JP2001261995A - Method for producing green pigment composition - Google Patents

Abstract

(57) [Problem] To have a clear hue when dispersed in a vehicle,
Provided is a green pigment composition in which a blue pigment and a yellow pigment do not cause color separation. A method for producing a green pigment composition, comprising coupling and synthesizing a yellow pigment in the presence of a blue pigment, wherein a water slurry of a blue pigment and a diazo or tetrazo solution of the yellow pigment are independently formed. For producing a green pigment composition, which is poured into a yellow pigment coupler solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a green pigment obtained by mixing a blue pigment and a yellow pigment. More specifically, the present invention relates to a method for producing a green pigment, wherein the blue pigment and the yellow pigment are not separated and are dispersed in a vehicle. The present invention relates to a green pigment composition having a clear hue and not causing color separation.

[0002]

2. Description of the Related Art The green color of printed matter, colored matter, etc. is due to phthalocyanine green obtained by highly chlorinating phthalocyanine.
It is obtained by mixing phthalocyanine blue and disazo yellow. One method of obtaining a green color by mixing is to mix a yellow pigment slurry obtained in the pigment production step with a blue pigment slurry, and then filter, dry, pulverize, or dry the yellow pigment and dry. And pulverizing by mixing with a blue pigment. As another method, there is a method of mixing a pigment dispersion containing a blue pigment and a pigment dispersion containing a yellow pigment in an ink-forming step or a paint-forming step.

[0003] However, pigments obtained by these methods may cause separation of a yellow pigment and a blue pigment upon drying,
In the case of using ink or paint, there is a disadvantage that the hue is unclear and yellow and blue color separation occurs upon storage.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a green pigment which does not separate blue pigments and yellow pigments when dried, and which has a clear hue when dispersed in a vehicle and which does not cause color separation. An object of the present invention is to provide a production method for producing a pigment composition with low energy.

[0005]

SUMMARY OF THE INVENTION The present invention relates to a method for producing a green pigment composition, comprising coupling and synthesizing a yellow pigment in the presence of a blue pigment. Furthermore, the present invention
The present invention relates to a method for producing the above-mentioned green pigment composition, wherein a water slurry of a blue pigment and a diazo solution or a tetrazo solution of a yellow pigment are added to a coupler solution of the yellow pigment, and the yellow pigment is subjected to a coupling reaction. Further, the present invention relates to a method for producing the green pigment composition, wherein a water slurry of a blue pigment and a diazo solution or a tetrazo solution of a yellow pigment are independently injected into a coupler solution of a yellow pigment. Furthermore, the present invention relates to a method for producing the green pigment composition, wherein the blue pigment is a phthalocyanine pigment. Furthermore, the present invention relates to a method for producing the above-mentioned green pigment composition, wherein the yellow pigment is at least one selected from the group consisting of a monoazo type, a disazo type and a benzimidazolone type. Further, the present invention relates to a green pigment composition obtained by the above production method.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The blue pigment used in the present invention is
There are phthalocyanine pigments, sullen pigments, indigo pigments and the like, but phthalocyanine pigments are preferred. As phthalocyanine pigments, those in which the central metal is copper are common as blue pigments, but the central metals are nickel, cobalt, iron,
It may be a metal such as aluminum or a non-metal. Hereinafter, as an example of the blue pigment that can be used in the present invention, a color index name (CI Generic Nam) is used.
Although e) is shown, the present invention is not limited to these.

The phthalocyanine blue pigments include C.I.
I. Pigment Blue 15, 15: 1, 15: 2, 1,
5: 3, 15: 4, 15: 5, 15: 6 and 16.
The color index name of the slender pigment is C.I. I. Pigment Blue 60, and the indigo pigment is C.I. I. Pigment Blue 66.

The blue pigment of the present invention has an average particle size of 20 to
It is preferable to use one having a thickness of 100 nm. A blue pigment having such an average particle size can be obtained by physically or chemically pulverizing a crude pigment. For example, pigment particles having a small average particle size can be obtained by wet-grinding a crude pigment together with a water-soluble solvent such as ethylene glycol and a water-soluble inorganic salt such as sodium chloride.

Further, it can also be obtained by dissolving a crude pigment in a strong acid such as concentrated sulfuric acid to form a uniform solution, and then pouring and reprecipitating it in a large amount of water.

The yellow pigment of the present invention is not limited as long as it is obtained by a coupling reaction between a diazotized or tetrazotized component of an amine and a coupler component.
For example, there are monoazo-based, disazo-based, and benzimidazolone-based yellow pigments, which can be selected according to a target hue, required heat resistance, light resistance, and the like.

The amine forming the diazo component includes o
-Nitro-p-methylaniline, o-nitro-p-chloroaniline, o-nitroaniline, o-methyl-p-chloroaniline, o-nitro-p-methoxyaniline, o
-Methoxy-p-nitroaniline, 3,5-methoxycarbonylaniline, o-carboxyaniline, 2,5-
Examples include methoxycarbonylaniline and 2-methoxyaniline.

As the amine forming the tetrazo component,
3,3'-dichlorobenzidine, 2,2 ', 5,5'-
Examples include tetrachlorobenzidine, 3,3'-disulfobenzidine and the like. These diazo or tetrazo components are prepared as an acidic aqueous solution.

The coupler components include acetoacetoanilide, acetoaceto-o-toluidide, acetoaceto-m-xylide, acetoaceto-o-anisidide, acetoaceto-p-anisidide, acetoaceto-o-chloroanilide, and acetoaceto-2,5. Acetoacetanilides such as -dimethoxy-4-chloroanilide and acetoaceto-2-methyl-3-chloroanilide; Also, acetolone having a benzimidazolone ring can be used. Two or more couplers may be used in combination.

When the yellow pigment of the present invention is represented by a color index name, C.I. I. Pigment Yellow 1, 2, 3,
10, 74, 97, 98, 120, 151, 154, 1
2, 13, 14, 17, 55, 81 83, 167, 1
80, 181, 61, 169, 100, 183, 191
Etc.

The green pigment composition of the present invention can be obtained by the following production method. (1) A water slurry of a blue pigment and a diazo solution or a detrazo solution of a yellow pigment are independently and simultaneously added to a coupler solution of a yellow pigment. (2) A yellow pigment diazo solution or a tetrazo solution containing a blue pigment is added to the yellow pigment coupler solution. (3) A diazo solution or a tetrazo solution of a yellow pigment is added to a coupler solution of a yellow pigment containing a blue pigment. (4) A diazo solution or tetrazo solution of a yellow pigment and a coupler solution are independently and simultaneously added to a buffer solution containing a blue pigment.

Of the above production methods, the method (1) is preferred in that the effect of the blue pigment on the coupling reaction of the yellow pigment is relatively small. In the production method (1) above, the pigment water slurry may be injected at any time during the coupling, but preferably, the injection is started at the same time as the start of the coupling reaction, and the injection is stopped at the same time as the end of the coupling reaction. Is good. Further, the aqueous slurry of the blue pigment may be dropped on the liquid surface of the coupling reaction solution of the yellow pigment, or may be dropped below the liquid surface.

When the blue pigment is used alone or together with other components in a slurry state, the concentration of the blue pigment is preferably a viscosity (1 to 100 ps) that can be transferred by a pump.
The concentration of the pigment is preferably 1 to 15% by weight. The pH of the solution during the coupling reaction of the yellow pigment is 4
Positions 6 to 6 are preferred, and other conditions for the coupling reaction, such as temperature and time, can be adopted from conventionally known ranges. The green pigment slurry after the completion of the coupling reaction is filtered, dried and pulverized by a usual method.

In the green pigment composition of the present invention, the mixing ratio of the blue pigment and the yellow pigment can also be adjusted according to the target green hue. For example, the weight ratio may be in the range of blue pigment: yellow pigment = 90: 10 to 20:80.

The vehicle component used in the pigment dispersion of the present invention includes a vehicle for printing ink, a vehicle for gravure ink, a vehicle for paint, a resin for toner, and a resin for molded plastic.

As a vehicle for printing ink, there is a vehicle in which a rosin-modified phenol resin, a rosin-modified maleic resin, a petroleum resin, an alkyd resin and the like are combined with soybean oil, tung oil, linseed oil and the like as main components.

Examples of the gravure ink vehicle include lime rosin resin, polyamide resin, vinyl chloride resin, cyclized rubber, urethane resin, acrylic resin, maleic acid resin,
Nitrocellulose and other solvents such as aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ketones, esters, ethers, ether alcohols, ether esters, and water There is a vehicle or the like having a combination as a main component.

As a vehicle for coating, nitrocellulose lacquer, aminoalkyd resin, acrylic lacquer,
Amino acrylic resin, urethane resin, polyvinyl acetal resin, epoxy resin, polyester resin, vinyl chloride resin, vinylidene fluoride resin, vinyl fluoride resin, polyether sulfone resin, etc. and aliphatic hydrocarbons, aromatic hydrocarbons, halogens There is a vehicle whose main component is a combination with a solvent such as a fluorinated hydrocarbon, alcohol, ketone, ester, ether, ether-alcohol, ether-ester, or water.

As the resin for the toner, polystyrene,
Styrene-acrylic copolymer, chloride resin, styrene-vinyl acetate copolymer, rosin-modified maleic resin, phenolic resin, epoxy resin, polyester resin, low molecular polyethylene, low molecular polypropylene, polyurethane resin, silicone resin, rosin ester, There are rosin, etc., as plastic resins, polyethylene, polypropylene, ethylene-propylene copolymer, α-olefin and acrylic acid or maleic acid copolymer, ethylene-vinyl acetate copolymer, ethylene and acrylic acid or anhydride Polyolefin resins such as copolymers with maleic acid, vinyl resins such as polyvinyl chloride and polyvinyl acetate, acrylic resins such as polyacrylonitrile and methacrylic resin,
Styrene resins such as polystyrene and acrylonitrile-butadiene-styrene copolymer; polyester resins such as polyethylene terephthalate and polycarbonate;
Examples include nylon such as nylon, unsaturated polyester resin, epoxy resin, urea resin, melamine resin, and cellulose resin.

[0024]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the examples. In the examples, “parts” means “parts by weight” and “%” means “% by weight”.

EXAMPLE 1 30 parts of acetoaceto-o-toluidide are dissolved in about 300 parts of an aqueous solution containing 14.5 parts of sodium hydroxide. An acetic acid solution obtained by diluting 29 parts of 80% acetic acid with about 150 parts of water is gradually added to the alkaline solution to prepare a coupler solution in which acetoaceto-o-toluidide is reprecipitated. The pH of this coupler solution was 6.1, the amount of the solution was adjusted to about 800 parts, the temperature was adjusted to 25 ° C., and the solution was charged into a 3 L container equipped with a stirrer. The tetrazo solution is obtained by subjecting 19.5 parts of 3,3′-dichlorobenzidine to tetrazotization by a usual method, and the liquid volume is about 600 parts, and the temperature is 0 to 5 parts.
Adjusted to ° C.

As the phthalocyanine blue pigment, No. Three
Crude Blue 75 parts (manufactured by Toyo Ink Manufacturing Co., Ltd.), salt 5
50 parts and 100 parts of diethylene glycol were charged into a 1 L test kneader and kneaded at 100 ° C. for 6 hours.
After kneading, add about 2500 parts
The mixture was poured into warm water at ℃ C and stirred for about 30 minutes, and then filtered and washed with water to completely remove salt and diethylene glycol.
A blue pigment slurry was prepared by reslurrying the obtained wet cake in about 900 parts of water.

Injection tubes for the tetrazo solution and the phthalocyanine blue pigment slurry were set in the above coupler solution. These two solutions were simultaneously infused by the metering pump and ended in about 40 minutes. The flow rate of the tetrazo solution was 15 g / min, and the blue slurry was injected at 22.5 g / min. Injection temperature is 2
The temperature was 5 to 30 ° C., and the pH after the completion of the injection was 4.4. The obtained green pigment slurry was stirred at 80 ° C. for about 1 hour, filtered, washed with water, and dried at 80 to 90 ° C. overnight to obtain 115 parts of a green pigment composition.

Comparative Example 1 In Example 1, the phthalocyanine blue pigment slurry was not injected during the coupling,
Only the tetrazo solution was injected to synthesize a yellow pigment. The blue pigment slurry obtained in the same manner as in Example 1 was injected into the yellow pigment slurry at room temperature for about 10 minutes using a metering pump. The obtained green pigment slurry is heated at 80 ° C. for about 1 hour.
After stirring for an hour, the mixture was filtered, washed with water, and dried to obtain a green pigment composition.

(Comparative Example 2) Both the phthalocyanine blue pigment slurry obtained in Example 1 and the yellow pigment slurry synthesized in Comparative Example 1 were stirred at 80 ° C. for about 1 hour, respectively, and then filtered, washed with water, dried, and dried in blue. A lump composition of each of the pigment and the yellow pigment was obtained. Blue pigment: yellow pigment, which is a lump of these pigment compositions, was mixed in a ratio of 60 parts: 40 parts.

Example 2 Acetoacetanilide 40
Parts are dissolved in about 400 parts of an aqueous solution containing 18 parts of sodium hydroxide. An acetic acid solution obtained by diluting 35 parts of 80% acetic acid with about 200 parts of water is gradually added to the alkaline solution to prepare a coupler solution in which acetoacetanilide is reprecipitated. The pH of the coupler solution was 6.0, the amount of the solution was adjusted to about 1000 parts, the temperature was adjusted to 20 ° C., and the solution was charged into a 3 L container equipped with a stirrer.

The diazo solution contains 34 parts of o-nitro-p-
Methylaniline is diazotized by an ordinary method, and a liquid volume of about 90
0 parts and the temperature was adjusted to 0 to 5 ° C. As phthalocyanine blue pigments, 75 parts of 3 Crude Blue (manufactured by Toyo Ink Mfg. Co., Ltd.) was gradually added to 380 parts of 98% sulfuric acid, stirred at room temperature for about 2 hours, and then poured into 3000 parts of water to precipitate a phthalocyanine blue pigment. Thereafter, the slurry was stirred at 90 ° C. for about 1 hour, filtered, and washed with a large amount of water until neutral. Put the obtained wet cake in water for about 900
The blue pigment slurry reslurried in the part was adjusted.

In the above-mentioned coupler solution, respective injection tubes for the diazo solution and the phthalocyanine blue pigment slurry were set. These two solutions were simultaneously infused by the metering pump and ended in approximately 60 minutes. The flow rate of the diazo solution was 15 g / min, and the blue slurry was also injected at 15 g / min. Injection temperature is 2
The temperature was 5 to 30 ° C, and the pH after the completion of the injection was 4.3. The obtained green pigment slurry was stirred at 80 ° C. for about 1 hour, filtered, washed with water, and dried at 80 to 90 ° C. overnight to obtain 135 parts of a green pigment composition.

(Comparative Example 3) In Example 2, the phthalocyanine blue pigment slurry was not injected during the coupling,
Only the diazo solution was injected to synthesize a yellow pigment. The blue pigment slurry obtained in the same manner as in Example 2 was injected into this yellow pigment slurry at room temperature for about 15 minutes using a metering pump. After stirring the obtained green pigment slurry at 80 ° C. for about 1 hour, it was filtered, washed with water, and dried to obtain a green pigment composition.

Example 3 39.5 parts of acetolone is dissolved in about 400 parts of an aqueous solution containing 27 parts of sodium hydroxide. 26 parts of 80% acetic acid was added to this alkaline solution,
An acetic acid solution diluted with 0 parts is gradually added to prepare a coupler solution in which acetolone is reprecipitated. The pH of the coupler solution was 6.0, the amount of the solution was adjusted to about 800 parts, the temperature was adjusted to 20 ° C., and the solution was charged into a 3 L container equipped with a stirrer.

The diazo solution was prepared by diazotizing 35 parts of 3,5-methoxycarbonylaniline by an ordinary method, and adjusted to a liquid volume of about 800 parts and a temperature of 0 to 5 ° C. As phthalocyanine blue pigments, 50 parts of 3 Crude Blue (manufactured by Toyo Ink Mfg. Co., Ltd.), 350 parts of salt and 70 parts of diethylene glycol were charged into a 1 L test kneader and kneaded at 90 ° C. for 5 hours. After completion of the kneading, about 2000 parts of the dough cake was poured into warm water of 80 ° C., stirred for about 30 minutes, and then filtered and washed with water to completely remove salt and diethylene glycol. Put the obtained wet cake in water for about 600
The blue pigment slurry reslurried in the part was adjusted.

In the above-mentioned coupler solution, respective injection tubes for the diazo solution and the phthalocyanine blue pigment slurry were set. These two solutions were simultaneously infused by the metering pump and ended in about 40 minutes. The flow rate of the diazo solution was 20 g / min, and the blue slurry was injected at 15 g / min. Injection temperature is 20-3
It was 0 ° C. and the pH after the end of the injection was 4.3. After stirring the obtained green pigment slurry at 80 ° C. for about 1 hour,
Filtration, washing with water, drying at 80-90 ° C. overnight, 110
Parts of a green pigment composition were obtained.

(Comparative Example 4) In Example 3, the phthalocyanine blue pigment slurry was not injected during the coupling,
Only the diazo solution was injected to synthesize a yellow pigment. The blue pigment slurry obtained in the same manner as in Example 3 was injected into the yellow pigment slurry at room temperature for about 15 minutes using a metering pump. After stirring the obtained green pigment slurry at 80 ° C. for about 1 hour, it was filtered, washed with water, and dried to obtain a green pigment composition.

(Observation of Pigment) As a result of visually observing the lump of the pigment prepared in each example, Comparative Examples 1, 3 and 4 were observed.
The pigments of Example 1 were not completely green pigments because the yellow pigment was separated from the green pigment (Comparative Example 2 was excluded because of the mixture of the yellow pigment and the blue pigment), but the pigments of Examples 1 to 3 were yellow. There was no separation of pigment or blue pigment, and the color was completely green.

(Production of Pigment Dispersion) The pigment prepared in each example was pulverized with a wire mesh (mesh size: 110 μm), and each dispersion of paint, printing ink (gravure ink, offset ink) and plastic was prepared by the following method. And processed according to the following evaluation method.

(Preparation of paint) For 6 g of pigment, 94 g of paint vehicle and steel beads 300
g was placed in a 225 ml glass bottle and dispersed for 1 hour with a paint conditioner to prepare a coating composition. "Blending of vehicle for coating" 56 parts of alkyd resin varnish (60% non-volatile content) 28 parts of melamine resin varnish (50% non-volatile content) 10 parts of xylene

(Preparation of Gravure Ink) 65 g of an aqueous acrylic varnish, 20 g of water, 15 g of pigment and 150 g of alumina beads were charged into a 225 ml glass bottle, and dispersed for 1 hour with a paint conditioner to prepare an aqueous gravure ink.

(Preparation of offset ink) 15 g of pigment,
85 g of a varnish for offset ink was weighed on a burler roll adjusted to 60 ° C., premixed at a roll pressure of 10 bar for 5 minutes, and then subjected to 10 bar / 3 passes. As a result, the base ink in which pigment particles were dispersed to 7.5 μm or less was obtained. Obtained. Next, a varnish and a total of 10 g of an ink solvent were added to the base ink, and the ink tone was adjusted so that the tack became 6.0.

(Preparation of Plastic Dispersion) To 0.1 part of pigment, 100 parts of polypropylene resin and 0.1 part of zinc stearate were mixed with a tumbler, melted and extruded with an extruder, cooled, and then cut. A plastic pigment dispersion (colored pellet) was prepared.

(Evaluation of Pigment Dispersion) (Evaluation of Paint) As shown in Table 1, the paint using the pigment prepared in each of Examples and Comparative Examples was coated on coated paper, and was subjected to a color machine (Nippon Denshoku Co., Ltd.). The sharpness was measured with a gloss meter (UGV-5D, manufactured by Suga Test Instruments Co., Ltd.), and the gloss value was measured at 60 °. The paint was placed in a test tube and allowed to stand at room temperature for one month, and the presence or absence of color separation was observed.

[0045]

[Table 1]

(Evaluation of Aqueous Gravure Ink) The pigments prepared in Examples and Comparative Examples and a commonly used green pigment, Lionol Green Y-102 (C.I.
Pigment Green 7) was compared. The prepared ink was evaluated with a # 2 bar coater (film thickness: 12 μm) so that the pigment content was adjusted to the same density at the time of manila cardboard drawing. In order to obtain the same concentration as that of Y-102, the amount of the pigment used in the example was about 40%, and the amount of the pigment used in the comparative example was about 50%
%Met. In Table 2, the amount of each pigment required to obtain the same concentration as when Y-102 is 100 is shown in%. or,
As in the case of the evaluation of the paint, the sharpness, gloss, and presence of color separation were examined.

[0047]

[Table 2]

(Evaluation of offset ink) The prepared ink was spread on art paper with an RI tester, and the sharpness was measured with a color machine (Nippon Denshoku Co., Ltd. # 80), and the gloss value was measured with a gloss meter (Suga test). UGV-5D) and the density was measured with a Macbeth densitometer. The results are shown in Table 3.

[0049]

[Table 3]

(Evaluation of Colored Pellets) As shown in Table 4, the pigments prepared in the examples and comparative examples were compared with a commonly used green pigment, Lionol Green Y-102.
The sharpness of a dark plate obtained by injection molding these colored pellets at 200 ° C. was measured with a color machine. Further, the coloring power of the light-colored plate toned so that the ratio of pigment: white pigment (titanium white) was 1:20 was visually evaluated.

[0051]

[Table 4]

The method for producing the green pigment composition of the present invention comprises:
The presence of the blue pigment during the coupling synthesis of the yellow pigment does not require a special mixing step, so that the energy cost is small. In addition, the blue pigment and the yellow pigment are not separated by drying, and have an effect of not only having a clear hue even when dispersed in a vehicle, but also having coloring power and not causing color separation over time.

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Claims (7)

[Claims] 1. A method for producing a green pigment composition, comprising coupling and synthesizing a yellow pigment in the presence of a blue pigment. 2. The method for producing a green pigment composition according to claim 1, wherein a water slurry of a blue pigment and a diazo solution or a tetrazo solution of the yellow pigment are added to a coupler solution of the yellow pigment to perform a coupling reaction of the yellow pigment. . 3. The method for producing a green pigment composition according to claim 2, wherein the aqueous slurry of the blue pigment and the diazo or tetrazo solution of the yellow pigment are independently injected into the coupler solution of the yellow pigment. 4. The method for producing a green pigment composition according to claim 1, wherein the blue pigment is a phthalocyanine pigment. 5. The method for producing a green pigment composition according to claim 1, wherein the yellow pigment is at least one selected from the group consisting of a monoazo type, a disazo type and a benzimidazolone type. 6. A green pigment composition obtained by the production method according to claim 1. 7. A pigment dispersion comprising the green pigment composition according to claim 6 and a vehicle component.