JP5297527B2 - Green pigment, method for producing the same, coloring agent comprising the same, and coloring method using the same - Google Patents

Abstract

Disclosed is a green pigment characterized by consisting of a stacked composite which is composed of a polyhalogeno zinc phthalocyanine having an average number of substituent halogen atoms of 12 to 16 and a polyhalogeno non-zinc metal phthalocyanine having an average number of substituent halogen atoms of 12 to 16. The green pigment has both a clear yellowish green color tone and excellent physical properties, particularly, excellent fastnesses to heat and solvent, thus being advantageous for use particularly as a pigment for the green pixel of a color filter.

Description

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

  With the recent development of information devices, LCD color displays are used as information display members for personal computers, mobile information devices, televisions, projectors, monitors, car navigation systems, mobile phones, electronic calculators and electronic dictionaries. It is used in a wide variety of information display related equipment such as information bulletin boards, information bulletin boards, function display boards, sign boards, and other digital display screens. Along with this, color filters (hereinafter sometimes abbreviated as “CF”) mounted on liquid crystal color displays also have images such as high image quality, wide color gamut, high definition, color density, light transmission, and contrast. There is a demand for better quality in terms of performance. Regarding the green pigment used for the green pixel of CF mounted on these liquid crystal color displays, the conventional C.I. I. Pigment Green 36 (hereinafter sometimes referred to as “PG36”) has been used, but when a high image quality and a wide color gamut are desired, C.I. I. Pigment Green 58 (hereinafter sometimes referred to as “PG58”) has been evaluated for its color tone and sharpness of absorption wavelength.

  Polybromo / polychlorozinc phthalocyanine pigments such as PG58 are used as specific colors to complement the four primary color representations of yellow, red, blue and black, which are usually used in the coloring field such as paints and printing inks. As described above, recently, it has been used as a CF green pigment. However, it is inevitable depending on the conditions of use in the manufacturing process and storage of organic solvent-based colorants such as paints and printing inks, in the process of color processing and commercialization, and in the manufacturing process of CF color resists and CFs. It is easy to cause problems such as changes in color tone, deterioration of sharpness, and deterioration of stability due to problems of fastness such as solvent resistance and heat resistance. There has been a demand for the development of a green pigment having excellent physical properties while improving the defects in physical properties and maintaining a clear, yellowish green color tone.

  As a result of intensive studies to achieve the object of the present invention, the present inventors have stacked PG58 molecules with strong non-zinc metal pigment molecules having a similar molecular structure. It was found that by building a new composite pigment structure obtained, it was possible to impart fastness to organic solvents and heating while maintaining excellent color characteristics, and to solve the above-mentioned problems. It came to complete.

  That is, according to the first aspect of the present invention, a green pigment is provided, and the green pigment has a polyhalogeno zinc phthalocyanine having an average halogen group substitution number of 12 to 16 and an average halogen group substitution number of 12 to 16. It is characterized by being a composite stack with a certain polyhalogeno non-zinc metal phthalocyanine.

  According to another aspect of the present invention, there is provided a method for producing the above green pigment, which comprises dissolving the polyhalogeno zinc phthalocyanine and the polyhalogeno non-zinc metal phthalocyanine in a medium, The two molecules are co-deposited as a composite stack.

  According to still another aspect of the present invention, a green pigment dispersion composition is provided, the green pigment dispersion composition comprising an organic solvent-based, water-based or water-hydrophilic organic solvent mixed solvent-based liquid medium, and a polymerizable oligomer. Or a polymerizable liquid medium composed of a polymerizable monomer and a resin medium composed of a plasticizer, an oligomer, or a synthetic resin, and if necessary, a polymer system dispersant or a low molecular weight dispersion aid as a dispersion aid. Furthermore, it is characterized by comprising.

  According to another aspect of the present invention, a colorant is provided. The colorant further comprises a diluent medium, a thermoplastic polymer as a film-forming material, a reactive weight, and the green pigment dispersion composition. Comprising one or more materials selected from the group consisting of coalescing monomers, reactive oligomers, polymerizable monomers and crosslinking agents, and further comprising a curing catalyst or a polymerization catalyst as required. Features.

  According to still another aspect of the present invention, there is provided a coloring method for an article characterized by coloring the article using the above-described pigment dispersion composition or colorant, and a colored article formed thereby. .

This green pigment is excellent in physical properties, particularly fastness such as heat resistance and solvent resistance, while maintaining a clear and yellowish green color tone, and can be used particularly advantageously as a green pixel pigment for a color filter. Such an effect of the green pigment according to the present invention is not achieved by using a mixture of two pigments. The excellent effect of the green pigment according to the present invention is that a new composite pigment structure reinforced by intermolecular interaction is obtained by firmly stacking (stacking) the two pigment molecules constituting the pigment. It is assumed that it is provided by. In particular, two molecules are stacked with each other by π-π interaction, and both molecules are combined to form a crystal. Unlike the original pigment crystals, a new pigment is formed. It is done. However, the above theory is only an assumption, and the present invention is not limited to such a theory.

<Definition>
In the description of the present invention, polyhalogeno zinc phthalocyanine having an average halogen group substitution number of 12 to 16, poly (12 to 16) halogeno zinc phthalocyanine, and polyhalogeno non-zinc metal phthalocyanine having an average halogen group substitution number of 12 to 16 May be referred to as poly (12-16) halogeno non-zinc metal phthalocyanine. That is, “(12 to 16)” in these notations indicates the average number of halogen groups substituted in each pigment molecule. Also in the following, the numbers written in parentheses before the terms “halogeno”, “bromo”, and “chloro” are similarly used for the “halogen group”, “bromine group”, and “chlorine” in the pigment molecule. The average number of substituents of “group” is shown.

  In the present specification, when poly (12-16) halogeno zinc phthalocyanine and poly (12-16) halogeno non-zinc metal phthalocyanine are described with the intention of pigments that are aggregates of molecules, 12-16) Halogeno zinc phthalocyanine pigments and poly (12-16) halogeno non-zinc metal phthalocyanine pigments may be abbreviated as A pigments and B pigments, and the molecules constituting these pigments will be further described. In some cases, poly (12 to 16) halogeno zinc phthalocyanine and poly (12 to 16) halogeno non-zinc metal phthalocyanine may be referred to as compound names, or may be abbreviated to A and B molecules, respectively.

  In the present specification, a composite stack of a polyhalogeno zinc phthalocyanine having an average halogen group substitution number of 12 to 16 and a polyhalogeno non-zinc metal phthalocyanine having an average halogen group substitution number of 12 to 16 is a molecular level. Means a substance that forms a crystal by stacking, and is substantially synonymous with the eutectoid of these two pigments.

<Manufacturing method>
The green pigment according to the present invention is prepared, for example, by the following method. That is, a poly (12-16) halogeno zinc phthalocyanine pigment (A pigment) and a poly (12-16) halogeno non-zinc metal phthalocyanine pigment (B pigment) are dissolved in a medium in which both pigments are dissolved, and the A pigment The green pigment is obtained by eutecting so that both the A molecule of B and the B molecule of the B pigment are compositely stacked. As a medium for dissolving both pigments, an acid, preferably sulfuric acid, more preferably fuming sulfuric acid or 100% sulfuric acid is used.

In the green pigment eutectoid method according to the present invention, the A molecule and the B molecule are simultaneously dissolved so that the A molecules are deposited (stacked) by the B molecules. For example, a condition where only A molecules are precipitated and B molecules are not precipitated must be avoided. Examples of eutectoid methods include:
(1) A method in which a hydrous acid is added to an acid solution (preferably a high concentration acid solution) in which the A pigment and the B pigment are dissolved to decrease the acid concentration and precipitate both molecules.
(2) A method of precipitating both molecules by absorbing moisture in a high-concentration acid solution in which the A pigment and B pigment are dissolved to lower the acid concentration to lower the solubility.
(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 vigorously stirred or jetted water or ice water, and both molecules are instantaneously precipitated and stacked. Etc.

  In the above (3), the water for precipitation or ice water may contain an organic solvent. According to a preferred embodiment of the present invention, among the above, the method (3) is preferred. In particular, there is a method in which water is jetted at a high speed with a vacuum suction device such as an aspirator or an ejector, and a high-concentration sulfuric acid solution of the pigment is sucked by the pressure-reducing action and brought into contact with the water jetting at high speed, and diluted to precipitate pigment particles. preferable. Also, using a high-speed mixer such as a dissolver or homomixer, or in a mixing tank equipped with a high-efficiency stirrer such as “Max Blend” (trade name, manufactured by Sumitomo Heavy Industries, Ltd.), the water for precipitation is vigorously stirred. A preferred embodiment also includes a method in which an acid solution of a pigment is dropped, dropped or injected (hereinafter, “injection” is used to include dropping and flowing), and the pigment particles are diffused into water to precipitate the pigment particles. .

  According to a preferred embodiment of the present invention, in the eutectoid process or subsequent to the eutectoid process, as a pigmentation process (pigmentation) process, the process of removing impurities from the crude pigment to increase the purity of the pigment, It is preferable to carry out the step of preparing and / or the step of preparing crystals as a pigment. The pigmentation treatment in the eutectoid process is carried out by injecting or forcing contact with water or ice water containing a hydrophobic organic solvent and / or a hydrophilic organic solvent for co-deposition, and making the pigmentation treatment fine and crystallizing. And a method of adding the organic solvent to the treated water containing the eutectoid and bringing them into contact with each other. Following the eutectoid process, a known pigmentation treatment such as a solvent finish method such as a heat treatment in an organic solvent such as xylol or a crystallization treatment such as a heat treatment with xylol emulsion is carried out. One or more of agents, rosins, various resins, polymer dispersants, and pigment derivatives can be used in combination. Pigment refinement can be performed in the eutectoid process, and when it is performed subsequent to the eutectoid process, water-soluble salts can be added in a kneader such as a kneader by a dry grinding method or a salt milling method. Then, it may be carried out by a known pigment refining method such as kneading, grinding and refining with a water-soluble organic solvent. The average particle diameter of the primary particles of the refined pigment is 5 to 130 nm, preferably 10 to 110 nm.

<Green pigment>
In the polyhalogenozinc phthalocyanine pigment constituting the green pigment according to the present invention, the halogen group as a substituent means a chlorine group, a bromine group or both groups. In particular, since the color tone expected of the polyhalogeno zinc phthalocyanine pigment is a clear yellowish green, a phthalocyanine green pigment mainly composed of bromine groups is preferred, and bromine groups and chlorine groups are introduced (12 to less than 16, preferably 12 to 15.9) bromo- (0 exceeding 4 or less, preferably 0.1 to 4) chlorozinc phthalocyanine pigment and bromine-only (12 to 16) bromozinc phthalocyanine pigment are preferable. A more specific preferred pigment is PG58.

In addition, examples of the non-zinc metal of the poly (12-16) halogeno non-zinc metal phthalocyanine pigment constituting the green pigment according to the present invention include Group I metals such as copper, Group II metals such as magnesium , and aluminum . Examples include one or more metals selected from the group consisting of Group III metals, Group IV metals such as titanium and tin, and Group VIII metals such as iron, cobalt and nickel. The halogen group means a chlorine group, a bromine group or both. Preferable poly (12-16) halogeno non-zinc metal phthalocyanine for realizing the green pigment according to the present invention having high fastness is a poly (12 or more, less than 16, preferably 12 to 15.9) having a bromine group and a chlorine group introduced. ) Bromo (0 to 4 or less, preferably 0.1 to 4) chloro non-zinc metal phthalocyanine, bromine-only poly (12-16) bromo non-zinc metal phthalocyanine, and chlorine-only poly (12-16) A chloro non-zinc metal phthalocyanine is mentioned, and (14-16) bromo non-zinc metal phthalocyanine is particularly preferably used.

  Polybromochlorozinc phthalocyanine and polybromochloro non-zinc metal phthalocyanine can be obtained by a “post-bromination method” in which a phthalocyanine pigment is brominated. However, it is generally unavoidable that chlorination occurs along with bromination, and it is difficult to completely control the type of halogen and the number of substitutions, so the pigment of the desired color is selected from the obtained one. , Preferably used.

  In order to produce green pigments with more control over the type of halogen and the number of substitutions, brominated, chlorinated or brominated / chlorinated phthalic anhydrides, phthalimides, phthalodinitriles with the specified number of substitutions introduced Alternatively, it is desirable to carry out a condensation reaction using aminoiminoisoindolenine as a raw material to synthesize brominated or chlorinated, brominated / chlorinated zinc or non-zinc metal phthalocyanine pigment. In particular, polybromozinc phthalocyanine pigments or polybromo non-zinc metal phthalocyanine pigments having only a bromine group are tri- or tetrabromophthalic anhydride, tri- or tetrabromophthalimide, tri- or tetrabromophthalodinitriles, or tri- or tetrabromo. It is preferably obtained by a method for synthesizing a pigment by a condensation reaction using aminoiminoisoindolenine as a raw material together with zinc salt or non-zinc metal salt.

  The green pigment according to the present invention is excellent in fastness such as solvent resistance and heat resistance. The green pigment according to the present invention is such that the particle diameter of the pigment particles does not greatly expand before and after heating and boiling in an organic solvent, and the diffraction angle and diffraction intensity of X-ray diffraction do not substantially change. . As a method for confirming this, a heat treatment method in an organic solvent can be mentioned. When the polyhalogenozinc phthalocyanine pigment is present, the green pigment according to the present invention is heat-treated under a treatment condition in which crystal grains grow and become coarse. Changes in the obtained treated pigment particles can be confirmed and evaluated by the degree to which the pigment particles grow more coarsely like needles from an electron micrograph. In addition, the X-ray diffraction chart of the treated pigment or the coarse pigment portion separated therefrom does not substantially show diffraction at an angle characteristic only to the polyhalogeno zinc phthalocyanine pigment, or the mixture of pigment particles depending on the degree The degree of can be confirmed.

<Evaluation experiment>
PG36 pigment, PG58 pigment, and green pigment according to the present invention were prepared. For comparison, a simple pigment mixture prepared by kneading PG36 pigment and PG58 pigment in methanol paste was also prepared. Each pigment was added in a xylene solvent, heated and boiled to treat the pigment with a solvent, and changes in the particle diameter and crystal state of the treated pigment were examined.
Electron micrographs were taken at 60,000 times the PG36 pigment before solvent treatment, PG58 pigment, the green pigment according to the present invention, and a simple pigment mixture. The photographs showed that the pigments were fine or spherical, each having a size of approximately 30-50 nm (0.03-0.05 μm).

  Regarding the pigment subjected to the xylene boiling treatment, first, the treated pigment of PG58 had a large crystal particle and was coarsened. The electron micrograph was taken at a magnification of 10,000 times, the magnification being lower than that of other pigments. Electron micrographs showed no fine particles, but only needle-like or thicker glass fiber crystals on the entire surface. When the crystal was expressed by “length × width”, it was a large needle crystal having a size of about 1 μm × 0.05 μm to 7 μm × 0.2 μm, and further, it was observed to grow into the combined coarse crystal particles. Thus, PG58 pigment was shown to be very solvent labile. PG36 pigments, simple pigment mixtures and green pigment xylene boiling treated pigments according to the present invention were taken at 60,000 times as electron micrographs. The shape of the pigment particles of the treated pigment of PG36 was in the form of fine particles or spheres of about 30 to 70 nm as before the treatment, indicating that it was stable to the solvent. The mixture of PG36 pigment and PG58 pigment showed fine particles and needle-like or glass fiber-like crystal particles, showing a photograph in which both pigments were mixed.

  The green pigment according to the present invention showed fine particles or spheres of about 30 to 70 nm as before the treatment. However, in some cases, thin acicular crystals with a width of about 30 nm and a length of about 1 μm can be seen, and there is a mixture of non-stacked PG58 that may be caused by fluctuation of the stacking conditions. Was assumed. However, when used as a colorant, it has little effect on fastness and in many cases is used substantially equally.

  X-ray diffraction was measured for each pigment before and after the xylene boiling treatment. Tables 1 and 2 show the main diffraction peaks and relative intensities when the diffraction angles are substantially matched. In the table, “2θ” indicates the diffraction angle (°), the “%” column indicates the relative intensity of diffraction in%, the “shape” column indicates the pattern of the diffraction peak, and “s” is sharp. "B" represents a broad pattern.

  From the above results, it was shown that the PG36 pigment had almost the same diffraction angle and relative intensity before and after the treatment, except that the crystal pattern became slightly sharper. On the other hand, PG58 pigment showed a sharp and large diffraction pattern at many diffraction angles from X-ray diffraction, and it was shown that the crystal of the pigment grew greatly and the interplanar spacing was adjusted. In addition, the diffraction of the mixture of PG36 pigment and PG58 pigment is naturally shown as a combined pattern of the diffraction of both pigments.

  The green pigment according to the present invention exhibits diffraction that is completely different from that of the above mixture, indicating that the mixture is a crystal of a completely different dimension. Compared to the diffraction chart of PG36 pigment, the charts before and after the solvent treatment both show diffraction patterns similar to the diffraction chart of PG36 pigment, including diffraction angle and relative intensity. It is inferred that the diffraction pattern of the green pigment according to the present invention is slightly broad and shows a difference in sharpness, indicating an accumulation of non-zinc pigment molecules.

  Further, from the diffraction pattern of the green pigment according to the present invention, the stacking of the A pigment and the B pigment is considered as follows. That is, the green pigment according to the present invention has a difference in sharpness of diffraction compared to the PG36 pigment and PG58 pigment, and although there are some broad points, the overall diffraction pattern of these three types of pigments is different. Similar to each other, diffraction appears where diffraction angles almost coincide with each other, and their relative intensities are also similar. From this, it is inferred that the PG36 molecule and the PG58 molecule are molecules that tend to overlap each other in terms of molecular structure.

  The green pigment according to the present invention is expected to show a clear yellowish green color particularly as a green pigment for forming a green pixel for CF. In this application, it is advantageous in terms of physical properties that the particle diameter of the pigment particles does not greatly increase before and after the heat treatment in an organic solvent, and the diffraction angle and diffraction intensity of X-ray diffraction do not change greatly. It is. The green pigment according to the present invention can be used in the case where a slight mixture of non-stacked polyhalogenozinc phthalocyanine pigments does not substantially affect the colorant formulation, processing conditions, or application used. Mixing is allowed.

  Regarding the molar ratio of polyhalogeno zinc phthalocyanine to polyhalogeno non-zinc metal phthalocyanine, it is possible to retain the yellowish green color tone, which is an excellent property of polyhalogeno zinc phthalocyanine, or it is a range that does not inhibit, and is a disadvantage of polyhalogeno zinc phthalocyanine. In order to improve heat resistance and solvent resistance, it is desirable that the molar ratio is such that a structure that brings about the above performance and physical properties can be formed. In addition, the ratio of heat resistance and solvent resistance may be appropriately determined depending on the type of solvent used when forming the colorant, and the heat resistance may be appropriately determined depending on the heating conditions in the post-treatment when coloring. .

  According to a preferred embodiment of the present invention, the molar ratio of polyhalogeno zinc phthalocyanine (XnZnPc) to polyhalogeno non-zinc metal phthalocyanine (XnMePc) is XnZnPc: XnMePc = 30: 70 to 95: 5 for the purpose of stability. And preferably 40:60 to 90:10. In particular, when importance is attached to the color tone, 82:18 to 95: 5 is preferable.

<Application>
The green pigment according to the present invention is used as a colorant, for example, in coating, printing plate printing, dyeing, textile printing, character recording, drawing, ink jet printing, electrophotographic printing, and electrostatic printing. In addition to CF pixel forming ink, painting with paint, resin coloring with resin colorants, colorants such as printing ink, dyeing agent, and printing agent, stationery such as stationery and paint, ink for inkjet, electrophotography The use as coloring components, such as information recording materials, such as a developer for printing or a developer for electrostatic printing, is mentioned.

  Thus, according to another aspect of the present invention there is provided a colorant comprising a green pigment according to the present invention. In order to produce the colorant according to the present invention, a pigment composition may be prepared, and the pigment composition may include the green pigment according to the present invention. Thus, according to another aspect of the present invention, there is also provided a pigment dispersion composition comprising the green pigment according to the present invention. The form of the pigment dispersion composition may be an aqueous pigment dispersion composition, an oily pigment dispersion composition, a resin-dispersed processed pigment, an energy beam curable pigment dispersion composition, or the like. The pigment concentration is usually set as high as 10% to 50%, and the pigment may be finely dispersed in advance so that the colorant can be easily produced. The pigment composition according to the present invention contains the green pigment according to the present invention, and an appropriate liquid medium of an organic solvent system, an aqueous system or a water-hydrophilic organic solvent mixed solvent system as a medium; a polymerizable oligomer, a polymerizable monomer, etc. A polymerizable liquid medium, a plastic medium, a resin medium composed of an oligomer, a synthetic resin, and the like, and if necessary, a polymer system dispersant or a low molecular weight dispersion aid.

Appropriate materials selected from the pigment dispersion composition according to the present invention, further selected from a dilution medium, a thermoplastic polymer acting as a film-forming material, a reactive polymer, a reactive oligomer, a polymerizable monomer, and a crosslinking agent. And the like, and a curing catalyst, a polymerization catalyst and the like are further added as necessary, and the mixture is uniformly mixed and dispersed to produce the target colorant. According to one aspect of the present invention, in the colorant according to the present invention, the blending mass ratio of the pigment (P) and the coating film forming material (V) is appropriately determined in consideration of the application, required performance, and the like. In general, however, P: V is in the range of 80:20 to 1:99, preferably 70:30 to 10:90.

  In dispersing the pigment in the colorant or pigment dispersion composition according to the present invention, known additives may be added as needed in addition to the film-forming polymer. Examples of such additives include ionic pigment derivatives known as pigment dispersion stabilizers and their counterionic ionic polymer-based dispersants, surfactants, antifoaming agents, smoothing agents, adhesive agents, Various additives such as a silane coupling agent are included.

  Examples of the pigment dispersing machine used in the production of the pigment dispersion composition and the colorant include known dispersing machines, such as vertical media dispersing machines such as a ball mill, a sand mill and a bead mill, horizontal media dispersing machines such as a dyno mill and a horizontal bead mill, a roll mill, An ultrasonic mill, a high-pressure collision disperser, etc. are used. Dispersion processing is performed by a method of performing dispersion processing a plurality of times using one kind of the above-mentioned dispersers or a method of combining two or more kinds of dispersers. The average particle size is usually about 5 to 130 nm, preferably 10 to 110 nm.

  For the resin as the film-forming material contained in the colorant according to the present invention, known resin components corresponding to the respective applications may be used. For example, known coating film forming materials such as synthetic rubber resin, acrylic resin, vinyl resin, chlorinated rubber resin, alkyd resin, urethane resin, epoxy resin, silicon resin, fluorine resin, and ultraviolet curable resin system, electron beam curable Examples include resin-based energy ray-curable coating film forming materials. The film-forming material may further have a reactive group, and examples of the reactive group include a methylol group, an alkylmethylol group, an isocyanate group, a masked isocyanate group, and an epoxy group. In addition, oligomers and monomers are used depending on the application, and a cross-linking agent such as a methylol melamine-based, isocyanate-based, or epoxy-based cross-linking agent is also used in combination.

  When the colorant according to the present invention is a color filter colorant, any conventionally known film-forming material can be used and is not particularly limited. When the image forming ink is a photolithographic development type, an energy beam irradiation polymerization type ink collectively referred to as a photosensitive pixel forming ink is used. Examples of addition polymerization or addition crosslinkable inks include heat polymerization type, laser heat ray polymerization type, ultraviolet ray polymerization type, photocationic polymerization type, and electron beam polymerization type heating or energy ray curable inks. The film-forming material used for them is a monomer, oligomer and / or polymer having an unsaturated double bond or a polymerizable cyclic ether group having a conventionally known addition polymerization or addition crosslinkability, and further added if necessary. A polymerization initiator, an addition polymerization or addition crosslinkable fixing agent comprising a liquid medium.

  Specific examples of the film forming material include pentaerythritol di (meth) acrylate (“(meth) acrylate” represents acrylate and methacrylate), dipentaerythritol poly (4-6) (meth) acrylate, bisphenol type epoxy resin— Monomers such as di (meth) acrylate; (meth) acrylic acid ester- (meth) acrylic acid (co) polymer, (meth) acrylic acid ester-styrene- (meth) acrylic acid copolymer, etc .; polyester acrylate type Resins, polyepoxy acrylate resins, polyurethane acrylate resins, polyether acrylate resins, polyol acrylate resins, and the like; photosensitive phenol resins, unsaturated polyester resins, and the like. These may be used alone or in combination of two or more.

  Examples of the photopolymerization initiator include known photopolymerization initiators such as 1-hydroxy-cyclohexylphenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-di- Ethoxyacetophenone, 2-methyl-1- (4- (methyl-thio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2- (N, N-dimethylamino) -1- (4-morphe And linophenyl) -butanone-1. These may be used alone or in combination of two or more.

  Various articles | goods can be colored using the pigment dispersion composition by this invention, and the coloring agent using the same. When used for forming a green pixel of a color filter, a conventionally known green color resist is prepared in combination with a yellow pigment as known, and a conventionally known photoresist method on a CF substrate together with a red resist and a blue resist, Green, red, and blue pixels are formed by a method such as a transfer method, a pasting method, an ink jet printing method, or a printing method, but is not particularly limited thereto. For example, when a pixel pattern of a color filter is formed on a substrate, the photosensitive pixel forming ink is coated on the substrate using, for example, a spin coater, a roll coater, a slit coater, a printing machine, etc. Then, after pre-drying, a photomask is adhered, and exposure is performed using an ultra-high pressure mercury lamp to print a pattern. Subsequently, development and washing are performed, and post-baking is performed as necessary to form a color filter pattern.

  In the color filter, as a 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, azo pigments such as insoluble azo, soluble azo and high molecular weight azo, quinacridone red and quinacridone magenta quinacridone pigments, diketopyrrolopyrrole pigments, anthraquinone pigments, perylene pigments, phthalocyanines Blue-based phthalocyanine pigments, isoindolinone pigments, dioxazine pigments such as dioxazine violet, quinophthalone yellow pigments, complex pigments such as nickel azo yellow, and the like are used.

  Specific examples of pigments representative for transmissive R, G, and B pixels include PR177, PR242, and PR254 as red pigments, and PY83, PY138, PY139, PY150, as yellow pigments for complementary colors or single colors, PY185 and the like, PB15: 6, PB60, etc. as blue pigments, PV23 etc. as purple pigments for complementary colors or single colors, and the above-mentioned red pigments and yellow pigments, and blue pigments and purple pigments Examples include coprecipitated pigments, solid solution pigments, and mixed crystal pigments.

  In addition, the pixel formation of the color filter has been mainly described above. However, the pigment dispersion composition and the colorant according to the present invention are used in various other applications such as synthetic or natural resins, paints, plastic films, various papers, As printing inks for synthetic paper, etc., it is also suitable as colorants for paper, textile printing agents, writing inks, color copier toners, ink jet printer inks, thermal transfer ribbon inks, etc. Gives an excellent green colored article.

  Next, the present invention will be described in more detail with specific examples. In addition, unless otherwise indicated, the part and% in a sentence are a mass reference | standard. In addition, the number of bromine substitutions in the following polybromo non-zinc metal phthalocyanine indicates the number from the charge ratio of the condensation reaction.

Production Example 1 (Production of composite stacked green pigment of PG58 molecule and 16 bromocopper phthalocyanine molecule)
(1) Synthesis of 16 bromocopper phthalocyanine pigment As a synthetic reaction apparatus, a reaction vessel equipped with a stirrer, a backflow cooler, and a thermometer and a heating apparatus were prepared. Tetrabromophthalic anhydride having a bromine content of 69.0% and a bromine substitution number of 4.0 per molecule was prepared as a raw material. To the reaction vessel, 140.0 parts of nitrobenzene as a 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 cupric chloride were added. The reaction temperature was gradually raised from 100 ° C. to 175 ° C., and the mixture was stirred for 4 hours to continue the reaction. The reaction temperature immediately before completion of the reaction was 195 ° C. The yield of crude pigment was 44.8 parts, and the crude pigment yield was 97.4%. Separately, 95% sulfuric acid and 20% fuming sulfuric acid were blended to prepare 100% sulfuric acid. 10 parts of the obtained crude pigment was dissolved in 100 parts of 100% sulfuric acid, stirred at 70 ° C. for 1 hour, precipitated in 10 times ice water, filtered and washed with water (hereinafter referred to as “sulfuric acid purification”). Called). It was then washed with dilute aqueous sodium hydroxide and ethanol and dimethylformamide. The yield of purified 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 bromine substitution number per molecule calculated from the analytical value of the obtained 16 bromocopper phthalocyanine green pigment was 16.1, indicating that the phthalocyanine skeleton was completely substituted with 16 bromines. Hereinafter, this is referred to as “16 bromo copper phthalocyanine coarse particle pigment”.

(2) PG58 and 16 Bromocopper Phthalocyanine Molecule 16.13 g of PG58 having an average number of bromine substitutions of about 13 and an average number of chlorine substitutions of 3 (0.000 as the calculated value from the average number of substituents). 10060 mol, the same applies hereinafter) and 3.61 g (0.00196 mol) of 16 bromocopper phthalocyanine coarse particle pigment obtained by the synthesis reaction of (1) above were dissolved in 140 g of 20% fuming sulfuric acid, and 70 ° C. The mixture was stirred for 2 hours and allowed to cool to room temperature. Water was jetted at high speed with an aspirator, the fuming sulfuric acid solution of the above pigment was sucked through a reduced-pressure thin tube, contacted with water jetted at high speed, diluted to precipitate pigment particles, and filtered and washed with water. Subsequently, pigmentation was performed by a xylene-emulsion method to obtain a green pigment. Hereinafter, this is referred to as “green stacked crude pigment-1”.

(3) Preparation of composite stacked green particulate pigment by salt milling refinement treatment Pressing 100 parts of green stacked crude pigment-1 obtained in (2) above with 600 parts of sodium chloride powder and 110 parts of diethylene glycol We prepared a kneader with a lid. Uniformly premixed until a wet mass was formed in the kneader, followed by kneading and grinding while pressing the contents under a pressure of 6 kg / cm ² by closing the pressure lid. Kneading and grinding were performed for 2 hours while controlling the temperature so that the contents were 92 to 98 ° C. The obtained ground product was stirred in 3000 parts of 2% sulfuric acid heated to 80 ° C. for 1 hour, filtered and washed with water to remove sodium chloride and diethylene glycol, and the composite stack was refined. A pressed cake of a green pigment was obtained. In order to measure the particle diameter of the obtained pigment, 200% of a nonionic active agent is added to the pigment press cake with respect to the pigment, diluted with water, ultrasonically dispersed to prepare a pigment dispersion, and a particle size measuring instrument When the average particle size was measured by “Model N-4” (manufactured by Coulter), the average particle size was about 25 to 35 nm. The press cake was dried and pulverized to obtain a green pigment. Even when the obtained pigment was heat-treated in an organic solvent, no substantial change was observed in the particle diameter and crystal state of the pigment. Hereinafter, this is referred to as “green stacked pigment-1”.

Production Example 2 (Production of composite stacked green pigment of PG58 and 16 bromocopper phthalocyanine molecule)
(1) Stacking of PG58 molecule and 16 bromocopper phthalocyanine molecule It was obtained by the synthesis reaction of 16.81 g (0.00985 mol) of PG58 used in Production Example 1 (2) and Production Example 1 (1). 16.19 g (0.00173 mol) of 16 bromocopper phthalocyanine coarse particle pigment was dissolved in 200 g of 20% fuming sulfuric acid, stirred at 70 ° C. for 2 hours and allowed to cool to room temperature. The solution was poured into 2000 g of ice water containing 100 g of butyl cellosolve charged to Sumitomo Heavy Industries, Ltd., and filtered and washed with water. The press cake was dried and pulverized to obtain a green pigment. Hereinafter, this is referred to as “green stacked pigment-2”.

Production Example 3 (Production of composite stacked 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, 18.00 g (0.01054 mol) of PG58 used in Production Example 1 (2) and the average number of bromine substitutions were approximately 13. 2.00 g (0.00117 mol) of PG36 having an average number of chlorine substitutions of 3 was dissolved in 200 g of 20% fuming sulfuric acid, stirred at 70 ° C. for 2 hours, and allowed to cool to room temperature. . Water was jetted at high speed with an aspirator, the fuming sulfuric acid solution of the above pigment was sucked through a reduced-pressure thin tube, contacted with water jetted at high speed, diluted to precipitate pigment particles, and filtered and washed with water. Subsequently, pigmentation was performed by a xylene-emulsion method to obtain a green pigment. Hereinafter, this is referred to as “green stacked crude pigment-3”.

(2) Preparation of composite stacked green fine particle pigment by salt milling refinement treatment In the same manner as in Production Example 1 (3), 100 parts of the green stacked crude pigment-3 obtained in (1) above was added with sodium chloride. A kneader equipped with a pressure lid together with 600 parts of powder and 110 parts of diethylene glycol was charged and kneaded and ground in the same manner. In the same manner, after stirring in 2% sulfuric acid, filtration and washing were performed to remove sodium chloride and diethylene glycol, thereby obtaining a press cake of a finely layered composite stacked green pigment. The average particle size was approximately 30 nm. The press cake was dried and pulverized to obtain a green pigment. Even when the obtained pigment was heat-treated in an organic solvent, no substantial change was observed in the particle diameter and crystal state of the pigment. Hereinafter, this is referred to as “green stacked pigment-3”.

Production Example 4 (Production of composite stacked green pigment of PG58 molecule and 16 bromoaluminum phthalocyanine molecule)
(1) Synthesis of 16 bromoaluminum phthalocyanine pigment In the same manner as in Production Example 1 (1), the same number of nitrobenzene, tetrabromophthalic anhydride, urea, and titanium tetrachloride was changed to a reaction vessel, and aluminum chloride was replaced with copper chloride. 3.34 parts were charged. 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 crude pigment was 40.0 parts, and the crude pigment yield was 87.1%. The obtained crude pigment was purified by sulfuric acid 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 bromoaluminum phthalocyanine pigment”.

(2) Stacking of PG58 molecule and 16 bromoaluminum phthalocyanine molecule In the same manner as in Production Example 1 (2), 14.75 g (0.00864 mol) of PG58 and the 16 bromoaluminum phthalocyanine pigment of (1) above. 24 g (0.00288 mol) was dissolved in 140 g of 20% fuming sulfuric acid, stirred at 70 ° C. and allowed to cool. The fuming sulfuric acid solution of the above pigment was sucked using an aspirator, brought into contact with water jetted at high speed, and diluted to precipitate pigment particles. The precipitate was filtered, washed with water, and then pigmented by the xylene-emulsion method to obtain a green pigment. Hereinafter, this is referred to as “green stacked crude pigment-4”.

(3) Preparation of composite stacked green fine particle pigment by salt milling refining treatment In the same manner as in Production Example 1 (3), the green stacked crude pigment-4 obtained in (2) above was treated with sodium chloride powder and A kneader was charged together with diethylene glycol, and after preliminary mixing, kneading and grinding were performed. The obtained ground product was stirred in 2% dilute sulfuric acid, filtered, washed with water, dried and pulverized to obtain a green pigment. Even when the obtained pigment was heat-treated in an organic solvent, no substantial change was observed in the particle diameter and crystal state of the pigment. Hereinafter, this is referred to as “green stacked pigment-4”.

Production Example 5 (Production of composite stacked green pigment of PG58 molecule and 16 bromomagnesium phthalocyanine molecule)
(1) Synthesis of 16 bromomagnesium phthalocyanine pigment In the same manner as in Production Example 1 (1), the same number of nitrobenzene, tetrabromophthalic anhydride, urea, and titanium tetrachloride was changed to a reaction vessel, and magnesium chloride was replaced with copper chloride. 2.39 parts were charged. 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 yield of crude pigment was 39.9 parts, and the crude pigment yield was 88.7%. The obtained crude pigment was purified by sulfuric acid 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 bromomagnesium phthalocyanine pigment”.

(1) Stacking of PG58 molecule and 16 bromomagnesium phthalocyanine molecule In the same manner as in Production Example 1 (2), 6.43 g (0.00377 mol) of PG58 and the 16 bromomagnesium phthalocyanine pigment 13 of (1) above. .57 g (0.00754 mol) was dissolved in 140 g of 20% fuming sulfuric acid, stirred at 70 ° C. and allowed to cool. The fuming sulfuric acid solution of the above pigment was sucked using an aspirator, brought into contact with water jetted at high speed, and diluted to precipitate pigment particles. The precipitate was filtered, washed with water, and then pigmented by the xylene-emulsion method to obtain a green pigment. Hereinafter, this is referred to as “green stacked crude pigment-5”.

(3) Preparation of composite stacked green fine particle pigment by salt milling refining treatment In the same manner as in Production Example 1 (3), the green stacked crude pigment-4 obtained in (2) above was treated with sodium chloride powder and A kneader was charged together with diethylene glycol, and after preliminary mixing, kneading and grinding were performed. The obtained ground product was stirred in 2% dilute sulfuric acid, filtered, washed with water, dried and pulverized to obtain a green pigment. Even when the obtained pigment was heat-treated in an organic solvent, no substantial change was observed in the particle diameter and crystal state of the pigment. Hereinafter, this is referred to as “green stacked pigment-5”.

Example 1 (Preparation of high concentration dispersion of green pigment)
As a pigment dispersant, 30% propylene glycol monomethyl ether acetate of a butyl acrylate-styrene-hydroxyethyl acrylate-methacrylic acid (mass ratio: 50: 15: 10: 25, average molecular weight: 12,000) copolymer ( Hereinafter, abbreviated as “PGMA”.) A solution was prepared. Hereinafter, it is referred to as “resin dispersant PGMA solution-1”.
19 parts of “Green Stacked Pigment-1” obtained in Production Example 1 (3), 1 part of a green pigment sulfonated derivative, 12 parts of a cationic polymer dispersant (polyester amidated polyethyleneimine, 50% solution), 50 parts of “Resin Dispersant PGMA Solution-1” shown above and 18 parts of PGMA were blended and stirred for 2 hours with a dissolver. After confirming that the lump of the pigment had disappeared, the horizontal annular type bead mill disperser was made of zirconia. Using beads (diameter 0.65 mm), dispersion treatment was performed at a peripheral speed of 14 m / s to obtain a green high-concentration pigment dispersion, “Green Stacked Pigment High-Concentration Dispersion-1”.

Example 2 (Preparation of high concentration dispersion of each color pigment)
(1) Preparation of each color fine particle pigment by refinement treatment PR254, PY138, PB15-6 and PV23 were prepared. Each pigment powder was charged into a kneader equipped with a pressure lid together with sodium chloride powder and diethylene glycol, and kneaded and ground in accordance with the salt milling refinement treatment of the composite stacked green pigment in Production Example 1 (3). . The obtained ground product was similarly dissolved in salt and solvent, filtered and washed with water to obtain press cakes of the respective finer pigments. The average particle size of the fine pigments of each color was 30 to 40 nm. The press cake was dried and pulverized to obtain fine powder powder pigments.

(2) Preparation of pigment high-concentration dispersion In the same manner as in Example 1, PR254, PY138, PB15-6 and PV23 obtained in (1) above were used in place of the green stacked pigment-1 and the green pigment sulfonated derivative. In the same way, a cationic polymer dispersant, an acrylic resin and PGMA are blended using a known pigment sulfonated derivative, stirred with a dissolver, peptized, and dispersed with an annular type bead mill disperser. And a high concentration dispersion of each pigment was obtained. Hereinafter, “high-concentration dispersion-1” is displayed with each color name.

(3) Preparation of pixel-forming ink for pixels In order to form RGB pixels on the glass substrate of the color filter, according to the composition shown in Table 3 below, “green color pigment photosensitive dispersion-1”, “red color pigment photosensitivity” Dispersion 1 "and" blue pigment photosensitive dispersion 1 "were obtained.

Example 3 (Preparation of color filter)
The glass substrate treated with the silane coupling agent was set on a spin coater, and the condition of “red pigment photosensitive dispersion-1” in Example 2 (3) above was initially 300 rpm for 5 seconds and then 1200 rpm for 5 seconds. Spin coated with. Next, prebaking was performed at 80 ° C. for 10 minutes, a photomask having a mosaic pattern was brought into close contact, and exposure was performed using an ultrahigh pressure mercury lamp at a light amount of 100 mJ / cm ² . Next, development and washing were performed with a dedicated developer and a dedicated rinse to form a red mosaic pattern on the glass substrate.
Subsequently, the green mosaic pattern and the blue mosaic pattern were applied and baked in accordance with the above method using “Green Pigment Photosensitive Dispersion-1” and “Blue Pigment Photosensitive Dispersion-1” in Table 3. To obtain an RGB color filter. The resulting color filter has excellent spectral curve characteristics, excellent fastness such as light resistance and heat resistance, and excellent light transmission properties, and is excellent as a color filter for liquid crystal color displays. Showed the properties.

Example 4 (Preparation of color filter)
In place of the green stacked pigment-1 used in Example 1, the green stacked pigment-2 to 5 obtained in Production Examples 2 to 5 were used, and the same operations as in Examples 1 and 2 were performed. To obtain a green color pigment photosensitive dispersion, which is used together with the red color pigment photosensitive dispersion-1 and the blue color pigment photosensitive dispersion-1 to prepare a color filter in the same manner as in Example 3. A color filter for a liquid crystal color display was obtained having excellent spectral curve characteristics, excellent fastness such as light resistance and heat resistance, and excellent light transmission properties.

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 is approximately 30,000) is butyl acetate-methyl isobutyl ketone-xylene (43:20 20) Dissolved in 68 parts of a mixed solvent, added 5 parts of the green stacked pigment-1 obtained in Production Example 1 (3), charged in a ball mill and dispersed for 16 hours. Add 3 parts of silica, and add 12 parts of a 20% toluene solution of multi-branched polycarbodiimide-based cross-linking agent (reaction product of polyhexamethylene carbodiimide diisocyanate and dipentaerythritol monolaurate), and mix with yellowish green A gravure ink was used. As a vivid yellow-green special color gravure ink, gravure printing was performed on a vinyl chloride film together with other red, blue, yellow, brown and black gravure inks to obtain a beautiful multicolor printed vinyl chloride film.

  Moreover, it replaced with the green stacked pigment-1 used above, and prepared the green green gravure ink similarly to the above using the green stacked pigment-2-5 obtained by manufacture examples 2-5, and the same In addition, gravure printing was performed on the film to obtain a beautiful multicolored printing film.

Example 6 (paint and painting)
45 parts of ethyl acetate solution (solid content 60%) of methyl methacrylate-ethyl methacrylate-octyl methacrylate-hydroxyethyl methacrylate-methacrylic acid (44: 20: 10: 5) copolymer having a carboxyl group, 19.9 parts of xylene, 5 parts of green stacked pigment-1 obtained in Production Example 1 (3) and 15 parts of titanium oxide white pigment were added to a ball mill and dispersed for 16 hours. A yellow-green acrylic paint having a formulation of 15 parts of a 20% solution of a multi-branched polycarbodiimide-based crosslinking agent used in Example 5 and 0.1 part of a color separation preventing agent was prepared. Apply yellow-green paint to information-related products such as mobile phones and personal computers, various wooden products such as office supplies and household goods, metal products, and plastic products, and perform excellent coating such as weather resistance, durability, and water resistance. I was able to.

  Moreover, it replaced with the green stacked pigment-1 used above, and prepared the green-green acrylic paint similarly to the above using the green stacked pigment-2-5 obtained by manufacture examples 2-5, Similarly, various components were painted to obtain a beautiful yellow-green painted product.

Claims (26)

  A green pigment, which is a composite product of a polyhalogeno zinc phthalocyanine having an average halogen group substitution number of 12 to 16 and a polyhalogeno non-zinc metal phthalocyanine having an average halogen group substitution number of 12 to 16.   The green pigment according to claim 1, wherein a molar ratio between the polyhalogeno zinc phthalocyanine and the polyhalogeno non-zinc metal phthalocyanine is 30:70 to 95: 5.   The green pigment according to claim 1 or 2, wherein the halogen group of the polyhalogeno zinc phthalocyanine is a chlorine group, a bromine group or both.   The green pigment according to claim 3, wherein the polyhalogeno zinc phthalocyanine is a bromo zinc phthalocyanine having an average bromine group substitution number of 12 or more and 16 or less.   The green pigment according to claim 3, wherein the polyhalogeno zinc phthalocyanine is bromochlorozinc phthalocyanine having an average bromine group substitution number of 12 or more and less than 16, and an average chlorine group substitution number of more than 0 and 4 or less. The polyhalogeno zinc phthalocyanine is C.I. I. The green pigment according to claim 3 , which is CI Pigment Green 58. The non-zinc metal of the polyhalogeno non-zinc metal phthalocyanine is one or more metals selected from the group consisting of aluminum, magnesium, titanium, tin, iron, cobalt, nickel, and copper . The green pigment of any one of Claims . The green pigment according to any one of claims 1 to 7, wherein a halogen group of the polyhalogeno non-zinc metal phthalocyanine is a chlorine group or a bromine group or both.   The green pigment according to claim 8, wherein the polyhalogeno non-zinc metal phthalocyanine is a bromo non-zinc metal phthalocyanine having an average bromine group substitution number of 12 to 16.   The green pigment according to claim 8, wherein the polyhalogeno non-zinc metal phthalocyanine is a bromochloro non-zinc metal phthalocyanine having an average bromine group substitution number of 12 or more and less than 16, and an average chlorine group substitution number of more than 0 and 4 or less. The Poriharogeno non zinc metal phthalocyanine, those poly halogenoalkyl aluminum phthalocyanine, poly halogenoalkyl magnesium phthalocyanine, poly halogenoalkyl titanyl phthalocyanine, from the group consisting of poly-halogeno-phthalocyanine and Poriharogeno copper phthalocyanine of one or more selected, claim 9 Or the green pigment according to 10.   The particle diameter of pigment particles does not greatly expand before and after being heated or boiled in an organic solvent, and the diffraction angle and diffraction intensity of X-ray diffraction do not substantially change. The green pigment according to item 1.   From the solution obtained by dissolving the polyhalogeno zinc phthalocyanine pigment and the polyhalogeno non-zinc metal phthalocyanine pigment in a medium, the polyhalogeno zinc phthalocyanine and the polyhalogeno non-zinc metal phthalocyanine are co-deposited as a composite stack, The manufacturing method of the green pigment of any one of Claims 1-12.   The polyhalogeno zinc phthalocyanine pigment and the polyhalogeno non-zinc metal phthalocyanine pigment are dissolved in acid at a molar ratio of 30:70 to 95: 5, and the acid concentration in the resulting solution is reduced to reduce the polyhalogeno zinc phthalocyanine pigment. The production method according to claim 13, wherein the polyhalogeno non-zinc metal phthalocyanine is co-deposited as a composite stack.   The acid concentration in the solution is reduced by adding hydrous acid to the solution or absorbing moisture, or the solution is vigorously stirred or jetted in a large amount of water or ice water. The method for producing a green pigment according to claim 14, wherein the method is carried out by injecting into the water.   The non-zinc metal of the polyhalogeno non-zinc metal phthalocyanine pigment is one or more metals selected from the group consisting of aluminum, magnesium, titanium, tin, iron, cobalt, nickel, and copper. The manufacturing method of the green pigment of any one.   The method for producing a green pigment according to any one of claims 14 to 16, wherein the acid is fuming sulfuric acid or 100% sulfuric acid.   The method for producing a green pigment according to any one of claims 13 to 17, wherein a pigmentation treatment and / or a pigment refining step is performed simultaneously with or after the eutectoid.   The pigmentation treatment is performed at the same time as or after the eutectoid, and is brought into contact with water or ice water containing the hydrophobic organic solvent and / or the hydrophilic organic solvent with the object during or eutectoid. The manufacturing method of the green pigment of Claim 18 which is the process made to contact with an organic solvent.   A polymerizable liquid comprising the green pigment according to any one of claims 1 to 12, an organic solvent-based, water-based or water-hydrophilic organic solvent mixed solvent-based liquid medium, a polymerizable oligomer or a polymerizable monomer. Comprising a medium and a resin medium composed of a plasticizer, an oligomer or a synthetic resin, and further comprising a polymer system dispersing agent or a low molecular weight dispersing aid as a dispersing aid, if necessary Pigment dispersion composition.   The green pigment dispersion composition according to claim 20, a dilution medium, and a thermoplastic polymer as a coating film forming material, a reactive polymer, a reactive oligomer, a polymerizable monomer, and a crosslinking agent. A coloring agent, characterized by comprising one or more selected materials and further comprising a curing catalyst or a polymerization catalyst as required.   The ink for forming a color filter pixel, a paint, a resin colorant, a printing ink, a dyeing agent, a printing agent, a stationery, a paint, an inkjet ink, an electrophotographic printing developer, or an electrostatic printing developer. The coloring agent described in 1.   A method for coloring an article, comprising coloring the article using the green pigment dispersion composition according to claim 20 or the colorant according to claim 21.   The coloring method of the article according to claim 23, wherein the coloring of the article is performed by a method of forming pixels on a color filter substrate by a known photoresist method, transfer method, pasting method, ink jet printing method, or printing method.   24. The method for coloring an article according to claim 23, wherein the coloring of the article is performed by painting, resin coloring, printing plate printing, dyeing, textile printing, character recording, drawing, ink jet printing, electrophotographic printing, or electrostatic printing. .   A colored article formed by the coloring method according to any one of claims 23 to 25.