JP6547931B2 - Colored curable resin composition - Google Patents

Description

  The present invention relates to a colored curable resin composition used for manufacturing a color liquid crystal display device and a color filter used for a color imaging tube device and the like, and a color filter having a black matrix formed using the same. It is.

In the gaps between the red, green and blue filter segments of the color filter, a grid-like black pattern called a black matrix (hereinafter also referred to as “BM”) having a light shielding property is formed for the purpose of improving the contrast. It is common.
The BM is required to be excellent in the light shielding property in order to make the image quality of the liquid crystal display excellent. Among them, in recent years, in order to cope with higher definition and higher luminance, BM is formed on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device by a method of forming BM on a color filter substrate as in the prior art. The BOA (Black Matrix on Array) method has been studied. In this BOA method, the past laminating process for alignment with the element is not necessary, the pixel aperture ratio (aperture ratio) can be greatly increased, and the manufacturing process can be shortened, thereby achieving display Because the quality can be improved and the cost can be reduced, there are many advantages over the conventional method of forming a BM on a color filter substrate.

However, in the case of forming a BM on the array substrate side, the BM itself directly contacts the liquid crystal, which causes a display defect of the liquid crystal display when the insulation of the BM itself is low.
Moreover, since mask alignment performed at the time of BM formation is performed using an infrared camera, the light transmittance of a certain level near infrared region is also required. Therefore, with carbon black mainly used as a conventional BM material, it is difficult to perform alignment because it has a high dielectric constant and is poor not only in insulation but also in light transmittance in the near infrared region, It is difficult to use for a BOA type liquid crystal panel.
As a method of solving such a subject, the method (refer patent document 1) which gives light-shielding property by a specific organic pigment is disclosed.

Special table 2012-515233

  In addition, since BM is immersed in a solvent such as N-methyl-2-pyrrolidone (hereinafter, also simply referred to as “NMP”) that dissolves a polyimide precursor at the time of forming a polyimide film, solvent resistance is required for BM. The composition disclosed in Patent Document 1 is not sufficient in terms of solvent resistance. Therefore, it is desired to provide a colored curable resin composition for BM, which is excellent in light shielding property, insulating property and solvent resistance. The present invention provides a colored curable resin composition for producing a black matrix excellent in electrical insulation properties, light shielding properties, and solvent resistance, and a color filter provided with a black matrix formed using the same. To be an issue.

The present inventors have found that a compound (1) represented by the following formula (1), a polyfunctional polymerizable compound (B), a compound having an alicyclic structure or a heterocyclic structure, and two or more carboxy groups (C) And using a composition containing a dispersant (D) and an organic solvent (E), it is found that a colored curable resin composition having high electrical insulation, excellent light shielding properties and good solvent resistance can be obtained. The
That is, the present invention relates to the following [1] to [2].
[1] A compound (1) represented by the following formula (1), a polyfunctional polymerizable compound (B) having an ethylenically unsaturated bond, an alicyclic structure or a heterocyclic structure, and two or more carboxy groups Colored curable resin composition containing the compound (C) which has, a dispersing agent (D), and an organic solvent (E).

[In the above-mentioned formula (1), X represents a double bond, and each of them is an E form or a Z form independently as a geometrical isomer, and R ¹ is each independently a hydrogen atom, a methyl group, a nitro group, a methoxy group , Bromine atom, chlorine atom, fluorine atom, carboxy group, or sulfonic acid group, each R ² independently represents a hydrogen atom, a methyl group, or a phenyl group, and each R ³ independently represents a hydrogen atom , A methyl group or a chlorine atom. ]
[2] A color filter comprising a black matrix formed using the colored curable resin composition according to [1].

  According to the present invention, a colored curable resin composition for producing a black matrix excellent in electrical insulation properties, light shielding properties and solvent resistance, and a color filter having a black matrix formed using the same Can be provided.

  The colored curable resin composition of the present invention comprises a compound (1) represented by the following formula (1) (hereinafter, also simply referred to as a “compound (1)”) and a compound having two or more ethylenic unsaturated bonds Compound (C) having a functional polymerizable compound (B) (hereinafter, also simply referred to as “component (B)”), an alicyclic structure or a heterocyclic structure, and two or more carboxy groups (hereinafter referred to simply as “(C Component), a dispersant (D) (hereinafter, also simply referred to as "(D) component"), and an organic solvent (E) (hereinafter, simply referred to as "(E) component"). Do.

According to the present invention, it is possible to obtain a colored curable resin composition capable of producing a black matrix which is excellent in electrical insulation and light shielding properties and further excellent in solvent resistance. The reason why such an effect can be obtained is not clear, but is considered as follows.
By selecting the compound (1) as the black coloring material, excellent electrical insulation and light shielding properties can be obtained. On the other hand, although it tends to be inferior to solvent resistance by using the black color material concerned, the above-mentioned electric insulation and light-shielding property by using combining a specific (B) ingredient and a specific (C) ingredient High solvent resistance can be obtained. Since the compound of component (C) has two or more carboxy groups, the carboxylate anion of component (C) generated by a small amount of water in the system interacts with the lactam moiety of compound (1), and compound (1) (C) component is unevenly distributed near the surface of. As a result, it is presumed that the component (C) itself can obtain good curing characteristics with interaction with the component (B) and is excellent in solvent resistance. However, these are only estimates, and the present invention is not limited to these mechanisms.

[Compound (1)]
The composition of the present invention contains a compound (1) represented by the formula (1) as a black color material from the viewpoint of electrical insulation and light shielding.

In the above formula (1), X represents a double bond, and the stereochemistry of each double bond is independently an E form or a Z form, and R ¹ is each independently a hydrogen atom (-H), methyl group _(-CH 3), a nitro group (-NO ₂ group), a methoxy group (-OCH _3), bromine (-Br), chlorine atom (-Cl), a fluorine atom (-F), carboxy (-COOH ), or it shows a sulfonic acid group _(-SO 3 H), ^{R 2} each independently represent a hydrogen atom, a methyl group, or a phenyl group, ^{R 3} each independently represent a hydrogen atom, a methyl group, or Indicates a chlorine atom. From the viewpoint of the ease of preparation of compound (1), R ¹ is preferably bonded to the 6-position of the dihydroindolone ring, and R ³ is preferably bonded to the 4-position of the dihydroindolone ring. From the same point of view, R ¹ is preferably a hydrogen atom, and R ³ is preferably a hydrogen atom. R ² is preferably a hydrogen atom from the viewpoint of the interaction with the compound (C). The above compounds can be used alone or in combination of two or more.
The compound of the above formula (1) can be produced, for example, by the method described in International Publication WO 2000/24736 and International Publication WO 2010/081624.
The composition of the present invention may contain a black coloring material other than the above compound (1), as long as the effects of the present invention are not impaired. Other black coloring materials include carbon black, titanium black and the like.
In the present specification, the compound (1) and the other black colorants are collectively referred to simply as “black colorant (A)”.
In the black color material (A), the content of the compound (1) is preferably 80% by mass or more, more preferably 90% by mass or more, and 100% by mass or less, still more preferably 100% by mass.
From the viewpoint of enhancing the affinity between the black color material and the organic solvent, and enhancing the dispersibility and storage stability, as the black color material, those obtained by surface-treating the compound (1) with a resin or a polymer in advance, the compounds What derivatized a part of (1) etc. can also be used.

[Multifunctional polymerizable compound (B)]
The polyfunctional polymerizable compound has two or more ethylenically unsaturated bonds.
Examples of the site having an ethylenically unsaturated bond include a (meth) acrylate group and a vinyl group.
As a polyfunctional polymerizable compound, a polyfunctional (meth) acrylate type compound is preferably used.
From the viewpoint of solvent resistance, the number of ethylenically unsaturated bonds contained in the polyfunctional polymerizable compound is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, and preferably 8 Or less, more preferably 7 or less, and still more preferably 6 or less.

As this polyfunctional (meth) acrylate compound, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) Acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hex (Meth) acrylate, pentaerythritol di (meth) acrylate, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane , 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, Glycerin tri (meth) acrylate, glycerin polyglycidyl ether poly (meth) acrylate, reaction product of polyisocyanate and hydroxyalkyl (meth) acrylate (urethane (meth) acrylate), methylene vinyl (Meth) acrylamide, dimethylene ether bis (meth) acrylamide, a condensation product of a polyhydric alcohol and N- methylol (meth) acrylamide, triacrylformal and the like. These polyfunctional (meth) acrylate compounds can be used alone or in combination of two or more.
Among these, preferably, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate It is at least one selected from (hereinafter also referred to as “DPHA”), more preferably DPHA.
In the present specification, “(meth) acrylate” means at least one selected from acrylate and methacrylate. Also, “(meth) acrylamide” means at least one selected from acrylamide and methacrylamide.

[Compound (C)]
The compound (C) is a compound having an alicyclic structure or a heterocyclic structure, and two or more carboxy groups.
The alicyclic structure or heterocyclic structure possessed by the compound (C) is preferably a 5- or 6-membered ring, more preferably a 6-membered ring, from the viewpoint of solvent resistance.
The compound (C) has two or more carboxy groups from the viewpoint of solvent resistance. Having two or more carboxy groups, the interaction with the component (B) is intensified, and the elution of the compound (1) by a solvent (for example, NMP) from the cured film obtained from the colored curable resin composition is suppressed can do.
The number of carboxy groups contained in the compound (C) is two or more, preferably six or less, more preferably four or less, still more preferably three or less, from the viewpoint of solvent resistance and light shielding property. Still more preferably, it is three.

The compound (C) is preferably a compound having one or more nitrogen atoms in one molecule from the viewpoint of solvent resistance, and more preferably has at least one selected from a lactam structure, an amino group, and an amide group. The compound is a compound having a carboxyalkyl group bonded to a nitrogen atom of a lactam structure, an amino group or an amido group.
The carbon number of the alkanediyl group constituting the carboxyalkyl group is preferably 1 or more, more preferably 2 or more, preferably 8 or less, more preferably 6 or less, still more preferably 4 or less, from the viewpoint of solvent resistance. Still more preferably, it is 3 or less, still more preferably 2.

The compound (C) preferably has a heterocyclic structure from the viewpoint of solvent resistance.
The heterocycle in the present invention means one in which one or more hetero atoms other than carbon atoms are contained in the atoms constituting the ring. The heterocyclic ring may be a saturated ring or an unsaturated ring, and may be a single ring or a fused ring. The heterocyclic ring is preferably a non-aromatic ring from the viewpoint of solvent resistance.
The number of hetero atoms contained in one heterocyclic ring is preferably 1 or more, more preferably 2 or more, preferably 6 or less, more preferably 5 or less, still more preferably 4 or less, still more preferably 3 or less. And more preferably 3.
The hetero atom is preferably one or more selected from oxygen atom, nitrogen atom and sulfur atom, more preferably one or more selected from oxygen atom and nitrogen atom, and still more preferably nitrogen atom.
As a heterocyclic ring containing a nitrogen atom as a hetero atom, a saturated ring such as an aziridine ring, azetidine ring, pyrrolidine ring, piperidine ring, piperidine ring, piperazine ring, morpholine ring, imidazolidine ring, isocyanuric ring, 1H-azirine ring, 2H-azirine ring , Azole ring, pyrroline ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, pyrazolidine ring, pyrazoline ring, triazine ring, pyrrole ring, imidazole ring, imidazoline ring, imidazolidine ring, pyrazole ring, oxazole ring, thiazole ring, Isooxazole ring, isothiazole ring, triazole ring, thiadiazole ring, oxadiazole ring, quinoline ring, indole ring, isoindole ring, 1H-indazole ring, benzimidazole ring, indoline ring, isoindoline ring, carbazole ring, etc. of It includes saturated ring.
The compound (C) preferably has at least one selected from piperazine ring, imidazolidine ring, and isocyanuric ring from the viewpoint of solvent resistance, and more preferably has at least one selected from imidazolidine ring and isocyanuric ring. More preferably, it has an isocyanuric ring.

  The compound (C) is preferably trans-1,2-diaminocyclohexane-N, N, N ′, N′-tetraacetic acid monohydrate, bis (2-carboxyethyl) isocyanurate from the viewpoint of solvent resistance. And at least one selected from tris (2-carboxyethyl) isocyanurate, more preferably at least one selected from bis (2-carboxyethyl) isocyanurate and tris (2-carboxyethyl) isocyanurate. More preferably, it is tris (2-carboxyethyl) isocyanurate.

[Dispersing agent (D)]
The dispersant used in the present invention is, for example, a polyurethane based dispersant, a polyamide based dispersant, a polyimide based dispersant, or a poly (based) having poly (meth) acrylate, polylactone, polyalkylene oxide or the like as a main chain or side chain. Examples thereof include polycarboxylic acid-based dispersants such as meta) acrylic acid and poly (maleic anhydride), polyamine-based dispersants, and dispersants into which quaternary ammonium salts and the like are introduced. These dispersants can be used alone or in combination of two or more.

  As commercially available dispersants, “161”, “166”, “167” of “Disperbyk” series manufactured by BIC Chemie Japan Ltd., “55000” of “Sorsparse” series manufactured by Nippon Lubrizol, and “55,000” as a polyurethane-based dispersant 76500 etc .; as polycarboxylic acid dispersants, "106", "110", "111" of "Disperbyk" series manufactured by BIC Chemie Japan Ltd., "36000", "41000" of "Sorsparse" series manufactured by Japan Lubrizol Corporation. “EFKA-5060” manufactured by BASF Japan Ltd., etc .; “116” and “130” of the “Disperbyk” series manufactured by BIC Chemie Japan Ltd. as a polyamine-based dispersant, “24000” manufactured by Nippon Lubrizol “Sorsparse” series "," 32000 ", 33000 "," J200 ", BASF · Japan Co., Ltd." EFKA-4046 ", Ajinomoto Fine-Techno Co., Ltd." Ajisper PB "series" 821 ", and" 822 "," 824 "," 881 "and the like, and the like. Among these, from the viewpoint of dispersibility, it is preferably a polyamine dispersant, more preferably "EFKA-4046" and "Sol Sparse J200", still more preferably "Sol Sparse J200".

[Organic solvent (E)]
Examples of the organic solvent include monohydric alcohols such as ethanol and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as cyclohexane; and polyhydric alcohols such as propylene glycol; Other than ethers such as ethylene glycol diethyl ether, ethyl acetate, silicone oil, fats and oils, etc. and compounds represented by the following formula (2) may be mentioned.

〔式中、Ｒ^４及びＲ^５は、それぞれ独立して、水素が炭素数１〜３のアルコキシ基と置換していてもよい、炭素数１〜４の炭化水素基を示し、Ｒ^６は水素原子又はメチル基を示し、ｎは０〜３の整数を示す。〕

[Wherein, R ⁴ and R ⁵ each independently represent a hydrocarbon group having 1 to 4 carbon atoms in which hydrogen may be substituted with an alkoxy group having 1 to 3 carbon atoms, and R ⁶ is hydrogen An atom or a methyl group is shown, n shows the integer of 0-3. ]

In Formula (2), the hydrocarbon group having 1 to 4 carbon atoms of R ⁴ and R ⁵ is preferably an alkyl group, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 3-methoxybutyl group, isobutyl group, sec-butyl group, and tert-butyl group can be mentioned. Of these, methyl and ethyl are more preferred.
n is preferably 1 or 2.
The organic solvent is preferably ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (hereinafter also referred to as "PGMEA"), diethylene glycol mono from the viewpoint of the dispersibility of the coloring material and the solubility or dispersibility of the dispersant. At least one selected from the group consisting of butyl ether acetate, 3-methoxybutyl acetate and propylene glycol monoethyl ether acetate, more preferably PGMEA.
The above organic solvents can be used alone or in combination of two or more.

[Fluorine compound (F)]
The colored curable resin composition of the present invention preferably contains a fluorine compound from the viewpoint of further improving the solvent resistance. In the process of forming a coating film using a colored curable resin composition, drying and curing, the fluorine compound bleeds out on the BM surface to reduce the penetration of the solvent into the BM, thereby eluting the compound (1). Is considered to further suppress

As the fluorine compound, at least one selected from a surfactant having a fluorocarbon chain, a fluorine-based oligomer, a compound having a fluorocarbon chain and an ethylenically unsaturated bond, and the like can be mentioned.
As surfactants having a fluorocarbon chain, commercially available products include "430" and "431" of "Florinert FC" series manufactured by Sumitomo 3M Ltd., and "F142D" and "F171" of "Megafuck" series manufactured by DIC Corporation. , "F172", "F173", "F177", "F183", "F554", "R30", "301", "303" and "351" of the "F-top EF" series manufactured by Mitsubishi Materials Electronics Corporation. , “352”, “S-381”, “S-382”, “SC-101”, “SC-105”, “E-5844”, manufactured by Daikin Fine Chemical Research Institute, Inc. Etc.
As a fluorine-type oligomer, "S-611" of "Surflon" series by AGC Seimi Chemical Co., Ltd. series, "S-651" etc. are mentioned as a commercial item.
Examples of the compound having a fluorocarbon chain and an ethylenically unsaturated bond include “RS-72-K”, “RS-75”, and “RS-76-E” of “Megafuck” series manufactured by DIC Corporation.
In order to reduce the penetration of the solvent into the coating film, it is preferable that the solubility of the fluorine compound in the solvent be lower, and since it has a higher molecular weight than the activator, it can be cured simultaneously with the component (B) by the fluorinated oligomer and reactive group Therefore, compounds having a fluorocarbon chain and an ethylenically unsaturated bond are preferred.
Among the fluorine-based oligomers, "S-611" and "S-651" of the "Surflon" series are preferred. Among the compounds having a fluorocarbon chain and an ethylenically unsaturated bond, “RS-72-K”, “RS-75”, and “RS-76-E” of “Megafuck” series are preferable.
The fluorine compound used in the present invention may be one kind or a mixture of two or more kinds.

The colored curable resin composition of the present invention may contain, for example, an alkali-soluble resin, a photopolymerization initiator, a photoinitiation aid, and the like.
An alkali-soluble resin is used to dissolve an unexposed area in a developer when producing a color filter by photolithography. As the alkali-soluble resin, those generally used for negative resists can be used, and those having solubility in an aqueous alkaline solution, that is, 1% by mass at 20 ° C. in a 0.05% by mass aqueous solution of tetramethylammonium hydroxide It is not particularly limited as long as it dissolves as described above.
As the alkali-soluble resin used in the present invention, a copolymer of (meth) acrylic acid ester and (meth) acrylic acid is preferably used.
Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate and At least one selected from benzyl (meth) acrylate is mentioned. Among these, benzyl (meth) acrylate and methyl (meth) acrylate are preferable. That is, as a copolymer of (meth) acrylic acid ester and (meth) acrylic acid, a copolymer of benzyl (meth) acrylate and (meth) acrylic acid, and methyl (meth) acrylate and (meth) acrylic acid And copolymers thereof are more preferred.
It is preferable that it is 90/10-50/50, and, as for the copolymerization ratio (molar ratio) of acrylic acid ester and (meth) acrylic acid, it is more preferable that it is 80/20-70/30. The weight average molecular weight of the alkali soluble resin is preferably 5,000 to 50,000.
In the present specification, “(meth) acrylic acid” means at least one selected from acrylic acid and methacrylic acid. Also, "(meth) acrylate" means at least one selected from acrylate and methacrylate.

  A well-known polymerization initiator can be used as a photoinitiator, For example, 2-methyl 1- (4-methylthio phenyl) -2- morpholino propan 1-one, 2, 2- dimethoxy 1 , 2-Diphenylethan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone , 2-hydroxy-2-methyl-1-phenyl-propan-1-one, iodonium, (4-methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate, 2- [2-oxo] A mixture of 2-phenylacetoxyethoxy] ethyl ester and 2- (2-hydroxyethoxy) ethyl ester, phenyl glycolate, Benzophenone, and the like are preferable. As a commercially available photoinitiator, IRGACURE 369, 907, 651, 2959, 184, 250, 754; DAROCUR MBF, BP, 1173 (made by BASF Japan) etc. are preferable, for example. These photoinitiators can be used individually or in combination of 2 or more types.

You may combine a photoinitiator adjuvant with this photoinitiator.
As a photoinitiator adjuvant, for example, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid 2-ethylhexyl, 2-dimethylaminoethyl benzoate, N, N-dimethyl paratoluidine, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 9,10-dimethoxyanthracene, Examples thereof include 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene and the like. These photoinitiator adjuvants can be used individually or in combination of 2 or more types.

The solid content in the colored curable resin composition is preferably 10% by mass or more, more preferably 13% by mass or more, still more preferably 15% by mass or more, preferably 40% by mass or less, more preferably 30% by mass The content is more preferably 25% by mass or less.
The content of the compound (1) in the colored curable resin composition is preferably 4% by mass or more, more preferably 5% by mass or more, and still more preferably 8% by mass or more from the viewpoint of obtaining a good light shielding property. From the viewpoint of obtaining good solvent resistance, it is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.
The content of the compound (1) is preferably 20% by mass or more, more preferably 25% by mass or more, still more preferably from the viewpoint of obtaining a good light shielding property, with respect to the solid content in the colored curable resin composition. The content is 40% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass or less from the viewpoint of obtaining good solvent resistance.

The content of the black color material (A) in the colored curable resin composition is preferably 4% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, from the viewpoint of obtaining a good light shielding property. From the viewpoint of obtaining good solvent resistance, it is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.
The content of the black coloring material (A) is preferably 20% by mass or more, more preferably 25% by mass or more, and further preferably 25% by mass or more, with respect to the solid content in the colored curable resin composition The content is preferably 40% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass or less from the viewpoint of obtaining good solvent resistance.

The content of the polyfunctional polymerizable compound (B) in the colored curable resin composition is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, from the viewpoint of obtaining good film hardness. The content is preferably 0.7% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less.
The content of the polyfunctional polymerizable compound (B) is preferably 1.0% by mass or more, more preferably 2.% by mass with respect to the solid content in the colored curable resin composition from the viewpoint of obtaining good film hardness. The content is 0% by mass or more, more preferably 3.0% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.

The content of the compound (C) in the colored curable resin composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.3% by mass from the viewpoint of solvent resistance. % Or more, more preferably 0.4% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 1% by mass or less, still more preferably 0.8% by mass or less Still more preferably it is 0.6 mass% or less.
The content of the compound (C) is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably from the viewpoint of solvent resistance, with respect to the solid content in the colored curable resin composition. 2% by mass or more, more preferably 2.5% by mass or more, still more preferably 3% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less Still more preferably, it is 8% by mass or less, still more preferably 4% by mass or less.
The mass ratio [(C) / (B)] of the compound (C) to the polyfunctional polymerizable compound (B) in the colored curable resin composition is preferably 0.05 or more, more preferably from the viewpoint of solvent resistance. Preferably it is 0.08 or more, more preferably 0.12 or more, still more preferably 0.22 or more, preferably 0.90 or less, more preferably 0.60 or less, still more preferably 0.40 or less, more preferably More preferably, it is 0.30 or less.

The content of the dispersant (D) in the colored curable resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, from the viewpoint of good light shielding property and solvent resistance. The amount is preferably 1% by mass or more, and from the same viewpoint, preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less.
The content of the dispersant (D) is preferably 0.5% by mass or more, more preferably 2.% by mass with respect to the solid content in the colored curable resin composition, from the viewpoint of good light shielding property and solvent resistance. It is 5% by mass or more, more preferably 5% by mass or more, and from the same viewpoint, preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less.

  The content of the organic solvent (E) in the colored curable resin composition is preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably 75% by mass or more from the viewpoint of good light shielding properties. Preferably it is 95 mass% or less, More preferably, it is 90 mass% or less, More preferably, it is 85 mass% or less.

  The content of the fluorine-based compound (F) is preferably 0.2% by mass or more, more preferably 0 based on the solid content in the colored curable resin composition, from the viewpoint of good insulation and solvent resistance. .6 mass% or more, more preferably 1.0 mass% or more, preferably 10 mass% or less, more preferably 5 mass% or less, still more preferably 3 mass% or less.

The content of the alkali-soluble resin is preferably 5.0% by mass or more, and more preferably 10% by mass or more based on the solid content in the colored curable resin composition from the viewpoint of obtaining good developability and film hardness. More preferably, it is 15% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 35% by mass or less.
The content of the photopolymerization initiator in the colored curable resin composition is preferably 5 parts by mass with respect to 100 parts by mass of the component (B) in the colored curable resin composition, from the viewpoint of obtaining good film hardness. The content is more preferably 10 parts by mass or more, further preferably 20 parts by mass or more, preferably 70 parts by mass or less, more preferably 60 parts by mass or less, and still more preferably 50 parts by mass or less. By setting it as said range, sufficient heat resistance and chemical resistance can be acquired, a coating film formation ability can be improved, and a curing defect can be suppressed.
The content of the photopolymerization initiation aid in the colored curable resin composition is preferably 1 mass with respect to 100 parts by mass of the component (B) in the colored curable resin composition from the viewpoint of obtaining a good film hardness. It is preferably at least 30 parts by mass, more preferably at most 20 parts by mass, and still more preferably at most 15 parts by mass. By setting it as said range, sufficient heat resistance and chemical resistance can be acquired, a coating film formation ability can be improved, and a curing defect can be suppressed.

[Production method]
It is preferable that the manufacturing method of the colored curable resin composition of this invention has the following process.
Step 1: Compound (1), Compound (C), Dispersant (D), and Organic Solvent (E) are mixed and dispersed to obtain a dispersion Step 2: The above dispersion and the polyfunctional polymerizable compound ( B) mixing with

As the mixing and dispersing machine used in the dispersion of the above-mentioned step 1, various known dispersing machines can be used. For example, high-speed stirring and mixing devices such as homomixers, kneaders such as roll mills, kneaders and extruders, high pressure type dispersing machines such as high pressure homogenizers, and media type dispersing machines such as paint shakers and bead mills. These devices can also be used in combination.
Among these, from the viewpoint of uniformly mixing the black coloring material in the organic solvent, a high-speed stirring and mixing apparatus such as a homomixer, and a media type dispersing machine such as a paint shaker and a bead mill are preferable. Examples of commercially available media type dispersing machines include "Ultra Apex Mill" manufactured by Kotobuki Industry Co., Ltd., "Picomill" manufactured by Asada Iron Works Ltd., and the like.
When a media type dispersing machine is used, as the material of the medium used in the dispersing step, ceramics such as zirconia and titania, polymer materials such as polyethylene and nylon, metals and the like are preferable, and zirconia is preferable from the viewpoint of wearability. The diameter of the medium is preferably 0.003 mm or more, more preferably 0.01 mm or more, preferably 0.5 mm or less, more preferably 0, from the viewpoint of crushing aggregated particles in the black color material. .4 mm or less.
The dispersion time is preferably 0.3 hours or more, more preferably 1 hour or more, from the viewpoint of sufficiently miniaturizing the compound (1), and preferably 50 hours or less from the viewpoint of production efficiency of the pigment dispersion. The following are more preferable.

  The mixing method of step 2 is not particularly limited, and can be obtained, for example, by stirring with a roller stirrer. The stirring time is preferably 5 minutes or more, more preferably 15 minutes or more, and in terms of production efficiency, preferably 10 hours or less, and more preferably 1 hour or less.

[Color filter]
The colored curable resin composition of the present invention is used for the production of a color filter.
The method for producing a color filter having a black matrix formed by using the colored curable resin composition of the present invention comprises applying the colored curable resin composition of the present invention on a substrate, drying, photocuring and developing. A step (a) of obtaining a coating film, a step (b) of heating the coating film obtained in the step (a) to 200 to 300 ° C. to form a black matrix consisting of a cured film, and It is preferable to have the process (c) of coating the organic solvent solution of resin, and forming a resin film.

After the application in the step (a), it is preferable to dry the organic solvent and to heat or reduce the pressure from the viewpoint of the smoothness of the coating film and the productivity.
The said photocuring irradiates an ultraviolet-ray to a coating film, for example, the crosslinking reaction of the polyfunctional monomer in colored curable resin composition is carried out, and a coating film is hardened. It is preferable that the photocuring be performed to leave a pattern on the glass substrate in the subsequent development, and that a portion to be removed by the development is not cured by placing a photomask for preventing ultraviolet light.
The said development immerses the cured coating film after photocuring in alkaline aqueous solution, for example, rinses with water further, and removes an uncured part.
The step (b) is a post baking step, and by performing this step, a cured film having excellent hardness can be formed.
The resin of step (c) is, for example, polyimide. The organic solvent of step (c) is, for example, NMP.

  Preparation of coated substrate, measurement of optical density (hereinafter also referred to as "OD") and evaluation of solvent resistance, measurement of surface resistivity and evaluation of electrical insulation, measurement of weight average molecular weight and solid content by the following method Went by.

(1) Preparation of Coating Film Substrate A colored curable resin composition was coated on a glass substrate by a spin coater, allowed to stand on a horizontal stand for 5 minutes, and dried on a hot plate at 120 ° C. for 10 minutes. Furthermore, it was treated in a clean oven at 230 ° C. for 20 minutes to obtain a substrate having a coating on one side (also referred to as a “coating substrate”).

(2) Measurement of OD (light-shielding property evaluation) and evaluation of solvent resistance OD (pre-treatment OD) of the coated substrate was measured with a table-type transmission densitometer ("Model 361 T" manufactured by X-Rite, measurement wavelength 550 nm) It was measured. The larger the pre-treatment OD, the better the light shielding property.
Next, 50 μL of NMP droplets were formed on the coated film of the coated substrate using a microsyringe. After standing for 5 minutes, air was blown to remove the droplets, and the OD (post-treatment OD) of the portion where the droplets were formed was measured. The OD difference was determined by the following equation. The closer the OD difference to 0, the better the solvent resistance.
OD difference = post treatment OD-pre treatment OD

(3) Measurement of Surface Resistivity and Evaluation of Electrical Insulating Property After leaving a coated substrate to stand in an environment of 25 ° C. and 45% RH for 6 hours, an insulation resistor (“4329A” manufactured by Yokogawa-Hewlett-Packard Co.) The surface resistivity Ps (Ω / □) was measured in a resistance value measurement chamber (“Kawaguchi Denki Co., Ltd.“ Model P-601 ”, measurement voltage: 100 V) connected to to evaluate the electrical insulation. The larger the surface resistivity value, the better the electrical insulation.

(4) Measurement of weight average molecular weight The sample was diluted with N, N-dimethylformamide to prepare a solution having a solid concentration of 0.3 mass% of the sample, and 0.1 mL of the solution was used as a measurement solution. Gel permeation chromatography (hereinafter also referred to as "GPC") using a solution of phosphoric acid and lithium bromide dissolved in N, N-dimethylformamide so as to have concentrations of 60 mmol / L and 50 mmol / L, respectively, as the eluent. [Apparatus: “HLC-8120GPC” manufactured by Tosoh Corp., Column: “TSK-GEL, α-M” × 2 manufactured by Tosoh Corp., flow rate: 1 mL / min] using polystyrene as a standard substance.

(5) Measurement of solid content A glass rod and 10 g of dry anhydrous sodium sulfate were put in a petri dish, 2 g of a sample was weighed there, mixed with a glass rod, and dried with a vacuum dryer at 105 ° C. (pressure 8 kPa) for 2 hours. The mass after drying was measured, and the value obtained by the following equation was used as the solid content of the sample.
Solid content (mass%) = [[mass after drying− (dish of petri dish + glass rod + mass of anhydrous sodium sulfate)] / mass of sample] × 100

Synthesis Example 1 Synthesis of Compound (1) In a 5-liter four-necked flask equipped with a stirrer, a thermometer, a nitrogen blowing tube, a Dean-Stark tube, and a Dimroth tube, 2,5-dihydroxybenzene-1,4-diacetic acid ( A mixture of 115 g of Wako Pure Chemical Industries, Ltd., 150 g of isatin (manufactured by Tokyo Chemical Industry Co., Ltd.), 35 g of p-toluenesulfonic acid monohydrate and 3750 g of toluene is heated to 110 ° C. and stirred for 7 hours while dewatering And heated for an additional 10 hours. The mixture was cooled to room temperature, and the black suspension was filtered on filter paper No. It filtered by 2 (made by Advantec Toyo Corp.). The filtration residue was washed with 5 liters of methanol and dried at 60 ° C./104 Pa to obtain 236 g of a black substance of the following formula (a).
The black material was dissolved in dimethylformamide and subjected to ESI / MS measurement by liquid chromatography mass spectrometry to confirm that the molecular weight was 448.07.

Production Example 1 (Preparation of Black Color Material Dispersion 1)
10.0 g of the compound (1) obtained in Synthesis Example 1, 0.5 g of bis (2-carboxyethyl) isocyanurate, 2.0 g of "Sorspase J-200" manufactured by Japan Lubrizol Corporation, 37.5 g of PGMEA, and 100 g of zirconia beads (Nikkato "YTZ ball") of 0.3 mm in diameter was placed in a 250 mL poly container and stirred with a paint shaker for 3 hours, then the zirconia beads were removed by filtration to obtain a black colorant dispersion 1 .

Production Examples 2 to 11 and Comparative Production Examples 1 to 12 (Preparation of Black Color Material Dispersions 2 to 11 and 51 to 62)
Black colorant dispersions 2 to 11 and 51 to 62 were obtained in the same manner as in Production Example 1 except that the formulations described in Table 1 were substituted. The compounds used for the preparation are as follows.

A-1: Synthesis example 1
A-2: Carbon black; "Raven 1060" manufactured by Columbian Carbon Co., Ltd.
A-3: Aniline black; "No. 2 superblack" manufactured by Toda Kogyo Co., Ltd.
C-1: bis (2-carboxyethyl) isocyanurate
C-2: tris (2-carboxyethyl) isocyanurate
C-3: trans-1,2-diaminocyclohexane-N, N, N ', N'-tetraacetic acid monohydrate C-4: adipic acid C-5: 1,2,3-propanetricarboxylic acid C- 6: Trimellitic acid C-7: Benzoic acid C-8: Terephthalic acid C-9: Phthalic acid C-10: Isophthalic acid C-11: Ethylenediaminetetraacetic acid

Synthesis Example 2 [Synthesis of Alkali-Soluble Resin (Copolymer of Benzyl Methacrylate and Methacrylic Acid)]
In a separable flask equipped with a stirrer, reflux condenser, nitrogen inlet tube and thermometer, 3.6 g of methacrylic acid (hereinafter also referred to as "MAA") and 36.4 g of benzyl methacrylate (hereinafter also referred to as "BzMA") Then, 0.56 g of 3-mercaptopropionic acid and 40 g of PGMEA were charged, and nitrogen substitution was carried out while stirring.
The temperature is raised to 78 ° C. with stirring in the flask, and 14.4 g of MAA, 145.6 g of BzMA, 2.2 g of 3-mercaptopropionic acid, 160 g of PGMEA, and 2,2′-azobis (2,4-dimethylvaleronitrile ) (Wako Pure Chemical Industries, Ltd. “V-65” (hereinafter, also referred to as “V-65”)) A solution obtained by mixing 2.0 g is dropped over 3 hours, and after completion of the dropping, V-65 2 A mixed solution of 0. 0 g and 10.0 g of PGMEA was added. Stir for 1 hour at 78 ° C, V-65 1.0 g and PGMEA
10.0 g and mixed solution were added. The mixture was further stirred at 78 ° C. for 1 hour, 100 g of PGMEA was added, and cooled to obtain a PGMEA solution of a copolymer of BzMA and MAA (hereinafter, also referred to as “copolymer 1”). The solid content was 40.0% by mass, and the weight average molecular weight was 10,900.

Preparation Example 1 (Preparation of Clear Resist Solution)
A clear resist solution was obtained by uniformly mixing 211.0 g of the solution of copolymer 1 with a solid content of 40.0% by mass obtained in Synthesis Example 2, 33.2 g of DPHA, and 256.6 g of PGMEA.

Example 1 (Preparation of Colored Curable Resin Composition 1)
5.0 g of the pigment dispersion 1 obtained in Production Example 1, 3.2 g of the clear resist solution obtained in Preparation Example 1, and 1.8 g of PGMEA are put in a sample bottle and sealed up, and then they are sealed with a roller stirrer. The mixture was uniformly mixed for 20 minutes to obtain a colored curable resin composition 1 having the composition shown in Table 2. Using the obtained colored curable resin composition, a coated film substrate was prepared according to the above-mentioned method, and various evaluations were performed. The results are shown in Table 2.

Examples 2 to 11, Comparative Examples 1 to 12 (Preparation of Colored Curable Resin Compositions 2 to 11 and 51 to 62)
Colored curable resin compositions 2 to 11 and 51 to 62 were obtained in the same manner as in Example 1 except that the composition was changed according to the description in Table 2. The compounds used for the preparation are as follows. Using the obtained colored curable resin composition, a coated film substrate was prepared according to the above-mentioned method, and various evaluations were performed. The results are shown in Table 2.

Fluorinated compound (F)
F-1: "Surflon S-651" (polyethylene glycol chain-containing nonionic fluorine-based surfactant) manufactured by AGC Seimi Chemical Co., Ltd.
F-2: "Megafuck RS-72-K" manufactured by DIC (30% by mass PGMEA solution of nonionic fluorine-based oligomer containing a polyethylene glycol chain and a polymerizable group)

Table 2 shows that the coloring curable resin composition of an Example is excellent in electrical insulation, light-shielding property, and solvent resistance compared with the thing of a comparative example.
On the other hand, in Comparative Examples 1 and 4 which do not contain the compound (C) according to the present invention, the solvent resistance is inferior, and in Comparative Examples 2 and 3 which do not contain the compound (1) according to the present invention, light shielding or electrical insulation It turns out that either is inferior.

  According to the colored curable resin composition of the present invention, it is possible to provide a color filter provided with a black matrix excellent in electrical insulation property, light shielding property and solvent resistance.

Claims (6)

Compound (1) represented by the following formula (1), multifunctional polymerizable compound (B) having two or more ethylenic unsaturated bonds, bis (2-carboxyethyl) isocyanurate, tris (isocyanurate) -Carboxyethyl), and at least one compound (C) selected from trans-1,2-diaminocyclohexane-N, N, N ', N'-tetraacetic acid monohydrate , and dispersant (D) And an organic solvent (E), and a colored curable resin composition.

[In the above-mentioned formula (1), X represents a double bond, and each of them is an E form or a Z form independently as a geometrical isomer, and R ¹ is each independently a hydrogen atom, a methyl group, a nitro group, a methoxy group , Bromine atom, chlorine atom, fluorine atom, carboxy group, or sulfonic acid group, each R ² independently represents a hydrogen atom, a methyl group, or a phenyl group, and each R ³ independently represents a hydrogen atom , A methyl group or a chlorine atom. ]   The mass ratio [(C) / (B)] of the compound (C) to the polyfunctional polymerizable compound (B) in the colored curable resin composition is 0.05 or more and 0.90 or less. Curable resin composition.   The colored curable resin composition according to claim 1 or 2, wherein the polyfunctional polymerizable compound (B) is a polyfunctional (meth) acrylate compound.   The polyfunctional polymerizable compound (B) is trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa ( Colored curable resin composition in any one of Claims 1-3 which is at least 1 sort (s) chosen from meta) acrylate. Colored curable resin composition in any one of Claims 1-4 whose dispersing agent (D) is a polyamine type dispersing agent. The coloring according to any one of claims 1 to 5 , further comprising a surfactant having a fluorocarbon chain, and at least one fluorine compound (F) selected from a compound having a fluorocarbon chain and an ethylenically unsaturated bond. Curable resin composition.