JP2009235354A - Pigment composition - Google Patents

Abstract

Kind Code: A1 Pigment compositions useful for inks, paints, coloring compositions for color filters, organic solar cell materials, organic nonlinear optical materials, organic transistor materials, various chromic dyes, biomedical materials, and the like, coloring compositions for color filters A pigment composition having particularly good properties as a product is provided.
A pigment composition comprising at least two of six specific phthalocyanine compounds and having an average particle size of 0.5 μm or less.
[Selection] Figure 1

Description

  The present invention relates to a novel phthalocyanine pigment composition. More specifically, the present invention relates to a pigment composition containing the ink and paint for preparation, and a pigment dispersion in which the pigment composition is dispersed in a vehicle. The present invention also relates to color filter dyes, organic solar cell dyes, organic nonlinear optical materials, organic transistor materials, various chromic dyes, biomedical dyes, and the like containing the novel pigment composition.

  The present invention relates to a novel phthalocyanine pigment composition. Phthalocyanine is currently used in large quantities as a pigment having a hue from blue to green, but industrial production began in the late 1930s. Since then, vivid hues as pigments, great coloring power, and excellent durability have attracted attention in the field of color materials, and the demand has been increasing year by year.

  The pigment composition of the present invention has a high function as various colorants that are originally used for dyes. Applications for this colorant range from printing inks, paints and plastic coloring to cosmetics, stationery, leather, textiles, foods, etc., but the main applications are printing inks, paints and plastics. Coloring.

  In general, the coloring power and sharpness of pigments used in various ink compositions and paints are closely related to the properties of pigment particles. Usually, pigment particles form an aggregate of primary particles, and it is known that the finer the primary particles, the higher the coloring power of the pigment and the higher the sharpness. Therefore, in order to improve the coloring power and sharpness of the pigment, it is necessary to make the aggregation state of the primary particles finer. On the other hand, as the pigment particles become finer, aggregation between particles tends to occur. For this reason, it is necessary to stably disperse the pigment particles in the vehicle in a fine state. Various printing inks and paints are obtained by finely and stably suspending a solid pigment powder in a liquid vehicle. The dispersion process essentially comprises a three-stage process: wetting, refinement and stabilization. However, in an actual distributed system, each process occurs in parallel, and it is often difficult to strictly separate these processes.

  The above is known regarding the pigment particles and the dispersion process, but it is often difficult to prepare a stable dispersion by suspending fine pigment particles in a vehicle. Therefore, the quality of the dispersion stability of the pigment in the non-aqueous vehicle has a significant effect on the production process of printing inks and paints such as offset inks and gravure inks and the quality of products, and may cause various problems. It is known to cause.

  Dispersions containing fine pigment particles often exhibit high viscosity, which can make it difficult to remove from the preparation container or transfer between containers, possibly resulting in changes in state such as gelation. Quality may be lost. In addition, when pigments with different chemical structures are used in a mixed state, a phenomenon called color separation or sedimentation caused by aggregation of pigment particles occurs, resulting in a state such as a decrease in gloss or poor leveling on the surface of the developed paint film. May cause defects. Furthermore, when the dispersion stability of the pigment in the ink and the paint is low, the state of the pigment crystal may change due to the energy instability in the vehicle of the pigment particles. That is, the pigment crystal changes its aggregated state and shifts to a more stable state, thereby causing phenomena such as a change in hue, a decrease in coloring power and sharpness, and formation of agglomerated particles. May change and significantly impair commercial value.

  The coloring composition used for producing the color filter is particularly required to have a uniform coating film thickness in the production process due to the high functionality of products using the color filter. For this reason, the coloring composition for a color filter used in the color filter preparation step has a low viscosity, and the viscosity stability over time is particularly necessary. In addition, it is necessary to have light resistance, acid resistance, alkali resistance, and solvent resistance at the same time due to the limitation of the manufacturing process and use environment of the color filter.

  Phthalocyanine has extremely excellent properties as a pigment, but as one of uses other than pigments, research and development of organic photoconductive materials as electrophotographic photoreceptors have been conducted in recent years. Further, phthalocyanine has been studied in the field of energy conversion materials such as photoelectric conversion materials and photocatalysts because of its light absorption characteristics and electrical characteristics. In particular, information display technologies represented by various flat panel displays, and information recording technologies represented by recording media such as color copies, CD-Rs, and DVDs have recently made remarkable progress. Along with these developments, various functional materials are being researched and developed in the fields of electronics, optoelectronics, and information, and there is a remarkable progress in the development and practical application of these materials. is there. Furthermore, as newly developed materials, dyes for color filters used in color liquid crystal displays, energy conversion element materials used in dye-sensitized organic solar cells, organic nonlinear optical materials, organic transistor materials, photochromism, thermochromism, There are chromic dyes that express various chromisms such as electrochromism, medical diagnostic dyes, therapeutic dyes, and biomedical dyes such as dye-based medicines, and future development is expected. Therefore, the degree of dependence on functional materials, particularly new functional dyes, in these remarkable progress fields is high, and its importance is expected to increase in the future. The pigment composition of the present invention also exhibits a high function when used as a functional dye which is a central material in the above-mentioned fields which have been developed in recent years. That is, it can be applied as color filter dyes, organic solar cell materials, organic nonlinear optical materials, organic transistor materials, various chromic dyes, biomedical materials, and the like.

  As a patent relating to pigments and pigment derivatives containing a naphthalene ring in the phthalocyanine skeleton, JP-A-1-180388 discloses an optical information recording medium. In this patent, a mixture of a phthalic anhydride derivative, a phthalimide derivative or a diiminoisoindoline derivative is used as a raw material, and as a synthetic intermediate, a phthalocyanine derivative mixture in which a benzene ring and a naphthalene ring are mixed in one molecule in addition to phthalocyanine and naphthalocyanine. Synthesizing. This derivative mixture is produced by a method similar to the pigment composition of the present invention, but in this patent, it is used as a precursor for the synthesis of the phthalo-naphthalocyanine ring derivative used. That is, the phthalocyanine derivative mixture is further chlorosulfonated and then reacted with amines to synthesize a sulfonamide derivative, and this material alone or in combination with a polymer binder is disclosed as an information recording layer of an optical information recording medium. Has been. The patent does not suggest that the synthetic precursor is refined and used as a pigment composition having an average particle size of 0.5 μm or less.

  Japanese Patent Application Laid-Open No. 7-7019 discloses an organic thin film characterized by being a thin film layer containing a 2,3: 12,13-dibenzophthalocyanine-based compound, and a production characterized by forming the organic thin film by a vacuum deposition method A method is disclosed. In JP-A-6-200195, dibenzo [b, t] -phthalocyaninatomagnesium is converted to disubstituted lithium phthalocyanine with normal butyllithium, and various metals are reacted by reacting the disubstituted lithium complex with various metal ions or acids. Methods for converting to phthalocyanine or metal-free phthalocyanine are disclosed. Japanese Unexamined Patent Publication No. 2000-44883 discloses a heat ray blocking organic film in which a metal naphthalocyanine derivative is dispersed in a binder resin. Japanese Patent Application Laid-Open No. 11-302284 discloses a sulfoxylated naphthalocyanine derivative and an ink-jet ink comprising the same. Japanese Patent Application Laid-Open No. 11-231510 discloses a photothermal conversion material containing metal-free or metal naphthalocyanine, halogenated metal-free or metal naphthalocyanine, and direct plate-making characterized by containing this material. A lithographic printing original plate is disclosed. Japanese Patent Application Laid-Open No. 10-88017 discloses a method for producing a metal-free or metal naphthalocyanine derivative with high purity and high yield. Japanese Patent Application Laid-Open No. 09-263658 discloses a gold infrared absorbing resin crude product containing metal-free or metal naphthalocyanine, halogenated metal-free or metal naphthalocyanine, and Japanese Patent Application Laid-Open No. 09-263717 is metal-free or metal-free. A near-infrared absorbent-dispersed aqueous coating material in which at least one of naphthalocyanine, halogenated metal-free or metallic naphthalocyanine is dispersed in an aqueous coating material is disclosed. Japanese Patent Laid-Open No. 5-150471 discloses an electrophotographic photosensitive member provided with a photosensitive layer containing a metal naphthalocyanine substituted with an alkyl group or a halogen atom as a stabilizer. Japanese Patent Application Laid-Open No. 3-21532 discloses an application of a metal-free, metal naphthalocyanine derivative as a third-order nonlinear optical material. Japanese Patent Laid-Open No. 3-130287 discloses a metal containing a perfluoroalkyl group, a metal-free naphthalocyanine derivative and a method for producing the same. JP-A-2-4865 discloses the use of a metal-free, metal naphthalocyanine derivative substituted with an alkoxyl group, aryloxy group or aralkyloxy group as a near-infrared absorber, and an optical recording medium comprising the recording layer in the recording layer. ing. Japanese Patent Laid-Open No. 2-92680 discloses a method for producing an optical recording medium, wherein a metal-free and metal naphthalocyanine having various substituents is coated on a substrate by using a peroxide. Japanese Unexamined Patent Publication No. 2-7242 discloses a multilayer recording medium for optical information having a layer containing metal-free and metal naphthalocyanine. Japanese Unexamined Patent Publication No. 63-231355 discloses an electrophotographic photosensitive member containing a metal naphthalocyanine derivative in a photosensitive layer on a conductive support. Japanese Patent Application Laid-Open No. 64-38853 discloses an electrophotographic photosensitive member having a photoconductive layer containing a specific metal naphthalocyanine derivative as an organic photoconductive material. Japanese Patent Application Laid-Open No. 61-186384 discloses an optical recording medium comprising a recording layer and a substrate containing a metal naphthalocyanine or a compound obtained by substituting a naphthalene ring of a metal naphthalocyanine with an anthracene ring. However, both are proposals using a naphthalocyanine compound, and did not suggest the use of a phthalo-naphthalocyanine ring derivative as a pigment composition.

  One of the characteristics of the chemical structure of currently used pigments, particularly, green pigments represented by C.I. Pigment Green 36, is that they contain a high proportion of halogen atoms such as chlorine and bromine. However, such a large amount of use of a pigment having a high halogen content can be one of the causes for pollution and destruction of the global environment from a long-term viewpoint. In recent years, destruction of the ozone layer that exists in the stratosphere of the earth has been regarded as a problem. The ozone layer absorbs much of the harmful ultraviolet rays from the sun and plays a role in protecting the terrestrial ecosystem. The ozone that forms the ozone layer is decomposed by hydroxy radicals, nitric oxide, chlorine atoms, etc., but the balance between generation and decomposition is maintained in the stratosphere. In recent years, it has been observed that ozone atoms in the ozone layer are promoted by chlorine atoms derived from chlorofluorocarbons and the like, and a part called an ozone hole in which the ozone concentration is extremely lowered is generated. It has been pointed out that such destruction of the ozone layer increases the amount of harmful ultraviolet rays on the surface and has an adverse effect on the human body. Therefore, it is desired to develop a pigment having excellent properties that does not contain a halogen atom that brings about such an action and has no problems with the global environment.

JP-A-1-180388 JP-A-7-7019 JP-A-6-200195 Japanese Patent Laying-Open No. 2005-241928 JP 2002-309131 A JP 2001-033944 A JP 2000-44883 A Japanese Patent Laid-Open No. 11-302284 JP-A-11-231510 JP-A-10-88017 JP-A-9-263658 Japanese Patent Laid-Open No. 9-263717 JP-A-5-150471 Japanese Patent Laid-Open No. 3-211532 Japanese Patent Laid-Open No. 3-130287 JP-A-2-4865 Japanese Patent Laid-Open No. 2-92680 Japanese Patent Laid-Open No. 2-7242 JP-A-63-231355 JP-A-64-38753 JP-A-61-186384

  Problems to be solved by the present invention include useful pigment compositions for inks, paints, coloring compositions for color filters, organic solar cell materials, organic nonlinear optical materials, organic transistor materials, various chromic dyes, biomedical materials, etc. To provide things. Furthermore, it is providing the pigment composition which has a particularly favorable characteristic as a coloring composition for color filters.

  As a result of intensive studies by the present inventors, a pigment composition comprising at least two of the compounds represented by the general formulas [1], [2], [3], [4], [5] and [6] The present invention has been found out that the product has the above-mentioned characteristics, and has led to the present invention.

  That is, the present invention comprises at least two kinds of compounds represented by the following general formulas [1], [2], [3], [4], [5] and [6], and has an average particle size of 0.5. The present invention relates to a pigment composition having a size of μm or less.

General formula [1]

General formula [2]

General formula [3]

General formula [4]

General formula [5]

General formula [6]

[Wherein, R ^{1 to} R ³⁶ each independently represents a hydrogen atom, an unsubstituted or substituted alkyl group, or an unsubstituted or substituted aryl group. M represents a metal atom. ]

  The present invention also includes at least [5] as an essential component among the compounds represented by the general formulas [1], [2], [3], [4], [5] and [6], and The present invention relates to the above pigment composition, wherein the total content of [5] and [6] is 50 mol% or more.

  The present invention also relates to a color composition for a color filter comprising a color material carrier comprising a transparent resin, a precursor thereof, or a mixture thereof, and the above pigment composition as a color material dispersed in the color material carrier.

  The pigment composition of the present invention has a high function as various colorants that are originally used for pigments, and can be applied to printing inks, paints, plastic coloring, etc. for cosmetics, stationery, leather, fibers, foods, etc. It can be used as a wide range of pigments. By using the pigment composition of the present invention, it is possible to obtain a higher effect on the fine and low viscosity dispersion of the pigment as compared with the conventional pigment, and the dispersion having high transparency and coloring power and good storage stability. The body can be prepared. In addition, by using the pigment composition of the present invention, it is possible to easily prepare high quality and highly stable products such as inks and paints.

  Furthermore, in the fields of electronics, optoelectronics, information and medical fields, which have been actively researched and developed in recent years, color filter dyes, organic solar cell materials, organic nonlinear optical materials, organic transistor materials, various chromic dyes, biomedicals By applying it to materials and the like, it can be used in a wide range as a pigment that exhibits a high function. In particular, when used as a coloring composition for a color filter, it is possible to provide a dispersion having a low viscosity and excellent temporal stability.

  The pigment composition of the present invention is a mixture of two or more phthalocyanine derivatives having different chemical structures. In general, it is known that phthalocyanine forms a regular laminated structure in a crystalline state, and the intermolecular force acting between unit molecules forming this laminated structure increases almost in proportion to the similarity of the structure. The pigment composition of the present invention contains at least two phthalocyanine derivatives having different chemical structures. Therefore, as described above, the intermolecular force in a system in which molecules having different chemical structures are mixed is smaller than the intermolecular force in a system composed of only molecules having a single chemical structure. As a result, the crystal structure formed by the pigment composition of the present invention has a more fragile property as compared to a crystal structure consisting of molecules of a single chemical structure. The pigment composition of the present invention having such a crystal structure has the convenience of use based on easy dispersibility for applications that require high dispersibility, such as inks, paints, and plastic colorants. Will be further enhanced. Furthermore, when the pigment composition of the present invention is used as various functional materials other than pigments, it is often applied as a thin film state. The above-described properties of the pigment composition of the present invention facilitate the formation of a thin film in such a case, and increase the convenience in use even when used as various functional materials. In addition, the pigment composition of the present invention is characterized in that it does not contain a halogen atom in its chemical structure. As already mentioned, it has been pointed out as a problem in use that a phthalocyanine-based green pigment represented by C.I. Pigment Green 36 has a relatively high halogen atom content. Furthermore, the pigment composition of the present invention has more excellent performance in terms of vividness and coloring power as a pigment as compared with C.I. Pigment Green 36 containing a halogen atom.

In the compounds represented by the general formulas [1], [2], [3], [4], [5] and [6] of the present invention, R ^{1 to} R ³⁶ are each independently a hydrogen atom, Alternatively, it represents an alkyl group having a substituent, an unsubstituted or substituted aryl group. M represents a metal atom.

  As the alkyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, Examples include isohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, and nonadecyl group.

  As the aryl group, a phenyl group, a biphenylyl group, a terphenylyl group, a quarterphenylyl group, a pentarenyl group, an indenyl group, a naphthyl group, a binaphthalenyl group, a tannaphthalenyl group, a quarternaphthalenyl group, an azulenyl group, a heptaenyl group, a biphenylenyl group, an indacenyl group Group, fluoranthenyl group, acephenanthrenyl group, aceanthrylenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarteranthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl Group, pyrenyl group, chrycenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexyl group Seniru group, rubicenyl group, coronenyl groups, trinaphthylenyl groups, heptacenyl groups, pyranthrenyl groups, ovalenyl group and the like.

  These alkyl groups and aryl groups may have a substituent.

  In this case, examples of the substituent include an alkyl group and an aryl group.

  Examples of the alkyl group that may have are the same as those already shown.

  Examples of the aryl group that may be included are the same as those already shown.

  Examples of the metal atom represented by M include two hydrogen atoms, two monovalent metals, a divalent metal atom, a trivalent monosubstituted metal atom, and a tetravalent disubstituted metal atom. Of these, divalent metal atoms are preferred because of their excellent resistance. Specific examples of the divalent metal atom include Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, etc. are mentioned. Examples of trivalent monosubstituted metal atoms include AlY, GaY, InY, TlY, FeY, RuY, MnY, ZnY, etc. Examples of tetravalent disubstituted metal atoms include SiY2, GeY2, SnY2, MnY2, CrY2, TiY2. , ZrY2, MnO, VO, TiO and the like. Here, Y is a monovalent ligand such as a halogen, a hydroxyl group, a halogen atom, or an alkoxy group.

  In the present invention, the pigment composition comprising at least two of the compounds represented by the general formulas [1], [2], [3], [4], [5] and [6] is, for example, It can manufacture by performing such a synthetic reaction.

Produced by heating a mixture of a phthalonitrile derivative represented by the following general formula [7] and a naphthalonitrile derivative represented by the following general formula [8] in a high boiling point solvent in the presence of a metal salt for several hours. be able to. In the following general formula [7] and general formula [8], R ^{37 to} R ⁴⁶ represent the same substituents as R ^{1 to} R ³⁶ described above.

General formula [7]

General formula [8]

In place of the phthalonitrile derivative represented by the general formula [7] and the naphthalonitrile derivative represented by the general formula [8], a phthalic anhydride derivative represented by the following general formula [9] and a general formula Naphthalene-2,3-dicarboxylic acid anhydride represented by [10] can also be used. In addition, R ^{47 to} R ⁵⁶ in the following general formula [9] and general formula [10] represent the same substituents as R ^{1 to} R ³⁶ described above.

General formula [9]

General formula [10]

Further, instead of the phthalonitrile derivative represented by the general formula [7] and the naphthalonitrile derivative represented by the general formula [8], the phthalimide derivative represented by the following general formula [11] and the general formula [12] It is also possible to use a naphthalene-2,3-dicarboximide derivative represented by the formula: Here, R ^{57 to} R ⁶⁶ in the following general formula [11] and general formula [12] represent the same substituents as R ^{1 to} R ³⁶ described above.

General formula [11]

General formula [12]

Further, instead of the phthalonitrile derivative represented by the general formula [7] and the naphthalonitrile derivative represented by the general formula [8], a diimide isoindoline derivative represented by the following general formula [13] and a general formula A benzodiiminoisoindoline derivative represented by [14] can also be used. Here, R ^{67 to} R ⁷⁶ in the following general formulas [13] and [14] represent the same substituents as R ^{1 to} R ³⁶ described above.

General formula [13]

General formula [14]

  Examples of the high boiling point solvent that can be used include halogenated hydrocarbons, diphenyl, diphenyl ether, high boiling point alcohols, N-alkylpyrrolidone, N, N-dimethylformamide, benzoic acid, and benzoic acid esters. However, it is not limited to these.

  Although the typical example of the pigment composition of this invention is specifically illustrated in the following Table 1, this invention is not limited to the following representative examples. Table 1 shows phthalonitriles, phthalimides, diiminoisoindolines, dicyanonaphthalenes, anhydrous naphthalenedicarboxylic acids, naphthalenedicarboximides, benzodiiminoisoindolines used as raw materials for the production of the pigment composition of the present invention. Examples, the molar ratio when using them as raw materials, and metals.

Table 1

  The pigment composition of the present invention may contain a yellow pigment or a blue pigment for the purpose of adjusting the hue. The yellow pigment and blue pigment used at this time are not particularly specified, but the following are preferable. Examples of yellow pigments include C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 199, and the like. Examples of blue pigments include C.I. I. Pigment blue 15, C.I. I. Pigment blue 16 and the like. These pigments may be used alone or in combination of two or more.

  As addition amount of a yellow pigment and a blue pigment, the quantity of 0-50 weight part with respect to 100 weight part of pigment compositions of this invention can be used with a desired hue.

  The pigment composition of the present invention and the yellow pigment and blue pigment to be contained in the pigment composition may be used as they are, but are used after the pigment particles are refined by a method such as solvent salt milling or dry milling as necessary. Also good. When using for the coloring composition for color filters, since a color filter with high transparency can be obtained by using a refined pigment, it is preferable to use a finer pigment.

  When refining by solvent salt milling, a mixture of an organic pigment, a water-soluble inorganic salt and a water-soluble solvent is kneaded using a kneader such as a kneader. Next, the kneaded mixture is poured into water and stirred with various stirrers to form a slurry. The inorganic salt and the solvent are removed by filtering this. Through the above steps, a refined organic pigment can be obtained. In this pigment refinement method, the pigment may be a single component or a mixture of two or more.

  Sodium chloride, potassium chloride, etc. can be used as a water-soluble inorganic salt in said refinement | miniaturization process. These inorganic salts are used in the range of 1 to 20 times the weight of the organic pigment. When the inorganic salt to be used is small, sufficient refinement is not performed, and when there is a large amount of inorganic salt, labor is required for removing the inorganic salt and the processing efficiency is lowered, which is not preferable in terms of productivity. As the water-soluble solvent, it is preferable to use a solvent having a boiling point in the range of 120 to 250 ° C. from the viewpoint of safety. Examples of solvents having such properties include 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, di Examples include propylene glycol monoethyl ether.

  The pigment dispersion formed by dispersing the pigment composition of the present invention in a medium is obtained by dispersing a mixture of the pigment composition of the present invention, a pigment derivative, and a resin with an organic solvent as required by various dispersing machines. Can be prepared. Further, a surfactant, a resin-type dispersant and the like may be further added to the above raw material and then dispersed. During the preparation, the pigment composition and the pigment dispersant of the present invention may be added as a pigment composition obtained by mixing in advance, or may be dispersed after separately added. Moreover, there are no particular limitations on the order of addition and the method of adding each raw material.

  The pigment derivative is a compound in which an amino group, a sulfone group, or a carboxyl group is bonded to an organic pigment residue via a linking group or directly.

  Organic pigments constituting the organic pigment residue include azo pigments such as azo, disazo, polyazo, phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, and metal-free phthalocyanine, aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, Anthraquinone pigments such as flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone, quinacridone pigment, dioxazine pigment, perinone pigment, perylene pigment, thioindigo pigment, isoindoline pigment, isoindolinone pigment, quinophthalone Pigments, selenium pigments, metal complex pigments and the like.

  Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalene sulfonate, sodium alkyldiphenyl ether disulfonate, monododecyl sulfate. Anionic properties such as ethanolamine, triethanolamine dodecyl sulfate, ammonium dodecyl sulfate, monoethanolamine stearate, sodium stearate, sodium dodecyl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Surfactant: Polyoxyethylene oleyl ether, polyoxyethylene dodecyl ether, polyoxyethylene nonylphenyl ether Nonionic surfactants such as tellurium, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts Agent: Examples include amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaine and alkylimidazolines, which can be used alone or in admixture of two or more.

  The resin-type pigment dispersant has a pigment affinity part that has the property of adsorbing to the pigment and a part that is compatible with the pigment carrier, and acts to stabilize the dispersion of the pigment on the pigment carrier by adsorbing to the pigment. It is something to do. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Oil-based dispersants such as salts; water-soluble such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based or the like is used. These can be used alone or in admixture of two or more.

  Examples of the resin used to prepare the pigment dispersion of the present invention include petroleum resin, casein, back rack, rosin modified maleic resin, rosin modified phenolic resin, nitrocellulose, cellulose acetate butyrate, cyclized rubber , Chlorinated rubber, oxidized rubber, hydrochloric acid rubber, phenol resin, alkyd resin, polyester resin, unsaturated polyester resin, amino resin, epoxy resin, vinyl resin, acrylic resin, methacrylic resin, polyurethane resin, silicone resin, fluorine resin, drying oil Synthetic drying oil, styrene-modified maleic acid resin, pyramide resin, polyimide resin, benzoguanamine resin, melamine resin, urea resin, chlorinated polypropylene, butyral resin, vinylidene chloride resin and the like.

  The resin can be used in an amount of 10 to 800 parts by weight with respect to 100 parts by weight of the pigment.

    In order to adjust the pigment dispersion for a color filter, high transparency is also required for the resin. The transparent resin is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Transparent resins include thermoplastic resins, thermosetting resins, and active energy ray curable resins, and precursors thereof include monomers or oligomers that are cured by irradiation with active energy rays to form transparent resins. These can be used alone or in admixture of two or more. The pigment carrier can be used in an amount of preferably 50 to 700 parts by weight, more preferably 100 to 400 parts by weight with respect to 100 parts by weight of the total pigment.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. Acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  Active energy ray-curable resins include (meth) acrylic compounds having reactive substituents such as isocyanate groups, aldehyde groups, and epoxy groups on polymers having reactive substituents such as hydroxyl groups, carboxyl groups, and amino groups. Or a resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reacting with cinnamic acid. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

  As monomers and oligomers, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate , Polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol Tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopenty Luglycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate, epoxy (meth) acrylate, urethane Various acrylates and methacrylates such as acrylates, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide , N-vinylformamide, acrylonitrile and the like, and these can be used alone or in admixture of two or more.

  The organic solvent used for preparing the pigment dispersion of the present invention is not particularly limited. Any of those generally used as a solvent can be used. For example, cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, toluene, xylene, ethyl cellosolve, methyl ethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, propylene glycol monomethyl ether, acetic acid Examples include ethyl, butyl acetate, hexane, methanol, ethanol, isopropyl alcohol, butanol, dioxane, dimethylformamide, and petroleum solvents. These solvents can be used either alone or in combination.

  When the organic solvent is used, it is preferably used in an amount of up to 4000 parts by weight with respect to 100 parts by weight of the pigment.

  The disperser used for preparing the pigment dispersion of the present invention is not particularly specified. For example, a horizontal sand mill, a vertical sand mill, an annular bead mill, an attritor, a microfluidizer, a high speed mixer, a homomixer, a ball mill, Examples thereof include a roll mill, a stone mill, an ultrasonic disperser, and a paint conditioner. Usually, any disperser or mixer used in preparing various dispersions can be used. Further, before dispersion by various dispersers, a pre-dispersion by a kneader mixer such as a kneader or a three roll mill, or a solid dispersion by a two roll mill or the like may be performed. In addition, after being dispersed with various dispersers, post-processing for about several hours to one week in a heated state at 30 to 80 ° C., processing using an ultrasonic disperser or a collision type beadless disperser, etc. It is effective for imparting dispersion stability to the pigment dispersion.

  It can manufacture by forming a filter segment by the printing method or the photolithographic method on a transparent or light reflective board | substrate using the coloring composition for color filters of this invention.

  When forming a filter segment by a photolithography method, a known photopolymerization initiator, sensitizer, the above-mentioned monomers, oligomers and the like can be added.

  When the filter segment is formed by a printing method, it is preferable to have a composition that does not dry and solidify the ink on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  In the present invention, the average particle diameter means that 100 particles are randomly observed using a transmission electron microscope (TEM), and the distance between the two most distant points of the outer shape of each particle is the micron marker on the screen. Measured based on the length of and averaged.

  In the pigment composition of the present invention, the content of the components corresponding to the general formulas [1] to [6] is measured with a time-of-flight mass spectrometer (TOF-MS) for the pigment composition of the present invention. This is the ratio of the signal intensity of the specific component to the sum of the signal intensities of the components corresponding to the general formulas [1] to [6], which is obtained by performing the above process.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these. In addition, the number of an Example is the same number as the pigment composition number in Table 1 already shown.

Example 1
25.6 g of phthalonitrile, 35.6 g of 2,3-dicyanonaphthalene and 10.9 g of cuprous chloride were suspended in 282 g of quinoline with stirring. The mixture was heated with stirring, stirred at 200 ° C. for 5 hours, and then cooled to room temperature. The precipitate was filtered, washed with room temperature methanol, 50 ° C. N-methylpyrrolidone and room temperature methanol and then dried at 70 ° C. 35.8 g of blue-green crystals were obtained.

  Mass spectrometry was performed on the obtained crystal, and it was confirmed that this crystal was a mixture composed of five types of molecular weight compounds. Furthermore, it confirmed that those molecular weight corresponded to the following 6 types of compounds which can be produced | generated from said synthesis reaction.

Example 2
6.4 g of phthalonitrile, 62.3 g of 2,3-dicyanonaphthalene and 10.9 g of cuprous chloride were suspended in 316 g of quinoline with stirring. The mixture was heated with stirring, stirred at 200 ° C. for 5 hours, and then cooled to room temperature. The precipitate was filtered, washed with room temperature methanol, 50 ° C. N-methylpyrrolidone and room temperature methanol and then dried at 70 ° C. 41.1 g of green crystals were obtained.

  The compounds represented by the general formulas [1], [2], [3], [4], [5] and [6] that can be produced from the raw materials used by mass spectrometry of the obtained crystals Among them, it was confirmed that two or more kinds of compounds including [5] were included.

Example 3
7.1 g of 4-methylphthalonitrile, 62.3 g of 2,3-dicyanonaphthalene and 14.8 g of cupric chloride were suspended in 319 g of quinoline with stirring. The mixture was heated with stirring, stirred at 200 ° C. for 6 hours, and then cooled to room temperature. The precipitate was filtered, washed with room temperature methanol, 50 ° C. N-methylpyrrolidone and room temperature methanol and then dried at 70 ° C. 40.2 g of green crystals were obtained.

  The compounds represented by the general formulas [1], [2], [3], [4], [5] and [6] that can be produced from the raw materials used by mass spectrometry of the obtained crystals Among them, it was confirmed that two or more kinds of compounds including [5] were included.

Example 4
7.7 g of phthalonitrile, 65.3 g of 2,3-dicyano-6-methyl-naphthalene and 10.9 g of cuprous chloride were suspended in 336 g of quinoline with stirring. The mixture was heated with stirring, stirred at 200 ° C. for 6 hours, and then cooled to room temperature. The precipitate was filtered, washed with room temperature methanol, 50 ° C. N-methylpyrrolidone and room temperature methanol and then dried at 70 ° C. 42.8 g of green crystals were obtained.

  The compounds represented by the general formulas [1], [2], [3], [4], [5] and [6] that can be produced from the raw materials used by mass spectrometry of the obtained crystals Among them, it was confirmed that two or more kinds of compounds including [5] were included.

Example 5
8.2 g of 3,4-dicyanobiphenyl, 64.1 g of 2,3-dicyanonaphthalene and 10.9 g of cuprous chloride were suspended in 333 g of quinoline with stirring. The mixture was heated with stirring, stirred at 200 ° C. for 6 hours, and then cooled to room temperature. The precipitate was filtered, washed with room temperature methanol, 50 ° C. N-methylpyrrolidone and room temperature methanol and then dried at 70 ° C. 42.1 g of green crystals were obtained.

  The compounds represented by the general formulas [1], [2], [3], [4], [5] and [6] that can be produced from the raw materials used by mass spectrometry of the obtained crystals Among them, it was confirmed that two or more kinds of compounds including [5] were included.

Example 6
4.3 g of 4-methyl-phthalonitrile, 71.0 g of 2,3-dicyano-6-methylnaphthalene and 14.8 g of cupric chloride were suspended in 346 g of quinoline with stirring. The mixture was heated with stirring, stirred at 200 ° C. for 6 hours, and then cooled to room temperature. The precipitate was filtered, washed with methanol at room temperature, N-methylpyrrolidone at 50 ° C. and methanol at room temperature, and then dried at 70 ° C. 44.8 g of green crystals were obtained.

  The compounds represented by the general formulas [1], [2], [3], [4], [5] and [6] that can be produced from the raw materials used by mass spectrometry of the obtained crystals Among them, it was confirmed that two or more kinds of compounds including [5] were included.

Example 9
6.2 g of 4,5-dimethylphthalonitrile, 64.1 g of 2,3-dicyanonaphthalene and 10.9 g of cuprous chloride were suspended in 323 g of quinoline with stirring. The mixture was heated with stirring, stirred at 200 ° C. for 7 hours, and then cooled to room temperature. The precipitate was filtered, washed with room temperature methanol, 50 ° C. N-methylpyrrolidone and room temperature methanol and then dried at 70 ° C. 41.6 g of green crystals were obtained.

  The compounds represented by the general formulas [1], [2], [3], [4], [5] and [6] that can be produced from the raw materials used by mass spectrometry of the obtained crystals Among them, it was confirmed that two or more kinds of compounds including [5] were included.

Example 10
3.1 g of 4,5-dimethylphthalonitrile, 78.3 g of 2,3-dicyano-6,7-dimethylnaphthalene and 10.9 g of cuprous chloride were suspended in 374 g of quinoline with stirring. The mixture was heated with stirring, stirred at 200 ° C. for 8 hours, and then cooled to room temperature. The precipitate was filtered, washed with room temperature methanol, 50 ° C. N-methylpyrrolidone and room temperature methanol and then dried at 70 ° C. 46.8 g of green crystals were obtained.

  The compounds represented by the general formulas [1], [2], [3], [4], [5] and [6] that can be produced from the raw materials used by mass spectrometry of the obtained crystals Among them, it was confirmed that two or more kinds of compounds including [5] were included.

Example 11
7.4 g of phthalic anhydride, 69.3 g of naphthalene-2,3-dicarboxylic acid anhydride, 10.9 g of cuprous chloride and 2.0 g of titanium tetrachloride were suspended in 353 g of quinoline with stirring. The mixture was heated with stirring, stirred at 200 ° C. for 8 hours, and then cooled to room temperature. The precipitate was filtered, washed with methanol at room temperature, N-methylpyrrolidone at 50 ° C. and methanol at room temperature, and then dried at 70 ° C. 44.8 g of green crystals were obtained.

  The compounds represented by the general formulas [1], [2], [3], [4], [5] and [6] that can be produced from the raw materials used by mass spectrometry of the obtained crystals Among them, it was confirmed that two or more kinds of compounds including [5] were included.

Example 12
7.4 g of phthalimide, 69.0 g of naphthalene-2,3-dicarboximide, 10.9 g of cuprous chloride and 2.0 g of titanium tetrachloride were suspended in 351 g of quinoline with stirring. The mixture was heated with stirring, stirred at 200 ° C. for 8 hours, and then cooled to room temperature. The precipitate was filtered, washed with room temperature methanol, 50 ° C. N-methylpyrrolidone and room temperature methanol and then dried at 70 ° C. 43.6 g of green crystals were obtained.

  The compounds represented by the general formulas [1], [2], [3], [4], [5] and [6] that can be produced from the raw materials used by mass spectrometry of the obtained crystals Among them, it was confirmed that two or more kinds of compounds including [5] were included.

Example 13
7.3 g of diiminoisoindoline, 68.3 g of benzodiiminoisoindoline, 10.9 g of cuprous chloride and 2.0 g of titanium tetrachloride were suspended in 351 g of quinoline with stirring. The mixture was heated with stirring, stirred at 200 ° C. for 8 hours, and then cooled to room temperature. The precipitate was filtered, washed with room temperature methanol, 50 ° C. N-methylpyrrolidone and room temperature methanol and then dried at 70 ° C. 43.6 g of green crystals were obtained.

  The compounds represented by the general formulas [1], [2], [3], [4], [5] and [6] that can be produced from the raw materials used by mass spectrometry of the obtained crystals Among them, it was confirmed that two or more kinds of compounds including [5] were included.

Example 14
5.1 g of phthalonitrile, 64.1 g of 2,3-dicyanonaphthalene and 26.1 g of nickel chloride hexahydrate were suspended in 318 g of quinoline with stirring. The mixture was heated with stirring, stirred at 200 ° C. for 6 hours, and then cooled to room temperature. The precipitate was filtered, washed with room temperature methanol, 50 ° C. N-methylpyrrolidone and room temperature methanol and then dried at 70 ° C. 39.8 g of green crystals were obtained.

  The compounds represented by the general formulas [1], [2], [3], [4], [5] and [6] that can be produced from the raw materials used by mass spectrometry of the obtained crystals Among them, it was confirmed that two or more kinds of compounds including [5] were included.

Example 15
5.1 g of phthalonitrile, 64.1 g of 2,3-dicyanonaphthalene and 20.2 g of zinc acetate were suspended in 318 g of quinoline with stirring. The mixture was heated with stirring, stirred at 200 ° C. for 5 hours, and then cooled to room temperature. The precipitate was filtered, washed with room temperature methanol, 50 ° C. N-methylpyrrolidone and room temperature methanol and then dried at 70 ° C. 40.1 g of green crystals were obtained.

  The compounds represented by the general formulas [1], [2], [3], [4], [5] and [6] that can be produced from the raw materials used by mass spectrometry of the obtained crystals Among them, it was confirmed that two or more kinds of compounds including [5] were included.

Example 16
5.7 g of 3-methylphthalonitrile, 64.1 g of 2,3-dicyanonaphthalene and 10.9 g of cuprous chloride were suspended in 321 g of quinoline with stirring. The mixture was heated with stirring, stirred at 200 ° C. for 6 hours, and then cooled to room temperature. The precipitate was filtered, washed with room temperature methanol, 50 ° C. N-methylpyrrolidone and room temperature methanol and then dried at 70 ° C. 40.6 g of green crystals were obtained.

  The obtained crystals are subjected to mass spectrometry, and can be generated from the raw materials used, and are represented by general formulas [1], [2], [3], [4], [5] and [6] It was confirmed that two or more kinds of compounds including [5] were included among the compounds.

Example 17
4.7 g of 3,6-dimethylphthalonitrile, 65.9 g of 2,3-dicyanonaphthalene and 10.9 g of cuprous chloride were suspended in 325 g of quinoline with stirring. The mixture was heated with stirring, stirred at 200 ° C. for 5 hours, and then cooled to room temperature. The precipitate was filtered, washed with room temperature methanol, 50 ° C. N-methylpyrrolidone and room temperature methanol and then dried at 70 ° C. 39.4 g of green crystals were obtained.

  The compounds represented by the general formulas [1], [2], [3], [4], [5] and [6] that can be produced from the raw materials used by mass spectrometry of the obtained crystals Among them, it was confirmed that two or more kinds of compounds including [5] were included.

Example 18
7.4 g of 3,4,5,6-tetramethylphthalonitrile, 64.1 g of 2,3-dicyanonaphthalene and 15.8 g of cuprous bromide were suspended in 329 g of quinoline with stirring. The mixture was heated with stirring, stirred at 200 ° C. for 8 hours, and then cooled to room temperature. The precipitate was filtered, washed with room temperature methanol, 50 ° C. N-methylpyrrolidone and room temperature methanol and then dried at 70 ° C. 41.4 g of green crystals were obtained.

  The compounds represented by the general formulas [1], [2], [3], [4], [5] and [6] that can be produced from the raw materials used by mass spectrometry of the obtained crystals Among them, it was confirmed that two or more kinds of compounds including [5] were included.

Example 19
7.1 g of 4-methylphthalonitrile, 72.1 g of 6,7-dimethyl-2,3-dicyanonaphthalene and 22.0 g of cupric acetate monohydrate were suspended in 364 g of quinoline with stirring. The mixture was heated with stirring, stirred at 200 ° C. for 6 hours, and then cooled to room temperature. The precipitate was filtered, washed with room temperature methanol, 50 ° C. N-methylpyrrolidone and room temperature methanol and then dried at 70 ° C. 45.1 g of green crystals were obtained.

  The compounds represented by the general formulas [1], [2], [3], [4], [5] and [6] that can be produced from the raw materials used by mass spectrometry of the obtained crystals Among them, it was confirmed that two or more kinds of compounds including [5] were included.

Example 20
3.8 g of phthalonitrile, 94.0 g of 5-phenyl-2,3-dicyanonaphthalene and 10.9 g of cuprous chloride were suspended in 450 g of quinoline with stirring. Next, the mixture was heated with stirring, stirred at 200 ° C. for 8 hours, and then cooled to room temperature. The precipitate was filtered, washed with room temperature methanol, 50 ° C. N-methylpyrrolidone and room temperature methanol and then dried at 70 ° C. 53.3 g of green crystals were obtained.

  The compounds represented by the general formulas [1], [2], [3], [4], [5] and [6] that can be produced from the raw materials used by mass spectrometry of the obtained crystals Among them, it was confirmed that two or more kinds of compounds including [5] were included.

Example 21
6.2 g of 4-ethylphthalonitrile, 64.1 g of 2,3-dicyanonaphthalene and 14.8 g of cupric chloride were suspended in 323 g of quinoline with stirring. The mixture was heated with stirring, stirred at 200 ° C. for 7 hours, and then cooled to room temperature. The precipitate was filtered, washed with room temperature methanol, 50 ° C. N-methylpyrrolidone and room temperature methanol and then dried at 70 ° C. 40.1 g of green crystals were obtained.

  The compounds represented by the general formulas [1], [2], [3], [4], [5] and [6] that can be produced from the raw materials used by mass spectrometry of the obtained crystals Among them, it was confirmed that two or more kinds of compounds including [5] were included.

  As mentioned above, although the synthesis examples 1-21 were demonstrated, the target object can be obtained with the same manufacturing method also about another compound.

  Next, examples of the composition, particle size and sharpness evaluation of the pigment composition of the present invention are shown.

  FIG. 1 shows the results obtained by measuring the pigment composition 2 of the present invention with a time-of-flight mass spectrometer (TOF-MS) autoflex II manufactured by Bruker Daltonics.

  Here, the measurement result of TOF-MS is the ion amount at each molecular weight, and in the molecular weight range of the present invention, each molecule is detected in a monovalent ion state by performing an appropriate measurement. For this reason, the measurement result of TOF-MS can be substituted as a molar ratio.

  In FIG. 1, numbers 1 to 4 are assigned to four peaks corresponding to each detected signal. From the molecular weights corresponding to these four detection signals, 1 has a copper phthalocyanine derivative having 3 benzene rings and 1 naphthalene ring in one molecule, and 2 has 2 benzene rings and 2 naphthalene rings in 1 molecule. Copper phthalocyanine derivative 3 is a copper phthalocyanine derivative having one benzene ring and three naphthalene rings in one molecule, and 4 is equivalent to copper naphthalocyanine. At this time, the content ratio (mol%) of the compounds represented by the general formulas [5] and [6] is to calculate the ratio of the sum of the peak heights of 3 and 4 to the sum of the four peak heights. Is the value obtained by Such a measurement was performed on other pigment compositions in the present invention, and the sum of the content ratios of the compounds represented by the general formulas [5] and [6] was determined.

  Next, 35 g of the pigment composition of the present invention was charged with 170 g of salt and 30 g of diethylene glycol in a kneader, and pulverized at 80 ° C. for 6 hours. The pigment particles obtained by such treatment were observed with a transmission electron microscope JEM-1010 manufactured by JEOL, and the average particle size was calculated by the method described above.

  The sum of the content ratios of the compounds represented by the general formulas [5] and [6] and the average particle size values obtained by the above measurement are shown in Table 2 as Examples 22 to 33.

Table 2

  Next, an Example when a resistance test is applied to the pigment composition of the present invention is shown.

Light Resistance 0.5 g of the pigment composition of the present invention and 2.0 g of varnish for printing ink were kneaded using a Hoover Mahler by repeating 100 rotations 4 times. Printing was performed on white paper using the ink thus prepared. The printed paper was irradiated with light for 192 hours using a Suga Test Instruments UV Long Life Fade Meter FAL-3C. The color difference was obtained from the colorimetric values before and after UV irradiation, and this value was used as an index of light resistance. That is, the smaller the color difference, the higher the light resistance.

Acid resistance, alkali resistance and solvent resistance 300 g of the filtrate obtained by shaking 0.1 g of the pigment composition of the present invention and 20 g of the following test liquid in a glass bottle at room temperature for 2 hours, followed by filtration. The maximum absorbance in the wavelength region of 800 nm was measured. The greater the absorbance value, the lower the resistance. The test liquid is as follows.
Acid resistance: Hydrochloric acid consisting of 2 g of hydrogen chloride and 98 g of water Alkali resistance: Aqueous solution in which 2 g of sodium hydroxide is dissolved in 98 g of water Solvent resistance: Ethanol, xylene, ethyl acetate, methyl ethyl ketone

Examples 34-54 and Comparative Example 1
The results of the above light resistance, acid resistance, alkali resistance and solvent resistance test are shown in Table 3 as Examples 34 to 54. Table 3 also shows the results of a similar test performed on CIPigment Green 36 as a comparative example.

Table 3

  As shown in Table 3, it can be seen that the pigment composition of the present invention is superior in light resistance, acid resistance, alkali resistance and solvent resistance as compared with C.I. Pigment Green 36.

  Next, examples of measuring absorption characteristics of the pigment composition of the present invention will be shown.

Example 55 and Comparative Example 2
0.5 g of the pigment composition 1 of the present invention and 2.0 g of ditrimethylolpropane tetraacrylate polymer were kneaded by repeating 100 rotations 4 times using a Hoover-Muller. The obtained pigment dispersion was applied onto a slide glass to form a thin film, and the absorbance of this thin film sample was measured. Moreover, the same sample was produced using CI Pigment Green 36 as a comparative example, and the same measurement was performed. Table 4 shows wavelengths corresponding to the maximum absorbance and the minimum absorbance obtained from this measurement.

Table 4

  From Table 4, it can be seen that the difference between the minimum absorption wavelength of the pigment composition 1 of the present invention and C.I. Pigment Green 36 is 2.5 nm, and the hue as the pigment is almost equal.

  Next, Examples when the pigment composition of the present invention is used as a pigment dispersion are shown.

Preparation of Acrylic Resin Solution 400 g of cyclohexanone was added to a four-necked flask equipped with a thermometer, a condenser tube, a nitrogen gas inlet tube, and a stirrer, and heated to 100 ° C. under nitrogen gas injection. At this temperature, a mixture of 30 g of methacrylic acid, 32.5 g of methyl methacrylate, 32.5 g of butyl methacrylate, 30 g of 2-hydroxyethyl methacrylate, 5 g of 2,2′-azobisisobutyronitrile was dropped over about 1 hour. A polymerization reaction was performed. After completion of the dropwise addition, the mixture was further stirred for 3 hours, a solution in which 2 g of 2,2′-azobisisobutyronitrile was dissolved in 25 g of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour, and the weight average molecular weight was about A 40,000 acrylic resin solution was obtained.

  After cooling to room temperature, about 2 g of the resin solution was sampled and heated to dryness at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexane was added to the previously synthesized resin solution so that the nonvolatile content was 20%. An acrylic resin solution was prepared.

Preparation of treated pigment A mixture of 200 g of the pigment composition of the present invention, 800 g of sodium chloride and 100 g of diethylene glycol was kneaded at 120 ° C. for 2 hours using a stainless gallon kneader (manufactured by Inoue Seisakusho). Next, this kneaded material was put into 3 liters of warm water and stirred at 70 ° C. for 1 hour. Thereafter, filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying at 80 ° C. for 24 hours to obtain 192 g of treated pigment.

Examples 56 to 76 and Comparative Example 3
The pigment composition of the present invention, the treated pigment alone having the above-mentioned adjustment or a pigment mixed with 10% by weight of the above-mentioned yellow pigment, and a pigment dispersant PB821 (Ajinomoto Co.) in an amount corresponding to 10% by weight of this pigment. Fine techno), cyclohexanone as an acrylic resin solution and a solvent as shown above are mixed in the amounts shown in Table 2 below, put into a 140 ml screw bottle with 150 g of zirconia beads having a diameter of 1.25 mm, and 15 with a paint conditioner. A pigment dispersion was obtained by time dispersion.

The viscosity and thixotropic index value (hereinafter referred to as TI value) of the pigment dispersion thus obtained were measured with a B-type viscometer. Further, after the pigment dispersion was stored at 40 ° C. for one week, the viscosity was measured again, and the result of the viscosity increase rate was evaluated in three stages of A to C according to the following criteria.
A: Almost no thickening is observed B: Some thickening is observed, but it is in a usable range C: Thickening is remarkably unusable

  The above evaluation results are summarized and shown in Table 5 below.

Table 5

  As shown in Table 5, it is understood that those using the pigment composition of the present invention have a low viscosity, a small TI value, and excellent fluidity. Furthermore, the viscosity stability over time showed good results, and it can be seen that it is excellent as a coloring composition for color filters.

  The pigment composition of the present invention can be used as a pigment dispersant, a pigment composition, and a pigment dispersion, and is a pigment dispersant effective for the preparation of inks and paints, and a pigment composition containing the same. Application to a pigment dispersion in which a pigment composition is dispersed in a vehicle is possible. By using the pigment composition of the present invention, it is possible to easily obtain products such as inks and paints that are non-aggregating, non-crystalline, low viscosity, low thixotropic and have good viscosity stability over time. . The pigment dispersant, pigment composition and pigment dispersion of the present invention are gravure ink, general paint for automobiles, wood and metal, magnetic tape back coat paint, radiation cure ink, ink jet printer ink, color filter ink It can be applied to other uses.

  The pigment composition of the present invention is used as an organic solar cell material, organic nonlinear optical material, organic transistor material, and other chromic dyes as novel functional dyes in electronic engineering, optoelectronics, information-related fields, and the like. It can be used as a biomedical material such as a dye for medical diagnosis.

FIG. 1 shows the measurement results of the pigment composition 2 of the present invention using a time-of-flight mass spectrometer (TOF-MS).

Claims (3)

A pigment comprising at least two kinds of compounds represented by the following general formulas [1], [2], [3], [4], [5] and [6] and having an average particle diameter of 0.5 μm or less Composition.
General formula [1]

General formula [2]

General formula [3]

General formula [4]

General formula [5]

General formula [6]

[Wherein, R ^{1 to} R ³⁶ each independently represents a hydrogen atom, an unsubstituted or substituted alkyl group, or an unsubstituted or substituted aryl group. M represents a metal atom. ]   Of the compounds represented by the general formulas [1], [2], [3], [4], [5] and [6], at least the general formula [5] is an essential component, and the general formula [1 ], [2], [3], [4], [5] and [6], the sum of the contents of the general formulas [5] and [6] is 50 mol% or more. The pigment composition according to claim 1.   A coloring composition for a color filter, comprising: a coloring material carrier comprising a transparent resin, a precursor thereof or a mixture thereof; and the pigment composition according to claim 1 as a coloring material dispersed in the coloring material carrier. .

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