
An adhesion agent or the like is added and used.

Examples of the resin varnish include photosensitive cyclized rubber resins, photosensitive polyamide resins, unsaturated polyester resins, cellulose acetate resins, polyvinyl butyral resins, and water-soluble aminoalkyd resins. . Such a color filter ink can be spin-coated on a glass substrate and then subjected to post-processing to obtain a color filter. In addition, a high-concentration aqueous liquid of the pigment desalted and purified by the method of the present invention can be prepared and dyed on a fiber material, especially cellulose fiber, by a conventionally known method such as exhaustion dyeing or printing.

[0022]

EXAMPLES Next, the present invention will be described more specifically with reference to Reference Examples and Examples. The parts and percentages in the text are based on weight. Reference Example Polymer A: Cationic granular polymer 4-vinylpyridine 10 parts Divinylbenzene 1 part Acrylamide 1 part 2,2'-azobis (2-amidinopropane) dihydrochloride 0.2 part Water 500 parts

The above components were charged into a flask and polymerized at 80 ° C. for 8 hours under a nitrogen stream. The polymerization product was purified by dialysis to obtain a particulate polymer having an internally cross-linked structure. The particle size of the granular polymer is about 200 nm and its coefficient of variation is 2
It was 0%.

Polymer B: Cationic granular polymer 4-vinylpyridine 10 parts 2,2'-azobis (2-amidinopropane) dihydrochloride 0.2 parts Water 500 parts

The above components were charged into a flask and polymerized at 80 ° C. for 8 hours under a nitrogen stream. The polymerization product was purified by dialysis to obtain an uncrosslinked granular polymer. The particle size of the granular polymer was about 350 nm, and the coefficient of variation was 35%.

Polymer C: anionic linear polymer sodium styrene sulfonate 36 parts acrylamide 12 parts 2,2'-azobis (2-amidinopropane) dihydrochloride 1 part water 300 parts For 8 hours. The number average molecular weight of the produced polymer was about 50,000.

Polymer D: anionic granular polymer styrene 62.4 parts acrylonitrile 10.6 parts hydroxyethyl methacrylate 12.1 parts divinylbenzene 13.0 parts potassium persulfate 0.78 parts water 1,500 parts Then, a soap-free emulsion polymerization reaction was carried out at 80 ° C. for 8 hours under a nitrogen stream to obtain an emulsion polymerization liquid. The particle size of the obtained polymer was about 180 nm, and the coefficient of variation was 20%.

The above polymer was dried and pulverized, and 62 parts of a white polymer obtained was gradually added to 400 parts of 98% concentrated sulfuric acid. The mixture was stirred at 50 ° C. for 24 hours and at 80 ° C. for 3 hours, and cooled. Then, the reaction mixture was poured into a large amount of ice water to precipitate a polymer in a granular form. The mixture was further neutralized with sodium carbonate.
The mixture was filtered through a Millipore filter and washed thoroughly with water.
The obtained granular polymer can be confirmed by analysis such as infrared absorption spectrum and ion chromatography that almost one sulfone group has been introduced into the aromatic ring and that the nitrile group has been converted to an amide group. Was. The particle size of this granular polymer is about 240 nm, and its coefficient of variation is 7
It was 0%.

Polymer E: styrene-butadiene copolymer
Body styrene - butadiene copolymer latex (solids 4
5%, average particle size 0.1 μm, glass transition point (Tg) 0
° C) Polymer F: acrylonitrile-butadiene copolymer acrylonitrile-butadiene copolymer latex (solid content 42%, average particle size 0.06 µm, glass transition point (Tg) -20 ° C)

Reference Examples 1 to 3 Charged mosaic films used in the present invention were prepared by the following film forming method. The composition of the raw materials used is shown in Table 1. (Preparation of membrane) A mixed solution having the composition shown in Table 1 was 340 mm ×
The film is spread on a 560 mm glass plate so as to be 100 g / m ² at the time of drying, and a film is formed by a dryer. After leaving the glass plate with the film in an acidic atmosphere with concentrated hydrochloric acid for 3 days,
The glass plate with the film is immersed in an aqueous solution of 10% sodium acetate to neutralize and sufficiently washed. After drying the glass plate with the membrane, it is left to stand in an atmosphere of diiodobutane and methanol for 7 days. Subsequently, the glass plate with the film was allowed to stand in an atmosphere of methyl iodide and methanol for 3 days, and then 3 of Reference Examples 1 to 3
A kind of charged mosaic membrane was obtained.

[0031]

[Table 1]

Example 1 The charged mosaic membrane obtained in Reference Example 1 was set in the dialysis apparatus (membrane area: 12 cm ² ) of FIG. 1 to purify blue direct dye by desalting. When the content of the salt in this dye was measured by an ion chromatography method, it was 10.1% by weight in total of sodium chloride and sodium sulfate.

In a container 1, 200% by weight of a 10% by weight aqueous dye solution was added.
ml and 200 ml of deionized water.
Here, the deionized water in container 2 and 1000 m in another container
1 deionized water is connected with a magnet circulation pump and
The dialysis water was replaced with deionized water every hour. The exchange was performed twice. As a result, the content of salt in the dye after desalination purification was 0.08% by weight in total of sodium chloride and sodium sulfate.

Example 2 The charged mosaic membrane obtained in Reference Example 2 was set in the dialysis apparatus (membrane area: 12 cm ² ) of FIG. 1 to obtain an azo black acid dye (CI acid black 24). Desalting purification was performed. The content of the salt of this dye was measured by ion chromatography to find that the total of sodium chloride and sodium sulfate was 8.1% by weight.

A 5% by weight aqueous dye solution is placed in a container 1 for 200 m.
and 200 ml of deionized water in container 2 and 25
The mixture was stirred at ordinary temperature under a normal pressure to perform desalination purification. The dialysis water in container 2 was replaced with deionized water every 24 hours. The exchange was performed five times. As a result, the separability between the dye and the salt was good and no leakage of the dye was observed. The content of the salt in the dye after desalting and purification was measured by ion chromatography to find that the total amount of sodium chloride and sodium sulfate was 0.07% by weight.

3 parts of the purified black acidic dye obtained above, 62 parts of ethylene glycol and 35 parts of deionized water were stirred and mixed so as to be homogeneous to obtain an ink for ink jet recording. When the storage stability of this ink was tested, it did not discolor even after long-term storage at 0 ° C. for 1 month and at 50 ° C. for 6 months. there were. Next, use this ink for 24 hours.
When inkjet recording was performed for a long time, clear recording could be obtained without causing clogging at the tip of the nozzle.

Example 3 The insoluble yellow azo pigment was desalted and purified using the charged mosaic film obtained in Reference Example 3. Container 10 was charged with a 10% by weight pigment dispersion ultrasonically dispersed for 2 hours, and the other conditions were the same as in Example 2. The content of the salt in this pigment was 0.3% by weight in total of sodium chloride and sodium sulfate. The content of salt in the pigment after desalination purification is 50 ppm
Met.

The purified yellow insoluble azo pigment obtained above is combined with red, green, and blue pigments as correction pigments and a color filter colorant comprising an acrylic resin and N-methyl-2-pyrrolidone as a solvent. Obtained. This colorant was spin-coated on a glass plate treated with a silane coupling agent to form a mosaic pattern. The color filter thus obtained had an excellent spectral pattern, was excellent in robustness such as weather resistance and heat resistance, and also had excellent performance in light transmission.

Example 4 Using the charged mosaic membrane obtained in Reference Example 1, desalting and purification of a red reactive dye was carried out in the same manner as in Example 1. The content of salt in this dye was 7.6% by weight in total of sodium chloride and sodium sulfate. The content of salt in the dye after desalination purification was 0.1% by weight.

The purified red reactive dye obtained above was prepared so that the dye concentration was 20% by weight. The aqueous liquid thus obtained did not discolor even after long-term storage at 0 ° C. for 1 month and at 50 ° C. for 6 months, and had good storage stability without generating precipitates. . 50
Cotton was dyed using an aqueous liquid stored at 6 ° C. for 6 months. After completion of the dyeing, washing and drying were performed, and as a result, a red dyed product having no stain and having good light fastness was obtained.

[0041]

According to the present invention as described above, a salt is contained by using a charged mosaic membrane composed of a cationic polymer component and an anionic polymer component which are at least partially crosslinked granular polymers. The aqueous solution and / or aqueous dispersion of the dye can be easily and highly desalinated and purified, and the coloring property, solubility, long-term storage property of the coloring agent, and the physical properties of the colored article, such as insulating properties, can be obtained. , And an excellent colorant and a colored article were obtained.

[Brief description of the drawings]

FIG. 1 is a diagram illustrating a dialysis test device used in an example.

FIG. 2 is a diagram illustrating a pressure dialysis device used in the embodiment.

[Explanation of symbols]

1: Container 2: Container 3: Mosaic charged film 4: Magnetic stirrer 5: Motor for stirring 6: Mechanical seal 7: 250 ml pressure tank 8: Stirring shaft 9: Flange bottom 10: Packing 11: Mosaic charged film 12: Mosaic charged membrane backup (filter backup) 13: pressure gauge 14: clamp 15: gantry shaft 16: ring gantry N1-3: solution injection nozzle, nozzle for pressure reducing valve and nozzle for pressure valve

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Michie Nakamura 1-7-6 Nihombashi Bakurocho, Chuo-ku, Tokyo Inside Dainichi Seika Kogyo Co., Ltd. (72) Inventor Hitoshi Takeuchi 1-7 Nihonbashi Bakurocho, Chuo-ku, Tokyo No. 6 Dainichi Seika Industry Co., Ltd. (72) Inventor Naomi Oguma 1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo (72) Inventor Shojiro Horiguchi 1 Nihonbashi Bakurocho, Chuo-ku, Tokyo 7-7-6 Dainichi Seika Kogyo Co., Ltd.

Claims (8)

[Claims] An aqueous solution and / or aqueous dispersion of a salt-containing dye is prepared using a charged mosaic membrane comprising a cationic polymer component and an anionic polymer component which are at least partially crosslinked granular polymers. A method for purifying a dye, comprising desalting and purifying. 2. The method for purifying a dye according to claim 1, wherein the dye is a water-soluble dye, a water-dispersible dye and a pigment. 3. A purified dye which is desalted and purified using a charged mosaic membrane comprising a cationic polymer component and an anionic polymer component, which are at least partially crosslinked granular polymers. 4. The purified dye according to claim 3, wherein the dye is for ink jet recording ink. 5. The purified dye according to claim 3, wherein the dye is used for a color filter. 6. The purified dye according to claim 3, wherein the dye is for coloring an electric material such as an electric wire coating and a sealing material, and an electronic material. 7. A colorant comprising a pigment desalinated and purified using a charged mosaic membrane comprising a cationic polymer component and an anionic polymer component which are at least partially crosslinked granular polymers. . 8. A colored mosaic membrane comprising a cationic polymer component and an anionic polymer component, which are at least partially crosslinked granular polymers, and are colored with a desalted and purified dye. Goods.