TWI458783B - Green pigment, its manufacturing method and application thereof - Google Patents

Description

Green pigment, its manufacturing method and its application

The present invention relates to a green pigment, a method for producing the same, a coloring agent containing the same, and a coloring method for an article using the same. More specifically, the present invention relates to a green pigment in which a polyhalogenated zinc phthalocyanine molecule and a polyhalogenated non-zinc metal phthalocyanine molecule are compositely stacked, a green pigment composition containing the same, a method for producing the same, a coloring agent containing the same, and a use thereof The method of coloring the items and the colored items.

With the recent development of informational machines, liquid crystal color displays are used as information display components for display on personal computers, mobile information devices, televisions, projectors, monitors, car satellite navigation, mobile phones, electronic computers and electronic dictionaries. Screens; displays for information boards, guide boards, function boards, sign boards, etc.; all information such as digital cameras and video recorders have been used in a variety of related machines. A color filter (hereinafter, abbreviated as "CF") mounted on a liquid crystal color display is also required to have high image quality, wide color gamut, high definition, color density, light transmittance, and contrast. The image performance is superior to the quality. For the green pigment used for the CF green pixels mounted on the liquid crystal color display, CI Pigment Green 36 (hereinafter referred to as "PG36") has been used, but when high image quality and wide color gamut are desired, PG36 is more greenish-colored CI Pigment Green 58 (hereinafter, referred to as "PG58" is evaluated for its acuity and absorption wavelength acuity.

A polybromine-based/polychlorinated zinc phthalocyanine pigment such as PG58 is used as a specific color in the complementary colors of the four primary colors of yellow, red, blue, and black which are commonly used in the coloring field of paints and printing inks. Further, as described above, a pigment for green pixels which is CF is recently used. However, in the manufacturing stage and storage of the organic solvent-based coloring agent such as paints and printing inks, or in the coloring processing and product-forming step, and in the manufacturing steps of the color resist and CF for CF, it is easy to occur depending on the use conditions. Problems such as hue change, deterioration of sharpness, and decrease in stability due to inevitable and necessary problems such as solvent resistance and heat resistance. In order to improve the shortcomings of these physical properties, it is desired to develop a green pigment which is vivid and continues to maintain a yellowish green hue and is excellent in physical properties.

The inventors of the present invention have repeated efforts to achieve the object of the present invention, and have found that a new construction of a PG58 molecule and a non-zinc metal pigment molecule having a molecular structure similar to that of its molecular structure is stacked. The composite pigment construction can continue to maintain excellent color characteristics, imparts robustness to organic solvents and heating, and solves the above problems, and achieves the completion of the present invention.

That is, according to the first aspect of the present invention, a green pigment is provided, and the green pigment is characterized by a polyhalogenated zinc phthalocyanine having an average number of halo substituents of 12 to 16, and the number of substitutions with the average halo group is A composite deposit of 12 to 16 halogenated non-zinc metal phthalocyanines.

Further, according to another aspect of the present invention, there is provided a method for producing the green pigment, characterized in that the polyhalogenated zinc phthalocyanine and the polyhalogenated non-zinc metal phthalocyanine are dissolved in a medium, and From the solution, the above two molecules are co-precipitated in a composite deposit form.

Furthermore, according to another aspect of the present invention, there is provided a green pigment dispersion composition characterized by containing an organic solvent system, an aqueous system or a water-hydrophilic organic solvent mixed solvent liquid medium, and a polymerization medium. A polymer medium composed of a polymerizable monomer or a polymerizable monomer, and a resin medium made of a plasticizer, an oligomer or a synthetic resin, and further containing a polymerization system dispersant or a low molecular dispersion auxiliary agent as a dispersion, if necessary Auxiliary agent.

Further, according to another aspect of the present invention, there is provided a coloring agent characterized by further comprising a diluted medium, a thermoplastic polymer as a coating material, and a reactive polymerization in the green pigment dispersion composition. One or more materials selected from the group consisting of a bulk, a reactive oligomer, a polymerizable monomer, and a crosslinking agent are further contained, if necessary, a curing catalyst or a polymerization catalyst.

According to still another aspect of the present invention, there is provided a coloring method of an article in which an article is colored by using the above pigment dispersion composition or coloring agent, and a colored article formed therethrough.

This green pigment is vivid and continues to maintain a yellowish green hue, and is excellent in physical properties, particularly heat resistance and solvent resistance, and is particularly advantageous for use as a pigment for green pixels as a color filter. According to the effect of the green pigment of the present invention, the use of the two pigments in combination cannot be achieved. According to such an excellent effect of the green pigment of the present invention, it is predicted that two pigment molecules constituting the pigment are strongly piled together, and are provided by a new composite pigment structure enhanced by intermolecular interaction. In particular, the two molecules are deposited by π-π interaction with each other, and the two molecules recombine and form crystals, which are different from the crystals of the respective original pigments, and it is considered that a new pigment is formed. However, the above theory is based on assumptions, and the present invention is not limited by such theory.

<definition>

In the description of the present invention, a polyhalogenated zinc phthalocyanine having an average number of halo substituents of 12 to 16 is represented by poly(12-16)halogenated zinc phthalocyanine, and the average number of halo substituents is 12-16. The polyhalogenated non-zinc metal phthalocyanine is represented by a poly(12-16) halogenated non-zinc metal phthalocyanine. That is, "(12-16)" in the above expression means the average number of substituted halo groups in each pigment molecule. In the following, the terms "halogen", "bromo group" and "chlorine group" are indicated by the scratches and the numbers indicated in the front, which also indicate "halo" and "bromo" in the pigment molecule. And the average number of substituents of "chlorine".

Further, in the present specification, when a plurality of (12-16) halogenated zinc phthalocyanines and a plurality of (12-16) halogenated non-zinc metal phthalocyanines are described as molecular aggregate pigments, they are described as multiple (12). ~16) a halogenated zinc phthalocyanine pigment and a plurality of (12-16) halogenated non-zinc metal phthalocyanine pigments, or a brief description of A pigments and B pigments, and further described by molecules constituting the pigments, They are described by compound names of multiple (12-16) halogenated zinc phthalocyanines and poly(12-16) halogenated non-zinc metal phthalocyanines, or briefly described as A molecules and B molecules.

In the present specification, a composite of a polyhalogenated zinc phthalocyanine having an average number of halo substituents of 12 to 16 and a polyhalogenated non-zinc metal phthalocyanine having an average number of halo substituents of 12 to 16, It refers to a substance that crystallizes to form a crystal, and is substantially synonymous with the eutectoids of the two pigments.

<Manufacturing method>

The green pigment of the present invention is prepared, for example, according to the following method. That is, a poly(12-16)halogenated zinc phthalocyanine pigment (A pigment) and a poly(12-16) halogenated non-zinc metal phthalocyanine pigment (B pigment) are dissolved in a medium in which two pigments are dissolved, so that The A molecule of the A pigment and the B molecule of the B pigment are combined to form a green pigment by co-precipitation. As the medium for dissolving the two pigments, an acid, preferably sulfuric acid, more preferably fuming sulfuric acid or 100% sulfuric acid or the like is used.

In the eutectoid method of the green pigment of the present invention, the A molecule and the B molecule are not simultaneously soluble, and the A molecule is deposited by the B molecule. For example, it is necessary to avoid the condition in which only A molecules are precipitated and B molecules are not precipitated. As a method of eutectoid analysis, for example,

(1) a method of adding an aqueous acid to reduce the acid concentration in an acid solution (preferably a high-concentration acid solution) in which the A pigment and the B pigment are dissolved, and to precipitate two molecules,

(2) in a high-concentration acid solution in which A pigment and B pigment are dissolved, a method of absorbing water to lower the acid concentration and lowering the solubility, and depositing two molecules,

(3) A method in which a high-concentration acid solution in which A pigment and B pigment are dissolved is injected into a large amount of water or ice water which is vigorously stirred or sprayed, and two molecules are precipitated and accumulated in an instant.

In the above (3), the water for precipitation or the ice water may contain an organic solvent. According to a preferred aspect of the present invention, the above method (3) is preferred. In particular, the water is sprayed at a high speed by a vacuum suction device such as a suction device or an ejector, and the high-concentration sulfuric acid solution of the pigment is attracted by the decompression action and brought into contact with the water of the high-speed jet, and the method of diluting and precipitating the pigment particles is good. In addition, a high-speed mixer such as a dissolver or a homogenizer, or a mixing tank equipped with a high-efficiency mixer such as "Max Blend" (trade name, manufactured by Sumitomo Heavy Industries, Ltd.), is used to vigorously stir the water for precipitation. A method in which the acid solution of the pigment is dropped, flowed or injected (hereinafter, "injection" is used in the sense of dropping or flowing down), and the pigment particles are diffused and precipitated in water is also preferable.

According to a preferred embodiment of the present invention, in the eutectoidizing step or after the eutecting step, as a pigmentation treatment (forming pigmentation) step, a step of removing impurities in the crude pigment to improve the purity of the pigment, and a pigment are carried out. It is preferred to form a fine step and/or to arrange a step as a crystal of the pigment. The pigmentation treatment in the eutectoid step may be carried out by injecting or forcibly contacting water and ice water containing a water-repellent organic solvent and/or a hydrophilic organic solvent to carry out eutectoid precipitation while crystallizing and crystallizing. A method of treatment, or a method of adding such an organic solvent to the treated water containing the eutectoid and contacting the treatment. Further, after the eutectoid step, a known pigmentation treatment in which an organic solvent, for example, a mixed solvent of xylene is heat-treated, or a mixed xylene emulsion heat treatment or the like is crystallization is carried out, if necessary, One or more of a surfactant, a rosin, various resins, a polymer dispersant, and a pigment derivative may be used in combination. The finening of the pigment can also be carried out in the eutectoid step, and in the case of the subsequent step of the eutectoid step, the dry grinding method and the salt milling method are carried out in a kneader such as a kneader, with a water-soluble salt, A well-known pigment finening method such as kneading, grinding, and miniaturization with a water-soluble organic solvent may be carried out as needed. The primary particles of the finely divided pigment have an average particle diameter of 5 to 130 nm, preferably 10 to 110 nm.

<green pigment>

In the polyhalogenated zinc phthalocyanine pigment constituting the green pigment of the present invention, the halogen group as a substituent means a chlorine group, a bromine group or both. In particular, since the hue of the polyhalogenated zinc phthalocyanine pigment is a vivid yellowish green color, the phthalocyanine green pigment mainly composed of a bromine group is preferred, and the bromine group and the chlorine group are introduced (12 or more and less than 16. Preferably, it is 12 to 15.9) bromo group ‧ (more than 0 and 4 or less, preferably 0.1 to 4) chloro zinc phthalocyanine pigment, and bromine-based (12-16) bromo zinc phthalocyanine pigment It is better. More specifically, the preferred pigment is PG58.

In addition, examples of the non-zinc metal of the (12-16) halogenated non-zinc metal phthalocyanine pigment constituting the green pigment of the present invention include a first metal such as copper, a second metal such as magnesium, and aluminum. A metal of one or more kinds selected from the group consisting of Group IV metal, titanium, tin, etc., Group IV metal, iron, cobalt, nickel, and the like. Further, the halogen group means a chlorine group, a bromine group or both. The preferred bis(12-16)halogenated non-zinc metal phthalocyanine of the green pigment of the present invention having high robustness is exemplified by the introduction of a bromine group and a chlorine group (12 or more and less than 16, preferably 12). ~15.9) bromo group ‧ (more than 0 and less than 4, preferably 0.1 to 4) chloro-based non-zinc metal phthalocyanine, only bromine-based (12-16) bromo-non-zinc metal phthalocyanine, and only More chlorine (12~16) chlorine-based non-zinc metal phthalocyanine, especially (14~16) bromine-based non-zinc metal phthalocyanine.

Polybromochlorozinc phthalocyanine and polybrominated chloro-based non-zinc metal phthalocyanine are obtained by a post-bromination method in which a phthalocyanine pigment is brominated. However, it is generally impossible to avoid chlorination while causing chlorination, and it is difficult to completely control the kind and substitution number of the halogen, so that the desired color pigment is selected from the obtained material, and it is preferably used.

In order to control the type of halogen and the number of substitutions to produce green pigments, it is desirable to introduce a predetermined number of substituted brominated, chlorinated or brominated phthalic anhydrides, quinones, sebaconitriles or amine groups. Iminoisoindoles are used as starting materials and are subjected to condensation reaction to synthesize brominated or chlorinated, bromine ‧ zinc chloride or non-zinc metal phthalocyanine pigments. In particular, polybromozinc phthalocyanine pigments having a bromo group and polybrominated non-zinc metal phthalocyanine pigments, such as tri- or tetrabromophthalic anhydride, tri- or tetrabromo-imine, tri- or tetrabromo A method for synthesizing a pigment based on a dinitrile or a tris or tetrabromoaminoiminoisoindole as a raw material and co-condensed with a zinc salt or a non-zinc metal salt can be preferably obtained.

The green pigment of the present invention is excellent in robustness such as solvent resistance and heat resistance. The particle size of the pigment particles before and after the heating and boiling treatment of the green pigment of the present invention is not greatly elongated, and the diffraction angle and the diffraction intensity of the X-ray diffraction are substantially unchanged. As a method of confirming this, the method of heat-processing in an organic solvent is mentioned. When a polyhalogenated zinc phthalocyanine pigment is present, the crystal particles are greatly grown, and the green pigment of the present invention is heat-treated under the processing conditions of coarsening. The change of the obtained treated pigment particles can be confirmed by a procedure in which the pigment particles are further grown in a needle shape according to an electron micrograph. Further, an X-ray diffraction chart for treating a pigment or a portion of a coarse pigment separated therefrom can confirm the mixing of the pigment particles based on whether or not only the polyhalogenated zinc phthalocyanine pigment is substantially not shown or exhibits a characteristic angle of diffraction. The extent of existence.

<Evaluation experiment>

A PG36 pigment, a PG58 pigment, and a green pigment of the present invention are prepared. Further, a simple pigment mixture in which a comparative PG36 pigment and a PG58 pigment are kneaded as a methanol paste is also prepared. Each pigment was added to a xylene solvent, heated, and boiled to treat the pigment with a solvent, and the change in the particle size and crystal state of the treated pigment was investigated.

The PG36 pigment, the PG58 pigment, the green pigment of the present invention, and the simple pigment mixture before the solvent treatment were photographed by a 60,000-fold electron microscope. The photograph shows that the pigments are respectively microparticles or spheres having a size of about 30 to 50 nm (0.03 to 0.05 μm).

Regarding the pigment of the xylene boiling treatment, first, the treated pigment of PG58 is such that the crystal particles are very grown and coarsened. Its electron micrographs were photographed at a magnification that was 10,000 times lower than other pigments. No particulate matter was observed in the electrophotographic photograph, and the whole was only needle-like or thicker glass fiber crystal. When the crystal is expressed by "length × width", it is about 1 μm × 0.05 μm to 7 μm × 0.2 μm in needle crystals, and coarse crystal particles which have grown into a combination thereof are also observed. Therefore, it was shown that the PG58 pigment was very unstable in the solvent. The PG36 pigment, the simple pigment mixture, and the xylene boiling treatment pigment of the green pigment of the present invention were photographed by a 60,000-fold photographic electron microscope. The shape of the pigment particles of the treated pigment of PG36 is the same as that of the microparticles or spheres of about 30 to 70 nm before the treatment, and is shown to be stable in a solvent. The mixture of the PG36 pigment and the PG58 pigment showed fine particles and acicular or glassy fibrous crystal particles, and showed a photograph in which two pigments were mixed.

The green pigment of the present invention exhibits a microparticle shape or a spherical shape of about 30 to 70 nm as before the treatment. However, depending on the case, fine needle-like crystals having a width of about 30 nm and a length of about 1 μm were observed, and it was presumed that PG 58 which was not deposited due to blurring of the deposition conditions was mixed. However, when it is used as a coloring agent, the robustness is less affected by it, and in many cases, it is used substantially equally.

X-ray diffraction was measured for each of the pigments before and after the above-mentioned xylene boiling treatment. Tables 1 and 2 show the major diffraction peaks and relative intensities approximately coincident with the diffraction angle. In the table, "2θ" indicates the diffraction angle (°), the "%" column indicates the relative intensity of the diffraction in %, the "Shape" column indicates the pattern of the diffraction peaks, "s" indicates the sharp pattern, and "b" indicates the sharp pattern. Wide pattern.

From the above results, it was revealed that the PG36 pigment was almost completely unchanged at the diffraction angle and the relative intensity before and after the treatment, and the crystal pattern showed no change except for a slight sharpness. On the other hand, the PG58 pigment exhibits a sharp and large diffraction pattern by X-ray diffraction and many diffraction angles, indicating that the pigment crystals are greatly grown and the surface spacing is arranged. Further, the diffraction of the mixture of PG36 pigment and PG58 pigment is of course represented by a balanced pattern of diffraction of two pigments.

The green pigment of the present invention exhibits a diffraction that is completely different from the diffraction of the above mixture, showing crystals of completely different dimensions from the mixture. If compared to the diffraction diagram of the PG36 pigment, the graphs before and after the solvent treatment all contain diffraction angles, relative intensities, and a diffraction pattern showing a diffraction pattern close to the PG36 pigment. It is presumed that the diffractive shape of the green pigment of the present invention is broad and sharp in view of the difference, showing accumulation of non-zinc pigment molecules.

Further, when the diffraction pattern of the green pigment of the present invention is examined, the deposition of the A pigment and the B pigment is as follows. That is, the green pigment of the present invention differs from the PG36 pigment and the PG58 pigment in the sharpness of the diffraction shape, and is slightly wider, but the overall diffraction pattern of the three pigments is similar, at each diffraction angle. Diffraction occurs at the same point, and its relative intensity is similar. From this, it is speculated that the PG36 molecule and the PG58 molecule are molecules whose molecular structures are easy to accumulate with each other.

The green pigment of the present invention is particularly useful as a green pigment for green pixels for CF, and it is expected to exhibit a vivid yellowish green color. In this application, the particle diameter of the pigment particles before and after the heat treatment in the organic solvent is not greatly elongated, and it is also advantageous in that the diffraction angle and the diffraction intensity of the X-ray diffraction are not greatly changed. The green pigment of the present invention allows the mixing in the case where the undeposited polyhalogenated zinc phthalocyanine pigment is present in a slight mixing, depending on the formulation and processing conditions of the coloring agent or the use thereof, without substantially affecting it. presence.

Regarding the molar ratio of polyhalogenated zinc phthalocyanine to polyhalogenated non-zinc metal phthalocyanine, firstly, in the range of yellowish green shades which can maintain or not hinder the excellent properties of polyhalogenated zinc phthalocyanine, and It is desirable to improve the heat resistance and the solvent resistance of the polyhalogenated zinc phthalocyanine, and it is desirable to form a molar ratio which can bring about the above-mentioned properties and physical properties. In addition, the heat resistance, the solvent resistance, and the like may be appropriately determined depending on the type of the solvent to be used in forming the coloring agent or the heat resistance, depending on the heating conditions to be treated after the coloring.

According to a preferred aspect of the present invention, the molar ratio of polyhalogenated zinc phthalocyanine (XnMePc) to polyhalogenated non-zinc metal phthalocyanine (XnMePc), in the case of stability, XnZnPc: XnMePc= 30:70~95:5, preferably 40:60~90:10. Especially in the case of paying attention to color tone, it is better to use 82:18~95:5.

<Use>

The green pigment of the present invention can be used, for example, as a coloring agent for coating, printing, dyeing, dyeing, writing, drawing, inkjet printing, electrophotographic printing, or electrostatic printing. In addition, in addition to the ink for forming a CF pixel, a coloring agent such as a coating material, a resin coloring agent using a resin coloring agent, a printing ink, a coloring agent, a dyeing agent, a stationery, a drawing instrument, and the like may be used. Use of a coloring component such as an ink for ink, a developer for electrophotographic printing, or a developer for electrostatic printing.

Therefore, according to another aspect of the present invention, a coloring agent containing the green pigment of the present invention is provided. In order to produce the color former of the present invention, a pigment composition is prepared, and the pigment composition may also contain the green pigment of the present invention. Therefore, according to another aspect of the present invention, a pigment dispersion composition containing the green pigment of the present invention is further provided. The form of the pigment dispersion composition may be an aqueous pigment dispersion composition, an oil pigment dispersion composition, a resin dispersion type processing pigment, or an energy ray curable pigment dispersion composition. Further, the pigment concentration is usually set to be as high as 10% to 50%, and the pigment may be finely dispersed in advance to easily form a colorant. The pigment composition of the present invention contains the green pigment of the present invention, and contains an organic solvent system as a medium, an aqueous liquid or a water/hydrophilic organic solvent mixed solvent, and a suitable liquid medium; a polymerizable oligomer, a polymerizable monomer, etc. A resin medium composed of a polymerizable liquid medium, a plasticizer, an oligomer, a synthetic resin, or the like; a polymerization system dispersing agent or a low molecular weight dispersing aid as a dispersing aid as needed.

In the pigment dispersion composition of the present invention, a diluent medium, a thermoplastic polymer, a reactive polymer, a reactive oligomer, a polymerizable monomer, and a crosslinking agent which form a coating material are further blended. A coloring agent which is suitable for the purpose of production, and which is required to further add a curing catalyst, a polymerization catalyst, etc., and uniformly mix and disperse, and to produce a purpose. According to one aspect of the present invention, in the coloring agent of the present invention, the mass ratio of the pigment (P) to the coating film material (V) can be appropriately determined in consideration of the use, the required performance, and the like, and is generally P. :V=80:20~1:99, preferably 70:30~10:90.

When the pigment is dispersed in the coloring agent or the pigment dispersion composition of the present invention, a known additive may be added in addition to the film-forming polymer. Examples of such an additive include a known ionic pigment derivative as a pigment dispersion stabilizer, and an ionic ionic polymerization system dispersant, a surfactant, an antifoaming agent, a smoothing agent, and an adhesion agent. Various additives such as a decane coupling agent.

As the pigment dispersing machine used for producing the pigment dispersion composition and the coloring agent, a known dispersing machine such as a vertical medium dispersing machine such as ball milling, sanding, bead milling, DYNO-MILL, horizontal bead mill, or the like can be used. Horizontal media disperser, roller mill, ultrasonic mill, high pressure collision disperser, etc. The dispersion treatment is carried out by a method of dispersing a plurality of times using one type of dispersing machine or a method of combining two or more types of dispersing machines. The average particle diameter is usually about 5 to 130 nm, preferably 10 to 11 Onm.

As the resin for forming the coating material contained in the coloring agent of the present invention, a known resin component which is blended for various uses can also be used. For example, a known coating film material such as a synthetic rubber resin, an acrylic resin, a vinyl resin, a chlorinated rubber resin, an alkyd resin, a urethane resin, an epoxy resin, an anthracene resin, or a fluororesin may be mentioned. A coating material for forming an energy ray-curable property such as an ultraviolet curable resin or an electron beam curable resin. The above-mentioned formed film material may further have a reactive group, and examples of the reactive group include a methylol group, an alkylhydroxymethyl group, an isocyanate group, a masked isocyanate group, an epoxy group, and the like. . Further, an oligomer and a monomer may be used depending on the use, and a crosslinking agent may be used in combination, for example, a methylol melamine-based, an isocyanate-based or an epoxy-based crosslinking agent.

The coloring agent of the present invention is a coloring agent for a color filter, and any of the conventionally known ones can be used as the film forming material, and is not particularly limited. In the case where the pixel ink is formed into a photolithographic development type, the polymer ink is irradiated with an energy ray collectively referred to as a photosensitive pixel ink. Examples of the addition polymerization or addition-crosslinking ink include heat polymerization or energy ray-curable inks such as a thermal polymerization type, a laser heat polymerization type, an ultraviolet polymerization type, a photocation polymerization type, and an electron beam polymerization type. The film forming material used therein is a previously known addition polymerization or an unsaturated double bond having a crosslinkability or a monomer, oligomer and/or polymer having a polymerizable cyclic ether group, and optionally added The polymerization initiator or the liquid medium constitutes an addition polymerization or a crosslinkable solid adhesion agent.

Specific examples of the film forming material include pentaerythritol di(meth)acrylate ("(meth)acrylate" means acrylate methacrylate), dipentaerythritol poly(4~6) (meth)acrylate. Monomers such as bisphenol type epoxy resin-di(meth)acrylate; (meth) acrylate-(meth)acrylic acid (co)polymer, (meth) acrylate-styrene-( Methyl)acrylic acid copolymer, etc.; polyester acrylate resin, poly epoxy acrylate resin, polyurethane acrylate resin, polyether acrylate resin, polyol acrylate resin, etc.; A phenolic resin or an unsaturated polyester resin. They may be used alone or in combination of two or more.

Further, the photopolymerization initiator is a known photopolymerization initiator, and examples thereof include 1-hydroxy-cyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenyl-propane-1- Ketone, 2,2-diethoxyethyl benzene, 2-methyl-1-(4-methylthio)phenyl)-2- Lolinylpropan-1-one, 2-benzyl-2-(N,N-dimethylamino)-1-(4- Phenylphenyl)butanone-1 and the like. They may be used alone or in combination of two or more.

Various articles can be colored by using the pigment dispersion composition of the present invention and a coloring agent using the same. In the case of forming a green pixel of a color filter, a previously known green color photoresist can be modulated with a well-known yellow frequency material and combined with a red photoresist and a blue photoresist on a CF substrate to previously known photoresist. The method of forming a green, red, or blue pixel by a method such as a method, a transfer method, an attaching method, an inkjet printing method, or a printing method is not limited thereto. For example, in the case where a pixel pattern of a color filter is formed on a substrate, the photosensitive pixel ink is formed on the substrate, for example, using a spin coater, a roll coater, a slit coater, a printer, or the like. The coating is fully applied, the reticle is closed after preliminary drying, and the pattern is exposed and baked using an ultra-high pressure mercury lamp. Next, development and washing are performed, and post-baking is performed as needed to form a pattern of color filters.

In the color filter, as the pigment forming the red pixel (R) and the blue pixel (B) used together with the green pixel (G), many conventionally known pigments are used. For example, an azo-based pigment such as an insoluble azo-based, a soluble azo-based or a high-molecular-weight azo-based dye, a quinophthalone pigment such as quinophthalone red or quinophthalone purpura, or a diketopyrrolopyrrole is used. Pigment, anthraquinone pigment, anthraquinone pigment, phthalocyanine pigment such as phthalocyanine blue, isoindolinone pigment, two Purple et al A pigment, a quinoline ketone yellow pigment, a nickel azo yellow or the like, and the like.

Specific examples of representative pigments for penetrating R, G, and B pixels include PR177, PR242, and PR254 in red pigments, and PY83, PY138, PY139, PY150, and PY185 as yellow pigments for complementary color or individual color. For example, the blue pigment is PB15:6, PB60, etc., and the violet pigment used as the complementary color or the individual color is PV23 or the like, and the co-sinking pigment of the above red pigment and yellow pigment, and the blue pigment and purple are also mentioned. Co-precipitated pigments, solid solution pigments or mixed crystal pigments.

Further, the above mainly describes the pixel formation of the color filter, but the pigment dispersion composition and the color former of the present invention are also suitable for various other uses, for example, as synthetic or natural resins, paints, plastic films, various papers, synthetic papers, and the like. Printing inks, coloring agents for paper, dyeing agents for woven fabrics, inks for notes, toners for color photocopiers, inks for inkjet printers, inks for thermal transfer ribbons, etc. Green colored items.

[Examples]

Next, the present invention will be described in further detail by way of specific examples. In addition, the parts and % in the text are quality benchmarks unless otherwise specified. Further, the number of bromine substitutions of the following polybrominated non-zinc metal phthalocyanine indicates the number of loading ratios of the condensation reaction.

Production Example 1 (Manufacture of composite green pigment of PG58 molecule and 16 bromo ketone phthalocyanine molecule) Synthesis of (1) 16 bromo copper phthalocyanine pigments

As a synthesis reaction apparatus, a reaction vessel and a heating apparatus which are equipped with a stirring apparatus, a countercurrent cooler, and a thermometer are prepared. Tetrabromophthalic anhydride which has a bromine content of 69.0% as a raw material and a number of bromine substitutions per molecule of 4.0 is prepared. To the reaction vessel, 140.0 parts of nitrobenzene in the reaction medium, 46.4 parts of the above tetrabromophthalic anhydride, 27.0 parts of urea, 7.1 parts of titanium tetrachloride, and 3.4 parts of copper chloride were added. The reaction temperature was gradually raised from 100 ° C to 175 ° C, and the mixture was stirred for 4 hours as it was, and the reaction was continued. The reaction temperature before the end of the reaction was 195 °C. The yield of the crude pigment was 44.8 parts, and the yield of the crude pigment was 97.4%. Further, 100% sulfuric acid was prepared by mixing 95% sulfuric acid and 20% fuming sulfuric acid. 10 parts of the obtained crude pigment was dissolved in 100 parts of 100% sulfuric acid, and the mixture was stirred at 70 ° C for 1 hour, precipitated in 10 times of ice water, filtered, and washed with water (hereinafter referred to as "sulfuric acid purification"). Next, it was washed with a dilute aqueous solution of sodium hydroxide and ethanol and dimethylformamide. The yield of the refined pigment was 94.9%. According to elemental analysis, the content of copper element was 3.44% (theoretical value: 3.456%), and the content of bromine was 69.8% (theoretical value: 69.52%). The average number of bromine substitutions per molecule calculated from the analytical value of the obtained 16 bromo ketone phthalocyanine green pigment was 16.1, indicating that the phthalocyanine skeleton was completely substituted with 16 bromine groups. Hereinafter, this is referred to as "16 bromo ketone phthalocyanine coarse particle pigment".

(2) Stacking of PG58 and 16 bromo ketone phthalocyanine molecules

The average substitution number of bromine is about 13 and the average number of substitutions of chlorine is about 3, and PG58 is 16.39 g (as the calculated value of the average number of substituents is 0.00960 mol, the same below), and the synthesis reaction is carried out in the above (1). 16 bromo copper phthalocyanine coarse particle pigment 3.61 g (0.00196 mol), dissolved in 20% fuming sulfuric acid 140 g, and stirred at 70 ° C for 2 hours, and allowed to cool to room temperature. The water is sprayed at a high speed by a suction device, and the reduced pressure sulfuric acid solution is sucked by the reduced pressure capillary tube, and is contacted with the high-speed jet water to dilute and precipitate the pigment particles, and is filtered and washed with water. Next, pigmentation was carried out by a xylene emulsion method to obtain a green pigment. Hereinafter, this is called "green stacked crude pigment-1".

(3) Preparation of composite stacked green fine particle pigment by salt grinding and fine treatment

100 parts of the green-stacked crude pigment-1 obtained in the above (2) was placed in a kneader equipped with a pressure cap together with 600 parts of sodium chloride powder and 110 parts of diethylene glycol. The mixture was pre-mixed in a kneader to a uniformly wet block, and then a pressure cap was placed thereon and the contents were pressed at a pressure of 6 kg/cm ² and kneaded and ground. While the contents were managed at a temperature of 92 to 98 ° C, the mixture was incubated for 2 hours. The obtained ground product is stirred in 3000 parts of 2% sulfuric acid added at 80 ° C for 1 hour, and then filtered and washed with water to remove sodium chloride and diethylene glycol to obtain a fine composite stacked green pigment. Pressurized cake. In order to measure the particle size of the obtained pigment, 200% of the nonionic active agent relative to the pigment was added to the pigment press cake, and diluted with water to prepare a dispersion of the pigment by ultrasonic dispersion, and the particle size measuring machine "Model N-4" was used. When the average particle diameter is measured (manufactured by Coaler Co., Ltd.), the average particle diameter is about 25 to 35 nm. The pressed cake was dried and pulverized to obtain a green pigment. Even if the obtained pigment was heat-treated in an organic solvent, no substantial change was observed in the particle size and crystal state of the pigment. Hereinafter, this is called "green stacked pigment-1".

Production Example 2 (Manufacture of composite green pigment of PG58 and 16 bromo ketone phthalocyanine molecules) (1) Stacking of PG58 molecule and 16 bromo ketone phthalocyanine molecule

16.81 g (0.00985 mol) of PG58 used in Production Example 1 (2) and 3.19 g (0.00173 mol) of 16 bromo copper phthalocyanine coarse particle pigment obtained by the synthesis reaction of Production Example 1 (1) were dissolved in 20% fuming sulfuric acid 200 g, and stirred at 70 ° C for 2 hours, allowed to cool to room temperature, and then poured into a Max Mixing Stirring Tank (manufactured by Sumitomo Heavy Industries, Ltd.) containing 2000 g of butyl cellosolve. In gram ice water, filter and wash. The pressed cake was dried and pulverized to obtain a green pigment. Hereinafter, this is called "green stacked pigment-2".

Production Example 3 (Manufacture of composite green pigment of PG58 molecule and PG36 molecule) (1) Stacking of PG58 molecule and PG36 molecule

In the same manner as in Production Example 2, PG58 used in Production Example 1 (2) was 18.00 g (0.01054 mol), and the average number of substitutions of bromine was about 13, and the average number of substitutions of chlorine was about 3, and PG36 was 2.00 g (0.00117 mol). Ear), dissolved in 20% fuming sulfuric acid 200 g, and stirred at 70 ° C for 2 hours, allowed to cool to room temperature. The water is sprayed at a high speed by a suction device, and the reduced pressure sulfuric acid solution is sucked by the reduced pressure capillary tube, and is contacted with the high-speed jet water to dilute and precipitate the pigment particles, and is filtered and washed with water. Next, pigmentation was carried out by a xylene emulsion method to obtain a green pigment. Hereinafter, this is called "green stacked crude pigment-3".

(2) Preparation of composite stacked green fine particle pigment by salt grinding and fine treatment

In the same manner as in the production example 1 (3), 100 parts of the green-stacked crude pigment-3 obtained in the above (1), and 600 parts of sodium chloride powder and 110 parts of diethylene glycol were placed together in a kneading machine equipped with a pressure cap. The same treatment is carried out for mixing and grinding. The mixture was treated with a mixture of 2% sulfuric acid, and then filtered and washed with water to remove sodium chloride and diethylene glycol to obtain a pressed cake of a finely packed composite green pigment. The average particle size is approximately 30 nm. The pressed cake was dried and pulverized to obtain a green pigment. Even if the obtained pigment was heat-treated in an organic solvent, no substantial change was observed in the particle size and crystal state of the pigment. Hereinafter, this is called "green stacked pigment-3".

Production Example 4 (Manufacture of composite green pigment of PG58 molecule and 16 bromo aluminum phthalocyanine molecule) (1) Synthesis of 16 bromo aluminum phthalocyanine pigment

In the same manner as in Production Example 1 (1), the same number of parts of nitrobenzene, tetrabromophthalic anhydride, urea, and hafnium chloride were placed in the reaction vessel, and copper chloride was changed to 3.34 parts of aluminum chloride. The reaction temperature was raised from 100 ° C to 175 ° C and stirred for 5 hours, and the final reaction temperature was 200 ° C. The yield of the crude pigment was 40.0 parts, and the yield of the crude pigment was 87.1%. The obtained crude pigment was subjected to sulfuric acid purification in the same manner as in Production Example 1 (1), and the pigment precipitate was filtered, washed with water, dried, and pulverized. The pigment thus obtained is referred to as "16 bromo aluminum phthalocyanine pigment".

(2) Stacking of PG58 molecule and 16 bromo aluminum phthalocyanine molecule

In the same manner as in Production Example 1 (2), 14.75 g (0.00864 mol) of PG58 and 5.24 g (0.00288 mol) of the 16 bromo aluminum phthalocyanine pigment of the above (1) were dissolved in 20% of fuming sulfuric acid 140 g at 70 Stir in °C and let cool. The flammable sulfuric acid solution of the above pigment is sucked using an aspirator, and is contacted with water of a high-speed jet to dilute and precipitate the pigment particles. The precipitate was filtered, washed with water, and then pigmented by a xylene emulsion method to obtain a green pigment. Hereinafter, this is called "green stacked crude pigment-4".

(3) Preparation of composite stacked green fine particle pigment by salt grinding and fine treatment

In the same manner as in Production Example 1 (3), the green-stacked crude pigment-4 obtained in the above (2) was placed in a kneader together with sodium chloride powder and diethylene glycol, and pre-mixed, followed by kneading and grinding. The obtained ground product was stirred in 2% dilute sulfuric acid, filtered, washed with water, dried, and pulverized to obtain a green pigment. Even if the obtained pigment was heat-treated in an organic solvent, no substantial change was observed in the particle size and crystal state of the pigment. Hereinafter, this is called "green stacked pigment-4".

Production Example 5 (Manufacture of composite green pigment of PG58 molecule and 16 bromomagnesium phthalocyanine molecule) (1) Synthesis of 16 bromo magnesium phthalocyanine pigment

In the same manner as in Production Example 1 (1), the same number of parts of nitrobenzene, tetrabromophthalic anhydride, urea, and hafnium chloride were placed in the reaction vessel, and copper chloride was changed to 2.39 parts of magnesium chloride. The reaction temperature was raised from 100 ° C to 175 ° C and stirred for 4 hours, and the final reaction temperature was 195 ° C. The crude pigment yield was 39.9 parts and the crude pigment yield was 88.7%. The obtained crude pigment was subjected to sulfuric acid purification in the same manner as in Production Example 1 (1), and the pigment precipitate was filtered, washed with water, dried, and pulverized. The pigment thus obtained is hereinafter referred to as "16 bromo magnesium phthalocyanine pigment".

(2) Stacking of PG58 molecule and 16 bromo magnesium phthalocyanine molecule

With the treatment of Production Example 1 (2), 6.43 g (0.00377 mol) of PG58 and 13.57 g (0.00754 mol) of the 16 bromo magnesium phthalocyanine pigment of the above (1) were dissolved in 20% of fuming sulfuric acid 140 g at 70 Stir in °C and let cool. The flammable sulfuric acid solution of the above pigment is sucked using an aspirator, and is contacted with water of a high-speed jet to dilute and precipitate the pigment particles. The precipitate was filtered, washed with water, and then pigmented by a xylene emulsion method to obtain a green pigment. Hereinafter, this is called "green stacked crude pigment-5".

(3) Preparation of composite stacked green fine particle pigment by salt grinding and fine treatment

In the same manner as in Production Example 1 (3), the green-stacked crude pigment-5 obtained in the above (2) was placed in a kneader together with sodium chloride powder and diethylene glycol, and pre-mixed, followed by kneading and grinding. The obtained ground product was stirred in 2% dilute sulfuric acid, filtered, washed with water, dried, and pulverized to obtain a green pigment. Even if the obtained pigment was heat-treated in an organic solvent, no substantial change was observed in the particle size and crystal state of the pigment. Hereinafter, this is called "green stacked pigment-5".

Example 1 (Preparation of green pigment high concentration dispersion)

In advance, 30% propylene glycol monomethyl ether acetate of a copolymer of butyl acrylate-styrene-hydroxyethyl acrylate-methacrylic acid (mass ratio: 50:15:10:25, average molecular weight: 12,000) as a pigment dispersion was prepared. An ester (hereinafter, abbreviated as "PGMA") solution. Hereinafter, it is called "resin dispersing agent PGMA solution-1."

19 parts of "green-pigmented pigment-1" obtained in Production Example 1 (3), 1 part of a green pigment deuterated derivative, and a cationic polymer-based dispersing agent (polyester amide-polymerized ethyl imine, 50%) 12 parts of the solution, 50 parts of the "resin dispersing agent PGMA solution-1" and 18 parts of PGMA shown above, and stirred with a dissolving rod for 2 hours, and after confirming that there is no pigment block, in a horizontal ring type bead mill disperser The zirconia beads (0.65 mm in diameter) were dispersed at a peripheral speed of 14 m/s to obtain a green high-concentration pigment dispersion and a "green stacked pigment high-concentration dispersion-1".

Example 2 (Preparation of a high concentration dispersion of each color pigment) (1) Modulation of various color microparticle pigments treated by miniaturization

Prepare PR254, PY138, PB15-6 and PV23. According to the salt grinding and finening treatment of the composite deposited green pigment of Production Example 1 (3), each pigment powder is mixed with sodium chloride powder and diethylene glycol into a kneading machine equipped with a pressure cap, and kneaded and kneaded. grinding. The obtained ground material was also dissolved in a salt, a solvent, filtered, and washed with water to obtain a press cake of each fine pigment. The fine particles of the respective colors have an average particle diameter of 30 to 40 nm. The pressed cake was dried and pulverized to obtain a fine powder pigment of each pigment.

(2) Modulation of high concentration dispersion of pigment

In the same manner as in the treatment of Example 1, the fine particles of PR254, PY138, PB15-6 and PV23 obtained in the above (1) and each of the known pigment deuterated derivatives are used instead of the green deposited pigment-1 and the green pigment deuterated derivative. A cationic polymer dispersant, an acrylic resin, and PGMA were blended, and the mixture was stirred and degummed with a dissolving rod, and dispersed by a ring-type bead mill disperser to obtain a high-concentration dispersion liquid of each pigment. Hereinafter, the "high-concentration dispersion-1" is indicated by each color name.

(3) Modulation of pixels to form pixelated ink

In order to form RGB pixels on the glass substrate of the color filter, "green pigment photosensitive dispersion-1", "red pigment photosensitive dispersion-1", and "blue pigment photosensitive" were obtained according to the following Table 3. Sex dispersion-1".

In the above, TMPTA means trimethylolpropane triacrylate, HEMPA means 2-hydroxyethyl-2-methylpropionic acid, and DEAP means 2,2-diethoxyethyl benzene.

Example 3 (modulation of color filters)

The glass substrate subjected to the decane coupling agent treatment was attached to a spin coater, and the "red pigment photosensitive dispersion-1" of the above Example 2 (3) was initially rotated at 300 rpm for 5 seconds and then at 1200 rpm for 5 seconds. Tu. Next, prebaking was carried out at 80 ° C for 10 minutes, and a mask having a mosaic pattern was adhered, and exposure was performed using an ultrahigh pressure mercury lamp at a light amount of 100 mJ/cm ² . Next, development and washing are carried out with a dedicated developer and a dedicated rinse to form a red mosaic pattern on the glass substrate.

Then, using "green pigment photosensitive dispersion-1" and "blue pigment photosensitive dispersion-1" of Table 3, coating and baking were carried out according to the above method to form a green mosaic pattern and a blue mosaic pattern. RGB color filters. The obtained color filter has excellent spectral characteristics, excellent in light resistance and heat resistance, and excellent in light transmittance, and exhibits excellent properties as a color filter for liquid crystal color display.

Example 4 (modulation of color filter)

The green deposited pigments -2 to 5 obtained in Production Examples 2 to 5 were used instead of the green deposited pigment-1 used in the above Example 1, and the same operation as in the above-mentioned Example 1 and Example 2 was carried out to obtain a green pigment photosensitive dispersion liquid. And the red pigment photosensitive dispersion-1 and the blue pigment photosensitive dispersion-1 are simultaneously used, and the color filter is processed in the same manner as in the third embodiment, and has excellent spectral characteristics, and is resistant to light resistance and heat resistance. Excellent, and light penetrating properties are also excellent, and color filters for liquid crystal color displays are obtained.

Example 5 (gravure ink and gravure printing)

12 parts of a vinyl chloride-vinyl acetate-acrylic acid (89:6.7:4.3) copolymer having a carboxyl group (weight average molecular weight of about 30,000) was dissolved in butyl acetate-methyl isobutyl ketone-xylene (43: 20:20) 68 parts of a mixed solvent, and 5 parts of the green deposited pigment obtained in Production Example 1 (3) was added and placed in a ball mill and dispersed for 16 hours. Add 3 parts of cerium oxide, and then add a multi-branched polycarbodiimide cross-linking agent (reaction product of polyhexyl carbodiimide-diisocyanate and dipentaerythritol monolaurate) 20% toluene solution 12 parts, mixed, made into a yellow-green gravure ink. As a gravure ink of a distinctive yellow-green color, other red, blue, yellow, brown, and black intaglio inks are collectively printed with a vinyl chloride film or the like to obtain a film of a multi-color printing vinyl chloride or the like.

Further, the green deposited pigments -2 to 5 obtained in Production Examples 2 to 5 were used instead of the above-mentioned green deposited pigment-1, and the same film as the above-mentioned yellow-green intaglio ink was subjected to gravure printing to obtain a brilliant multicolor printed film. .

Example 6 (paint and coating)

Adding ethyl acetate solution of carboxyl group-methyl methacrylate-ethyl methacrylate-octyl methacrylate-hydroxyethyl methacrylate-methacrylic acid (44:20:10:5) copolymer (solid form) 45 parts by weight of 45 parts, 19.9 parts of xylene, 5 parts of green deposited pigment obtained in Production Example 1 (3), and 15 parts of titanium oxide white pigment were placed in a ball mill and dispersed for 16 hours. A yellow-green acrylic paint of 15 parts of a multi-branched polycarbodiimide cross-linking agent 20% solution used in Example 5 and a 0.1 part of a dispersing agent-preventing formulation were prepared. It can apply yellow-green coating to various wood products, metal products, and plastic products such as mobile phones, personal computers, and other related products, office supplies, and household goods, and can be coated with excellent weather resistance, durability, and water resistance.

Further, the green deposited pigments -2 to 5 obtained in Production Examples 2 to 5 were used instead of the above-mentioned green deposited pigment-1, and the yellow-green acrylic paint was prepared as described above, and the same various members were coated to obtain a brilliant yellow. Green coated products.

Claims (25)

A green pigment characterized by a composite of a polyhalogenated zinc phthalocyanine having an average number of halo substituents of 12 to 16 and a polyhalogenated non-zinc metal phthalocyanine having an average number of halo substituents of 12 to 16. Things. The green pigment according to claim 1, wherein the polyhalogenated zinc phthalocyanine and the polyhalogenated non-zinc metal phthalocyanine have a molar ratio of 30:70 to 95:5. The green pigment according to claim 1 or 2, wherein the halogenated group of the above polyhalogenated zinc phthalocyanine is a chlorine group or a bromine group or both. The green pigment according to claim 3, wherein the polyhalogenated zinc phthalocyanine is a bromozinc phthalocyanine having an average number of bromine substitutions of 12 or more and 16 or less. The green pigment according to claim 3, wherein the polyhalogenated zinc phthalocyanine is a bromochloro group having an average number of bromine substitutions of 12 or more and less than 16 and an average number of chlorine substitutions of more than 0 and less than 4 Zinc phthalocyanine. The green pigment according to item 3 of the patent application, wherein the polyhalogenated zinc phthalocyanine is CI. Pigment Green 58. The green pigment according to claim 1 or 2, wherein the non-zinc metal of the polyhalogenated non-zinc metal phthalocyanine is composed of aluminum, magnesium, titanium, tin, iron, cobalt, nickel, and copper. One or more metals selected. The green pigment according to claim 1 or 2, wherein the halogenated group of the above polyhalogenated non-zinc metal phthalocyanine is a chlorine group or a bromine group or both. The green pigment according to the eighth aspect of the invention, wherein the polyhalogenated non-zinc metal phthalocyanine is a bromine-based non-zinc metal phthalocyanine having an average number of bromine groups of 12 or more and 16 or less. The green pigment according to Item 8 of the patent application, wherein the polyhalogenated non-zinc metal phthalocyanine is a bromine group having an average number of bromine substitutions of 12 or more and less than 16 and an average number of chlorine substitutions of more than 0 and less than 4 Chloro-based non-zinc metal phthalocyanine. The green pigment according to claim 8 , wherein the polyhalogenated non-zinc metal phthalocyanine is a polyhalogenated aluminum phthalocyanine, a polyhalogenated magnesium phthalocyanine, a polyhalogenated oxytitanium phthalocyanine, or a polyhalogenated tin. One or more selected from the group consisting of phthalocyanine and polyhalogenated copper phthalocyanine. For example, the green pigment of claim 1 or 2, wherein the particle diameter of the pigment particles is not greatly elongated before and after heating or boiling treatment in an organic solvent, and the diffraction angle and diffraction intensity of the X-ray diffraction There is also virtually no change. A method for producing a green pigment, which is used for producing a green pigment according to the first aspect of the patent application, characterized in that the above polyhalogenated zinc phthalocyanine pigment and the above polyhalogenated non-zinc metal phthalocyanine pigment are dissolved in fuming A solution obtained by sulfuric acid or 100% sulfuric acid causes the polyhalogenated zinc phthalocyanine and the polyhalogenated non-zinc metal phthalocyanine to be co-precipitated as a composite deposit. A method for producing a green pigment, which is used for producing a green pigment according to item 2 of the patent application, characterized in that the above polyhalogenated zinc phthalocyanine pigment and the above polyhalogenated non-zinc metal phthalocyanine pigment are in the form of a molar Ratio 30:70~95: 5 is dissolved in fuming sulfuric acid or 100% sulfuric acid, and the acid concentration in the obtained solution is lowered, whereby the polyhalogenated zinc phthalocyanine and the polyhalogenated non-zinc metal phthalocyanine are co-emitted in a composite deposit form. The method for producing a green pigment according to claim 14, wherein the reduction in the acid concentration in the solution is carried out by adding an aqueous acid or absorbing water to the solution, or by injecting the solution into vigorous stirring or jetting. It is carried out in a large amount of water or ice water. The method for producing a green pigment according to claim 13 or 14, wherein the non-zinc metal of the polyhalogenated non-zinc metal phthalocyanine pigment is made of aluminum, magnesium, titanium, tin, iron, cobalt, nickel, and copper. One or more metals selected from the group consisting of. The method for producing a green pigment according to claim 13 or 14, wherein the pigmentation treatment and/or the finening step of the pigment are carried out simultaneously with or after the co-emination. The method for producing a green pigment according to the seventeenth aspect of the invention, wherein the pigmentation treatment is performed simultaneously with eutectoid precipitation or after eutectoid precipitation, and the eutectoid or organic solvent is contained; / or contact with water or ice water of a hydrophilic organic solvent, or contact with the above organic solvent. A green pigment dispersion composition comprising: a green pigment according to claim 1 or 2; an organic solvent system, an aqueous system or a water-hydrophilic organic solvent mixed solvent liquid medium; a polymerizable oligomer or a polymerizable property a polymerizable liquid medium composed of monomers; and a plasticizer, oligomer or synthetic resin The resin medium to be formed is further contained, if necessary, a polymerization system dispersant or a low molecular weight dispersing aid as a dispersion aid. A coloring agent comprising: a green pigment dispersion composition of claim 19; and a thermoplastic polymer, a reactive polymer, a reactive oligomer, a polymerizable monomer, and a coating film forming material; One or more selected from the group consisting of a crosslinking agent; further comprising a curing catalyst or a polymerization catalyst as needed. A coloring agent according to claim 20, which is used as a color filter pixel ink, a coating, a resin coloring agent, a printing ink, a coloring agent, a dyeing agent, a stationery, a painting tool, an inkjet ink, A developer for electrophotographic printing or a developer for electrostatic printing. A method of coloring an article, characterized in that the article is colored by using a green pigment dispersion composition of claim 19 or a coloring agent of claim 20th. The coloring method of the article of claim 22, wherein the coloring of the article is on a color filter substrate according to a known photoresist method, a transfer method, an attach method, an inkjet method, or a printing method. This is done by a method of forming a pixel. The coloring method of the article of claim 22, wherein the coloring of the article is based on coating, resin coloring, printing, dyeing, dyeing, writing, drawing, inkjet printing, electronic photo printing or static electricity. Printed. A colored article formed according to the coloring method of claim 22 of the patent application.