JP5015238B2 - Color filter composition and color filter - Google Patents

Description

  The present invention relates to a composition for a color filter used for pixels such as a color liquid crystal display, a cured product formed using the composition, and a color filter.

  Color filters used in liquid crystal displays are usually used in a pattern in which pixels of the three primary colors red, blue, and green are arranged in a mosaic pattern. These pixels are used in the pigment dispersion method, printing method, dyeing method, inkjet method, and electrodeposition. It is manufactured by the method etc. In particular, the pigment dispersion method in which an image is formed by photolithography to produce pixels of the three primary colors uses a pigment as a coloring material, and thus has excellent hue vividness, light resistance, heat resistance, and solvent resistance. For this reason, it has become the mainstream color filter manufacturing method.

  The pigment used in the color resist ink is selected so that its spectral transmission characteristics match the light emission characteristics of the backlight. There are various types of backlights, and high-color-rendering three-wavelength fluorescent lamps having sharp emission at wavelengths corresponding to the three primary colors of red, green, and blue (generally 610 nm, 545 nm, and 435 nm) are widely used. In addition, pigments are required to effectively transmit or block light of these three wavelengths. However, it is often difficult to adapt to the emission spectrum of the backlight with the current single pigment color, and color adjustment is often performed by using a plurality of pigments having different hues. For example, a green pixel mainly uses a green pigment and a yellow pigment, a red pixel mainly uses a red pigment and a yellow pigment, and a blue pigment mainly uses a blue pigment and a purple pigment.

  On the other hand, in recent years, as a means for expanding the color gamut, four or five color filters in which cyan and / or yellow pixels are added to red, green, and blue pixels have been proposed, and the hue of yellow pigments has been expanded. Has become an important issue.

  As described above, yellow pigments are one of the important elements in color filter pixel formation. With the recent demands for higher color saturation and color reproduction range of color filters, improvement of yellow pigment performance is an urgent issue. It is a problem. However, since yellow pigments used for current color filters are mainly three types of PY (Pigment Yellow) 138, 139, and 150 from the viewpoint of transmission waveform and fastness, the hue is limited.

By the way, the azomethine-based metal complex can have a wide range of hues depending on the presence or absence of a substituent and the metal species, but generally has low heat resistance and is difficult to disperse. As a known pigment of the azomethine-based metal complex, there is PY129 (azomethine copper complex). Patent Documents 1 and 2 disclose that PY129 is used as a composition for a color filter. However, for the above reasons, it is hardly used for current color filters.
JP-A-10-237326 JP-A-9-269410

  The present invention has been made in view of the disadvantages of the prior art. When used in a color liquid crystal display or the like, the present invention expands the color reproduction range and is formed using a novel color filter composition excellent in heat resistance. The object is to provide a color filter.

  As a result of studying to solve the above problems, the present inventors, in a composition for a color filter containing an azomethine zinc complex as a colorant component, have an unprecedented hue, heat resistance and dispersibility. The inventors have found that an excellent color filter can be produced and completed the present invention.

（但し、Ｒ¹は水素原子、ハロゲン原子、メチル基又はフェニル基を示し、Ｒ²は水素原子、ハロゲン原子、メチル基又はニトロ基を示し、Ｘはハロゲン原子又はメトキシ基を示す。）That is, the present invention is a color filter composition comprising (A) a colorant, (B) a curable polymer and / or a curable monomer, (C) a dispersant, and (D) a solvent, A color filter composition, wherein the colorant of A) contains an azomethine zinc complex represented by the following general formula (1) or (2).

(However, R ¹ represents a hydrogen atom, a halogen atom, a methyl group or a phenyl group, R ² represents a hydrogen atom, a halogen atom, a methyl group or a nitro group, and X represents a halogen atom or a methoxy group.)

  Moreover, this invention is a hardened | cured material obtained by hardening | curing the said composition for color filters, and also this invention is a color filter which the cured film which forms a pixel consists of the said hardened | cured material.

The color filter composition in the present invention is preferably a color difference ΔE * _ab (color difference defined by JIS Z 8730) before and after heat-curing a cured film obtained by curing the color filter composition at 250 ° C. for 1 hour. Is preferably 5 or less, and the color filter composition in the present invention is preferably such that the curable polymer and / or curable monomer (B) is composed of an epoxy acrylate having a fluorene skeleton. Good.

Hereinafter, the present invention will be described in detail.
The color filter composition of the present invention is obtained by dispersing a colorant containing an azomethine zinc complex represented by the general formula (1) or (2) in a resin composition. Here, the colorant usually means a pigment, a dye or the like, but the azomethine zinc complex means to be used as a pigment. Here, the pigment refers to a colorant that does not substantially dissolve in the solvent. The resin composition refers to a composition comprising components other than the colorant in the color filter composition of the present invention. (B) A curable polymer and / or a curable monomer (curable resin), ( C) A dispersant and (D) a solvent are contained as essential components, and other necessary components (polymerization initiator, additive, etc.) can also be blended.

  The metal species of the azomethine metal complex used in the present invention is limited to zinc. Zinc complexes have good heat resistance and dispersibility, but other metal species have poor heat resistance and are difficult to disperse, making it difficult to obtain good color filters. Furthermore, as the substituent of the azomethine zinc complex, X described above is preferably bromine because it similarly has good heat resistance and dispersibility.

  As a method for synthesizing the azomethine zinc complex, for example, the method described in Journal of the Chinese Chemical Society, 2001, 48, 153-158 can be used. Specifically, it can be obtained by heating and stirring each salicylaldehyde derivative, 2-hydroxynaphthaldehyde, 2-aminophenol derivative, zinc acetate dihydrate, and the like. The compound synthesized by the above method can be purified by washing with a solvent such as water, acetone or alcohol, and can be obtained with high purity. However, the synthesis method and the purification method are not limited to the above methods.

  The average particle size of the azomethine zinc complex is preferably 10 to 500 nm, and more preferably 50 to 400 nm. When the average particle diameter is smaller than 10 nm, the coloring power and weather resistance are insufficient, and when the average particle diameter is larger than 500 nm, the vividness and transparency of the hue are insufficient.

  As a method for pigmentizing the azomethine zinc complex, a known method can be used, and examples thereof include an acid pasting method, an acid slurry method, a dry milling method, a solvent milling method, a salt milling method, and a solvent salt milling method. The solvent milling method, salt milling method, solvent salt milling method and the like are particularly preferable in that a finely divided pigment having a controlled particle size can be obtained. However, the method of pigmentation is not particularly limited.

  When the purpose is to form a yellow pixel, the azomethine zinc complex in the present invention is preferably contained in an amount of 10% by weight or more, preferably 50% by weight or more in the total coloring material. If it is less than 10% by weight, the hue specific to the azomethine zinc complex cannot be exhibited. Moreover, although the said azomethine complex can be used individually as a coloring material component, another coloring material can also be used together. Other colorants suitable for forming a yellow pixel include Pigment Yellow 109, 110, 117, 128, 129, 138, 139, 150, 153, 155, and 173. 185 and the like. In addition, the colorant which can be used together is not limited to these.

  The azomethine zinc complex can be used in combination with other colorants for the purpose of color adjustment in the formation of green pixels, red pixels, and cyan pixels. From the viewpoint of hue, the compound represented by the general formula (1) Is preferably used in a red pixel or a green pixel, and the compound represented by the general formula (2) is preferably used in a green pixel or a cyan pixel. Coloring materials suitable for use in combination include Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60, 76, and 80. , Pigment Green 4, 7, 10, 36, Pigment Red 38, 48: 1, 53: 1, 57: 1, 112, 122, 144, 149, 168, 170, 175, 177, 242, 247, 254, 255, etc. can be mentioned, but the pigments that can be used in combination are not limited thereto.

  In the present invention, the mixing ratio of the colorant in the color filter composition is preferably 5 to 60% by weight and more preferably 10 to 50% by weight in the solid content of the color filter composition. . Here, solid content of the composition for color filters means components other than the solvent of the composition for color filters. When the content of the coloring material is less than 5% by weight, the coloring power is insufficient and a high-brightness color filter cannot be obtained. On the other hand, if it exceeds 60% by weight, the dispersion stability tends to deteriorate, and the relative amount of reactive components such as a curable polymer in the composition decreases, which causes a problem in pattern formation in the photolithography process. May occur.

  The curable polymer and / or monomer (B) is selected from, for example, at least one of a photopolymerizable polymer, a photopolymerizable monomer, and a photopolymerizable oligomer (hereinafter, these are collectively referred to as “photopolymerizable”. Examples of the resin having an ethylenically unsaturated bond may be mentioned. Specifically, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A type epoxy di (meth) acrylate, bisphenol F And (meth) acrylic acid esters such as bisphenol fluorene type epoxy di (meth) acrylate and the like. Also, vinyl polymers such as acrylic acid (co) polymer, (meth) acrylic acid (co) polymer, maleic acid (co) polymer, polyethylene oxide, polyvinylpyrrolidone, polyamide, polyurethane, polyether, polyester, etc. Mention may also be made of polymers having an ethylenic double bond in the side chain. These may be used alone or in combination of two or more. These polymers desirably have an alkali-soluble substituent such as a carboxyl group or a phenolic hydroxyl group in the side chain for the purpose of improving developability.

（式中、Ｒ³及びＲ⁴は水素原子、炭素数１〜５のアルキル基、フェニル基、又はハロゲン原子の何れかであり、Ｙは下記式（４）

を示し、ｎは０〜１０であり、ＡはＣＨ₂＝ＣＲ'−ＣＯ−を示し、Ｒ’は水素原子又はメチル基を示す。）In addition, in the color filter composition of the present invention, from the viewpoint that the cured product provides a high level of heat resistance and solvent resistance, an epoxy acrylate resin having a fluorene skeleton as at least one component is used as a photopolymerizable resin. It is advantageous to use. Preferred examples of the epoxy acrylate resin having a fluorene skeleton used include those obtained by reacting an epoxy (meth) acrylate represented by the following general formula (3) with a polybasic acid or an acid anhydride thereof. It is done.

(In the formula, R ³ and R ⁴ are any one of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a halogen atom, and Y represents the following formula (4):

, N is 0 to 10, A represents CH ₂ ═CR′—CO—, and R ′ represents a hydrogen atom or a methyl group. )

  The method for producing an epoxy acrylate resin having a fluorene skeleton by reacting the epoxy acrylate represented by the general formula (3) with a polybasic acid or an acid anhydride thereof is not particularly limited, and is a known method. Can be adopted. In addition, the epoxy acrylate resin as used in the field of this invention is used by the meaning containing the derivative of epoxy acrylate resins, such as an epoxy methacrylate resin.

  Here, examples of the polybasic acid or acid anhydride thereof include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, and methyltetrahydrophthalic acid. Examples include acids, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, and acid anhydrides thereof. In the present invention, it is particularly preferable to use (i) saturated dicarboxylic acids or (b) saturated tetracarboxylic acids for these polybasic acids or acid anhydrides thereof. Here, saturation of saturated dicarboxylic acids and saturated tetracarboxylic acids does not have an unsaturated bond (bond other than a single bond) other than a carbonyl group (> C═O) constituting a carboxyl group or an acid anhydride group. means. Examples of preferred saturated carboxylic acids include butanetetracarboxylic acid, hexahydrophthalic acid, succinic acid and acid anhydrides thereof. Tetrahydrophthalic acid is also exemplified as a preferred carboxylic acid.

  (I) Saturated dicarboxylic acids and (b) saturated tetracarboxylic acids can each be used in one or more types, and (a) the use ratio of (b) saturated dicarboxylic acids and (b) saturated tetracarboxylic acids is: The molar ratio of (b) is in the range of 0.1 to 10, preferably in the range of 0.2 to 1. The ratio of use can be selected for the optimal molecular weight, alkali developability, light transmission, heat resistance, solvent resistance, and pattern shape effects. However, the larger the ratio of saturated tetracarboxylic acids used, the greater the alkalinity. The solubility tends to increase and the molecular weight tends to increase. In addition, also when using dicarboxylic acids and tetracarboxylic acids other than saturated dicarboxylic acids and saturated tetracarboxylic acids, it is good to satisfy the said molar ratio.

  Moreover, about (B) component, polymers other than the said photocurable polymer, for example, a thermosetting polymer, can also be used. The thermosetting polymer is selected from at least one of a thermopolymerizable polymer, a thermopolymerizable monomer, and a thermopolymerizable oligomer, such as trimethylolpropane triglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl. Glycidyl group-containing compounds such as ether, bisphenol fluorenediglycidyl ether, glycidyl methacrylate (co) polymer, and alicyclic epoxy compounds such as 3,4-epoxycyclohexane and bis (3,4-epoxycyclohexylmethyl) adipate Although it is mentioned, well-known curable polymers other than the above can also be used.

  The component (B) curable polymer and / or monomer may include those that become a polymer in a cured state, and includes a case where only a component that is not resinated is included in an uncured state. The curable polymer and / or monomer may be appropriately selected in consideration of the color filter manufacturing process.

  The type of the dispersant for component (C) is not particularly limited, but one type selected from (a) poly (lower alkyleneamine) and (b) polyallylamine from the viewpoint of excellent dispersion stability. Alternatively, two or more kinds of nitrogen-containing compounds are reacted with one or more kinds of carboxyl group-containing compounds selected from (i) polyester having a free carboxyl group, (ii) polyamide, and (iii) polyester amide. Alternatively, it is preferable to use a graft polymer formed by forming a salt.

(A) Poly (lower alkyleneimine) is composed of primary (—NH ₂ ), secondary (—NH—) and tertiary (—N <) amino groups with a lower alkylene chain (—R—, for example —CH ₂ CH _2- ) is a polymer having a branched structure, and (b) polyallylamine is a polymer having a structure consisting of [—CH ₂ —CH (CH ₂ NH ₂ ) —] _n . In addition, the carboxyl group-containing compounds (i), (ii) and (iii) have at least one carboxyl group at the terminal or side chain, and this is at least one of —NH _{2 and the} like in (a) and (b). It reacts with a portion -NHCO- or NH ₃ ⁺ · ^- OCO- like form to a form a graft polymer.

  The mixing ratio of the dispersant (C) is 10 to 60% by weight, preferably 20 to 50% by weight, based on the colorant (A). When the content of the dispersant is less than 10% by weight with respect to the colorant (A), the dispersion stability of the pigment dispersion is insufficient. On the other hand, when the content exceeds 60% by weight, effective pixel formation in the photolithography process is achieved. The ability cannot be demonstrated. High viscosity substances such as resins generally have an action of stabilizing the dispersion, but those not having the ability to promote dispersion are not treated as dispersants. However, it is not limited to use for the purpose of stabilizing dispersion.

  As the solvent of component (D), esters, ketones, ethers, ether alcohols, ether esters, aromatic solvents, nitrogen-containing solvents, and the like can be preferably used. Specific examples of the esters include ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, and γ-butyrolactone. Examples of ketones include methyl isobutyl ketone, cyclohexanone, and isophorone. Examples of ethers include monoglyme, diglyme, triglyme, propylene glycol dimethyl ether, and dipropylene glycol dimethyl ether. Examples of ether alcohols include cellosolve, methyl cellosolve, carbitol, methyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and the like. Examples of ether esters include cellosolve acetate, propylene glycol monomethyl ether acetate, and 3-methoxybutyl acetate. Examples of the aromatic solvent include toluene, xylene, cumene and the like. Examples of the nitrogen-containing solvent include 2-pyrrolidone, N-methyl-2-pyrrolidone, N, N-dimethylformamide and the like. These may be appropriately selected according to the composition of the component (B) and other components to be blended, the coating properties of the color filter composition, etc., and may be used alone or in combination of two or more. Also good.

  In the composition for color filter of the present invention, for the purpose of improving the adsorptivity of the dispersant to the surface of the colorant, improving the wettability of the surface of the colorant, improving the dispersion stability due to electrostatic repulsion effect, etc. A modifier called a dispersion aid can also be blended. Here, as the dispersion aid, a pigment derivative type dispersion aid in which various functional groups are introduced into the pigment skeleton can be preferably used, but a yellow pigment derivative is more preferable in terms of hue, for example, a quinophthalone derivative, Examples thereof include isoindoline derivatives, isoindolinone derivatives, and azo pigment derivatives. The blending amount of these pigment derivative type dispersion aids is not particularly limited, but is preferably 0 to 30% by weight, preferably 0 to 20% by weight, based on the azomethine zinc complex in terms of dispersion stability. More preferably. The pigment derivative type dispersion aid used functions as a dispersion aid and simultaneously functions as a component of the colorant of the color filter composition.

  Moreover, a polymerization initiator can be mix | blended with the composition for color filters of this invention in consideration of the manufacturing process of a color filter. Examples of the polymerization initiator include acetophenones such as acetophenone and p-tert-butylacetophenone, benzophenones, benzophenones such as p, p'-bis (N, N-dimethylamino) benzophenone, benzoin ethyl ether, and benzoin-tert- Benzoin ethers such as butyl ether, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2- (N, N-dimethylamino) -1- ( Α-aminoalkylphenones such as 4-morpholinophenyl) butan-1-one, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl) -4 , 6-Bis (trichloromethyl) -1,3,5-triazine and other triazines, benzoic peroxide And organic peroxides such as yl, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, and sulfur compounds such as thioxanthone and 2,4-diethylthioxanthone. These may be used alone or in combination of two or more.

  The method for producing the composition for a color filter of the present invention is not particularly limited, but a dispersion in which a coloring material containing the azomethine zinc complex described above is dispersed in a solvent together with a dispersant is prepared in advance and cured. A method of preparing a color filter composition by blending a functional polymer and / or a curable monomer and other components added as necessary is advantageous. In addition, there is a method of preparing a color filter composition by directly dispersing a colorant in a curable polymer and / or a curable monomer, but the former method is used in terms of the stability of the color filter composition. preferable.

  The cured product obtained by curing the color filter composition of the present invention is obtained by applying the color filter composition to a substrate or the like and curing it by light irradiation, heating or the like. As a method for applying the color filter composition, a known method can be used, and examples thereof include application by a spin coater, a bar coater inkjet, and the like. Moreover, after application | coating, it is preferable to dry the composition for color filters using a hotplate, a vacuum dryer, etc. FIG. However, the coating and drying methods are not limited to the above.

  When curing by light irradiation, a known method can be used as a curing method, for example, light irradiation using a xenon lamp, a halogen lamp, a tungsten lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, etc. Can be mentioned. When such light irradiation is performed, image exposure can be performed using a photomask or the like, and an image can be formed on the substrate by processing with a developer. The developer is not particularly limited as long as it is a developer that dissolves an unexposed part and does not dissolve an exposed part, but is preferably an alkaline aqueous solution containing various additives. Here, examples of the developer additive include an organic solvent and a surfactant. As a developing method, a known method can be used, and examples thereof include immersion development, spray development, brush development, and ultrasonic development. The method of light irradiation and development is not particularly limited.

  Also in the case of curing by heat, a known method can be used, and examples thereof include, but are not limited to, heating and baking with a hot plate, a hot air oven, and the like.

There are no particular restrictions on the curing conditions of the color filter composition, but in order to prevent discoloration and discoloration of the color filter composition, light irradiation is 1000 mJ / cm ² or less, and heating is 270 ° C. or less within 1 hour. It is preferable to do.
In addition, a well-known method can be utilized as a method of manufacturing a color filter using the cured film of said color filter composition.

  The composition for a color filter in the present invention has an unprecedented hue, is excellent in heat resistance and dispersibility, and can produce a color filter.

  Hereinafter, the present invention will be described specifically by way of examples. In the following, “part” means part by weight. Moreover, the meaning of the abbreviation which represents a substituent is as follows. Me: methyl group, Ph: phenyl group.

(Preparation of color filter composition)
100 parts of azomethine zinc complex A (corresponding to R ¹ and R ² = H in the general formula (1)) is mixed with 50 parts of a cationic polymer dispersant and 850 parts of propylene glycol monomethyl ether acetate, and a paint shaker is used. For 3 hours to obtain 1000 parts of a dispersion. Here, 0.4 mmφ zirconia beads were used at a filling rate of 20% for the media of the paint shaker. Next, 69 parts of a 56.2% by weight propylene glycol monomethyl ether acetate solution (trade name: V-259ME, manufactured by Nippon Steel Chemical Co., Ltd.) of an epoxy acrylate resin having a bisphenolfluorene skeleton, 26 parts of dipentaerythritol hexaacrylate, a fluorene skeleton 6 parts of epoxy resin (trade name: ESF-300, manufactured by Nippon Steel Chemical Co., Ltd.), 6 parts of photoinitiator, 90 parts of propylene glycol diacetate, 1 part of surfactant and 2 parts of silane coupling agent are sufficient. To 200 parts of curable polymer. To this, 800 parts of the above dispersion was blended and stirred sufficiently to prepare 1000 parts of a color filter composition.

(Production of model color filter)
The composition for a color filter obtained by the above method was applied onto a 5 inch square, 1 mm thick blue plate glass using a spin coater to prepare a test piece. This test piece was dried on a hot plate at 80 ° C. for 3 minutes, and then covered with a photomask and exposed to ultraviolet light of 150 mJ / cm ² to cure the color filter composition in the exposed area. Next, development was performed by immersing the test piece in a 0.4% aqueous sodium carbonate solution for 60 seconds to remove the color filter composition in the unexposed area. Finally, the test piece was baked in a hot air oven at 230 ° C. for 20 minutes to produce a cured film (model color filter A) of the color filter composition as a model color filter. Further, this cured film was baked at 250 ° C. for 1 hour in a hot air oven.

In place of 100 parts of azomethine zinc complex A, 100 parts of azomethine zinc complex B (corresponding to R ¹ = Cl, R ² = H in the general formula (1)) was used, and the same treatment as in Example 1 was performed. The color filter composition was obtained and a model color filter B was produced.

In place of 100 parts of azomethine zinc complex A, 100 parts of azomethine zinc complex C (corresponding to R ¹ = H, R ² = Cl in the general formula (1)) was used, and the same treatment as in Example 1 was performed. A color filter composition was obtained and a model color filter C was produced.

In place of 100 parts of azomethine zinc complex A, 100 parts of azomethine zinc complex D (corresponding to R ¹ = Me, R ² = H in the general formula (1)) was used, and the same treatment as in Example 1 was carried out to obtain a dispersion. And the color filter composition was obtained, and the model color filter D was manufactured.

In place of 100 parts of azomethine zinc complex A, 100 parts of azomethine zinc complex E (corresponding to R ¹ = Cl, R ² = Me in the general formula (1)) was used, and the same treatment as in Example 1 was performed. A color filter composition was obtained and a model color filter E was produced.

In place of 100 parts of the azomethine zinc complex A, 100 parts of azomethine zinc complex F (corresponding to R ¹ = H, R ² = NO ₂ of the general formula (1)) is used, and the same treatment as in Example 1 is performed to perform dispersion. A liquid and a color filter composition were obtained, and a model color filter F was manufactured.

In place of 100 parts of azomethine zinc complex A, 100 parts of azomethine zinc complex G (corresponding to R ¹ = Ph, R ² = H in the general formula (1)) was used, and the same treatment as in Example 1 was carried out. A model color filter G was manufactured by obtaining a color filter composition.

Instead of 100 parts of azomethine zinc complex A, 100 parts of azomethine zinc complex H (corresponding to R ¹ and R ² = H, X = Br in the general formula (2)) was used, and the same treatment as in Example 1 was performed. A dispersion and a color filter composition were obtained to produce a model color filter H.

In place of 100 parts of azomethine zinc complex A, 100 parts of azomethine zinc complex I (corresponding to R ¹ = Cl, R ² = H, X = Br in the general formula (2)) was used, and the same treatment as in Example 1 was performed. Thus, a dispersion and a color filter composition were obtained to produce a model color filter I.

In place of 100 parts of azomethine zinc complex A, 100 parts of azomethine zinc complex J (corresponding to R ¹ = H, R ² = Cl, X = Br in the general formula (2)) was used, and the same treatment as in Example 1 was performed. Thus, a dispersion and a color filter composition were obtained, and a model color filter J was manufactured.

In place of 100 parts of azomethine zinc complex A, 100 parts of azomethine zinc complex K (corresponding to R ¹ = Cl, R ² = Me, X = Br in the general formula (2)) was used, and the same treatment as in Example 1 was performed. Then, a dispersion and a color filter composition were obtained to produce a model color filter K.

In place of 100 parts of azomethine zinc complex A, 100 parts of azomethine zinc complex L (corresponding to R ¹ = H, R ² = NO ₂ , X = Br in the general formula (2)) was used, and the same treatment as in Example 1 was performed. As a result, a dispersion and a color filter composition were obtained to produce a model color filter L.

In place of 100 parts of azomethine zinc complex A, 100 parts of azomethine zinc complex M (corresponding to R ¹ = Ph, R ² = H, X = Br in the general formula (2)) was used, and the same treatment as in Example 1 was performed. Then, a dispersion and a color filter composition were obtained to produce a model color filter M.

In place of 100 parts of azomethine zinc complex A, 100 parts of azomethine zinc complex N (corresponding to R ¹ = Cl, R ² = H, X = OMe in the general formula (2)) was used, and the same treatment as in Example 1 was performed. Thus, a dispersion and a color filter composition were obtained to produce a model color filter N.

In place of 100 parts of azomethine zinc complex A, 100 parts of azomethine zinc complex O (corresponding to R ¹ = H, R ² = Cl, X = OMe in the general formula (2)) was used, and the same treatment as in Example 1 was performed. Then, a dispersion and a color filter composition were obtained to produce a model color filter O.

[Comparative Example 1]
In place of 100 parts of azomethine zinc complex A, 100 parts of azomethine copper complex (R ¹ and R ² = H in general formula (1), Cu coordinated in place of Zn, Pigment Yellow 129) were used. The same treatment was performed to obtain a dispersion and a color filter composition, and a model color filter P was produced.

[Comparative Example 2]
In place of 100 parts of azomethine zinc complex A, 100 parts of azomethine nickel complex (R ¹ and R ² = H in general formula (1) = H, coordinated with Ni instead of Zn) is used, and the same treatment as in Example 1 is performed. Thus, a dispersion and a color filter composition were obtained to produce a model color filter Q.

[Comparative Example 3]
In place of 100 parts of the azomethine zinc complex A, 100 parts of [Pigment Yellow 150] was used, and the same treatment as in Example 1 was performed to obtain a dispersion and a composition for a color filter to produce a model color filter R. .

[Comparative Example 4]
In place of 100 parts of azomethine zinc complex A, 100 parts of [Pigment Yellow 139] was used and the same treatment as in Example 1 was carried out to obtain a dispersion and a composition for a color filter to produce a model color filter S. .

  Spectral transmittances of the model color filters manufactured in the above examples and comparative examples were measured using a chromaticity meter (trade name: Color Analyzer TC-1800MK2 manufactured by Tokyo Denshoku Co., Ltd.). At this time, the colorimetric light was the side color auxiliary illuminant C defined by the International Commission on Illumination (CIE).

Table 1 compares the color difference ΔE * _ab before and after baking at 250 ° C. for 1 hour for the model color filters (film thickness: 1 μm) obtained in Examples 1-15 and Comparative Examples 1-2. As shown in the table, Examples 1 to 15 have ΔE * _ab <3, but in the comparative example, ΔE * _ab > 3, which makes it possible to produce a color filter having excellent heat resistance. The color difference ΔE * _ab was measured according to JIS Z 8730.

  Table 2 compares wavelengths in the middle of the maximum and minimum values of the spectral transmission spectrum when the color filters obtained in Examples 1 to 15 and Comparative Examples 3 to 4 are measured with a chromaticity meter. When the hues are compared, since the rising waveforms of Examples 1 to 5, 7, and 11 to 15 are located in the middle of Comparative Examples 3 and 4, the color gamut represented by color mixing in the conventional yellow pigment is represented by a single color. It becomes possible. Further, Examples 6 and 8 to 10 have a rising waveform on the short wavelength or long wavelength side as compared with Comparative Example 4, and can represent a color gamut that cannot be represented by a conventional yellow pigment.

Claims (6)

A color filter composition comprising (A) a colorant, (B) a curable polymer and / or a curable monomer, (C) a dispersant, and (D) a solvent, wherein the colorant of (A) is A color filter composition comprising an azomethine zinc complex represented by the following general formula (1) or (2):

(However, R ¹ represents a hydrogen atom, a halogen atom, a methyl group or a phenyl group, R ² represents a hydrogen atom, a halogen atom, a methyl group or a nitro group, and X represents a halogen atom or a methoxy group.) The color difference ΔE * _ab (color difference defined by JIS Z 8730) before and after heat-treating the cured film obtained by curing the color filter composition according to claim 1 for 1 hour at 250 ° C. is 5 or less. A color filter composition. The color filter composition according to claim 1 or 2, wherein R ¹ and R ² of the azomethine zinc complex represented by the general formula (1) are independently a hydrogen atom or a chlorine atom, and X is a bromine atom.   The color filter composition according to claim 1 or 3, wherein (B) the curable polymer and / or the curable monomer comprises an epoxy acrylate having a fluorene skeleton and a derivative thereof.   Hardened | cured material obtained by hardening the composition for color filters in any one of Claims 1-4.   The color filter which the cured film which forms a pixel consists of hardened | cured material of Claim 5.