TWI634161B - Colored curable resin composition - Google Patents

Abstract

An object of the present invention is to provide a color hardening resin composition for producing a black matrix excellent in electrical insulating properties, light blocking properties, and solvent resistance, and a color filter including a black matrix formed using the colored curable resin composition. A method of producing an optical device and a color-curable resin composition.

The present invention [1] contains the compound (1) represented by the formula (1), a polyfunctional polymerizable compound (B) having two or more ethylenically unsaturated bonds, and a thiol compound having three or more mercapto groups (C). a color-curable resin composition of the dispersant (D) and the organic solvent (E); [2] a color filter including a black matrix formed using the color-curable resin composition of the above [1]; [3] A method for producing a colored curable resin composition comprising the following steps 1 and 2: Step 1: Dispersing a compound (1) represented by the formula (1), a thiol compound having three or more mercapto groups (C), and dispersing a step of mixing and dispersing the agent (D) and the organic solvent (E) to obtain a dispersion; and Step 2: mixing the dispersion and the polyfunctional polymerizable compound (B) having two or more ethylenically unsaturated bonds step.

Description

Colored curable resin composition

The present invention relates to a colored curable resin composition for use in a color liquid crystal display device, a color filter used in a color image sensor device, or the like, and a black matrix formed using the colored curable resin composition. A color filter and a method of producing a colored curable resin composition.

A black matrix (hereinafter also referred to as "BM (black matrix)") is generally formed in the gap portion of the red, green, and blue filter segments of the color filter to improve the contrast. A grid pattern of black.

In order to improve the image quality of the liquid crystal display, it is required to have excellent light blocking properties for BM. In recent years, in order to cope with higher definition and higher brightness, the method of forming BM on a color filter substrate as before has been changed to a driving substrate for a thin film transistor (TFT) type color liquid crystal display device. A BOA (Black Matrix on Array) method of BM is formed. With regard to the BOA method, the bonding step for alignment with the components is not required, and the pixel aperture ratio (opening ratio) can be greatly increased, and the manufacturing steps can be shortened, thereby improving display quality. The cost is cut, so there are more advantages than the previous method of forming BM on a color filter substrate.

However, when BM is to be formed on the side of the array substrate, since the BM itself is in direct contact with the liquid crystal, the display of the liquid crystal display is poor when the insulation of the BM itself is low.

Moreover, the mask alignment performed during the formation of the BM is performed using an infrared camera, and thus A light transmittance in the near-infrared region of a certain level is required. Therefore, the carbon black mainly used as the BM material not only exhibits a high dielectric constant, but also lacks insulation, and the light transmittance in the near-infrared region is also low, so that it is difficult to perform alignment, and it is difficult to use it in the BOA mode. LCD panel.

As a method for solving such a problem, a method of using a specific organic pigment to have a light-shielding property is disclosed (see Patent Document 1).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Special Table 2012-515233

That is, the present invention relates to the following [1] to [3].

[1] A colored curable resin composition comprising a compound (1) represented by the following formula (1), a polyfunctional polymerizable compound (B) having two or more ethylenically unsaturated bonds, and having three or more a mercapto thiol compound (C), a dispersing agent (D), and an organic solvent (E),

[In the above formula (1), X represents a double bond, and as a geometric isomer, each independently represents an E body or a Z body, and R ¹ independently represents a hydrogen atom, a methyl group, a nitro group, a methoxy group, a bromine atom, or a chlorine atom. An atom, a fluorine atom, a carboxyl group, or a sulfonic acid group, and R ² each independently represents a hydrogen atom, a methyl group, or a phenyl group, and R ³ each 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].

[3] A method for producing a color-curable resin composition, comprising the following steps 1 and 2: Step 1: a compound (1) represented by the formula (1), a thiol compound having three or more mercapto groups ( C) a step of mixing and dispersing the dispersing agent (D) and the organic solvent (E) to obtain a dispersion; and Step 2: dispersing the above-mentioned dispersion and a polyfunctional polymerizable compound having two or more ethylenically unsaturated bonds ( B) The step of mixing.

Further, BM is immersed in N-methyl-2-pyrrolidone which dissolves the polyimide precursor in the formation of the polyimide film (hereinafter, also referred to as "NMP (N-methyl-2-pyrrolidone)" In the solvent, the solvent resistance is required for BM, but the composition described in Patent Document 1 is not sufficient from the viewpoint of solvent resistance. Therefore, it is desirable to provide a color-curable resin composition for BM which is excellent in light-shielding property, insulating property, and solvent resistance. An object of the present invention is to provide a color hardening resin composition for producing a black matrix excellent in electrical insulating properties, light blocking properties, and solvent resistance, and a color filter including a black matrix formed using the colored curable resin composition. A method of producing an optical device and a color-curable resin composition.

The present inventors have found that a combination of a compound (1) represented by the following formula (1), a specific polyfunctional polymerizable compound, and a thiol compound having three or more mercapto groups, which is a black colorant, is used. A color-curable resin composition having high electrical insulating properties, excellent light-shielding properties, and excellent solvent resistance can be obtained.

That is, the present invention relates to the following [1] to [3].

[1] A colored curable resin composition comprising a compound (1) represented by the following formula (1), a polyfunctional polymerizable compound (B) having two or more ethylenically unsaturated bonds, and having three or more a mercapto thiol compound (C), a dispersing agent (D), and an organic solvent (E),

[In the above formula (1), X represents a double bond, and as a geometric isomer, each independently represents an E body or a Z body, and R ¹ independently represents a hydrogen atom, a methyl group, a nitro group, a methoxy group, a bromine atom, or a chlorine atom. An atom, a fluorine atom, a carboxyl group, or a sulfonic acid group, and R ² each independently represents a hydrogen atom, a methyl group, or a phenyl group, and R ³ each 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].

[3] A method for producing a color-curable resin composition, comprising the following steps 1 and 2: Step 1: a compound (1) represented by the formula (1), a thiol compound having three or more mercapto groups ( C) a step of mixing and dispersing the dispersing agent (D) and the organic solvent (E) to obtain a dispersion; and Step 2: dispersing the above-mentioned dispersion and a polyfunctional polymerizable compound having two or more ethylenically unsaturated bonds ( B) The step of mixing.

According to the present invention, it is possible to provide a color hardening resin composition for producing a black matrix excellent in electrical insulating properties, light blocking properties, and solvent resistance, and a color filter including a black matrix formed using the colored curable resin composition. Optical device, and color hardening resin combination The manufacturing method of the object.

The colored curable resin composition of the present invention contains a compound represented by the following formula (1) (hereinafter also referred to as "compound (1)"), and a polyfunctional polymerizable compound having two or more ethylenically unsaturated bonds. (B) (hereinafter also referred to as "(B) component"), a thiol compound (C) having three or more sulfhydryl groups (hereinafter also referred to as "(C) component"), and a dispersing agent (D) (hereinafter also referred to as It is "(D) component") and organic solvent (E) (hereinafter also referred to as "(E) component").

According to the present invention, it is possible to obtain a color-curable resin composition which can produce a black matrix which is excellent in electrical insulating properties and light-shielding properties and which is excellent in solvent resistance. The reason for this effect is not determined, consider the following.

By selecting the compound (1) as a black colorant, excellent electrical insulating properties and light blocking properties can be obtained. On the other hand, there is a tendency that solvent resistance is deteriorated by using the black coloring material, but by using the specific component (B) and the specific component (C), the electrical insulating properties and the light blocking property can be maintained. And obtain higher solvent resistance. First, the (C) component is biased near the surface of the compound (1) by the interaction of the thiol group of the thiol compound of the component (C) with the guanamine moiety of the compound (1). In addition, since the component (C) has three or more sulfhydryl groups, the component (C) itself promotes polymerization in response to the reaction with the olefin-thiol of the component (B) or a chain transfer reaction, and functions as a crosslinking agent efficiently. The crosslinking density near the surface of the compound (1) is increased. Therefore, it is estimated that good hardening characteristics can be obtained and the solvent resistance is excellent. However, these are inferred that the invention is not limited to such mechanisms.

[Compound (1)‧Black Color (A)]

The composition of the present invention contains the compound (1) represented by the formula (1) from the viewpoint of electrical insulating properties and light blocking properties.

[Chemical 3]

In the above formula (1), X represents a double bond, and as a geometric isomer, each independently represents an E body or a Z body, and R ¹ independently represents a hydrogen atom (-H), a methyl group (-CH ₃ ), a nitro group (- NO ₂ group), methoxy group (-OCH ₃ ), bromine atom (-Br), chlorine atom (-Cl), fluorine atom (-F), carboxyl group (-COOH), or sulfonic acid group (-SO ₃ H And R ² each independently represents a hydrogen atom, a methyl group, or a phenyl group, and R ³ each independently represents a hydrogen atom, a methyl group, or a chlorine atom. R ^{1 is} preferably bonded to the 6-position of the indanone ring, and R ^{3 is} preferably bonded to the 4-position of the indanone ring. These compounds may be used singly or in combination of two or more.

R ¹ , R ² and R ^{3 of the} above compound (1) are preferably a hydrogen atom.

The compound (1) can be produced, for example, by the method described in International Publication WO2000/24736 and International Publication WO2010/081624.

The composition of the present invention may contain a black coloring matter other than the above compound (1) within a range not inhibiting the effects of the present invention. Examples of other black colorants include carbon black and titanium black.

In addition, in this specification, the compound (1) and other black coloring materials are also collectively referred to as "black coloring material (A)".

In the black colorant (A), the content of the compound (1) is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 100% by mass.

Further, from the viewpoint of improving the affinity between the black colorant and the organic solvent, and improving the dispersibility and storage stability, it is also possible to use a derivative derived from a resin or a polymer or a compound (1). A black color material which is surface-treated in advance on the surface of the compound (1).

[Polyfunctional 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 the polyfunctional polymerizable compound, a polyfunctional (meth)acrylate compound can be preferably used.

The number of the ethylenically unsaturated bonds contained in one molecule of the polyfunctional polymerizable compound is preferably three or more, more preferably four or more, and still more preferably five or more, from the viewpoint of solvent resistance. It is preferably 8 or less, more preferably 7 or less, still more preferably 6 or less.

Examples of the polyfunctional (meth)acrylate compound include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate. , propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol Di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol Penta(meth) acrylate, dipentaerythritol hexa(meth) acrylate, pentaerythritol di(meth) acrylate, 2,2-bis(4-(methyl) propylene decyloxydiethoxy phenyl) Propane, 2,2-bis(4-(methyl)propenyloxypolyethoxyphenyl)propane, 2-hydroxy-3-(methyl)propenyloxypropyl (meth)acrylate, B Glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl diacetate di(meth)acrylate, glycerol tris(A) base) Acrylate, glycerol polyglycidyl ether poly(meth) acrylate, reaction of polyisocyanate with hydroxyalkyl (meth) acrylate ((meth) acrylate), methylene bis (A) Ethylene amide, dimethylene ether bis(meth) acrylamide, condensate of polyol and N-methylol (meth) acrylamide, tripropylene hydrazine Formaldehyde and the like. These polyfunctional (meth)acrylate compounds may be used singly or in combination of two or more.

Among these, it is preferably selected from trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate. And at least one of dipentaerythritol hexa(meth) acrylate (hereinafter also referred to as "DPHA (dipenta erythritol hexa (meth) acrylate)"), more preferably DPHA.

In the present specification, "(meth) acrylate" means at least one selected from the group consisting of acrylates and methacrylates. Further, "(meth)acrylamide" means at least one selected from the group consisting of acrylamide and methacrylamide.

[thiol compound (C)]

The thiol compound used in the present invention has three or more fluorenyl groups from the viewpoint of solvent resistance. When the number of the sulfhydryl groups is less than three, the crosslinking density is lowered, and the colored color-curable resin composition after curing is a solvent (for example, N-methyl-2-pyrrolidone (hereinafter also referred to as "NMP")). The swelling does not inhibit the dissolution of the black colorant.

The number of the thiol groups in one molecule of the thiol compound is three or more, preferably four or more, from the viewpoint of solvent resistance, and from the same viewpoint, it is preferably nine or less, and more preferably 8 or less, more preferably 7 or less, still more preferably 6 or less, still more preferably 5 or less, still more preferably 4 or less, and still more preferably 4 or more.

Examples of the thiol compound include an aliphatic thiol compound and a thiol compound having a cyclic structure such as a hetero ring or an aromatic ring. From the viewpoint of solvent resistance and ease of design of the thiol group of the thiol compound, it is preferred. It is an aliphatic thiol compound.

The thiol group in the thiol compound may be a primary, secondary or tertiary sulfhydryl group. From the viewpoint of solvent resistance, it is preferably one or more selected from the group consisting of a primary sulfhydryl group and a secondary fluorenyl group, and more preferably a primary fluorenyl group.

Further, the thiol compound preferably has a thiol group from the viewpoint of solvent resistance. The structure of the carboxylic acid is more preferably a structure derived from β-mercaptocarboxylic acid.

Examples of the aliphatic thiol compound include 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, and 1,2,3-trid. (3-mercaptopropylthio)propane, trimethylolpropane tris(2-mercaptoacetate), glycerol tris(2-mercaptoacetate), pentaerythritol tetrakis(2-mercaptoacetate), dipentaerythritol (2-mercaptoacetate), dipentaerythritol hexa(2-mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol (3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), dipentaerythritol hexakis(3-mercaptobutyrate), and the like.

Examples of the thiol compound having a heterocyclic ring include tris[(3-mercaptopropyloxy)-ethyl]isocyanurate and tris[(3-mercaptobutyloxy)-ethyl]isocyanate. Uric acid ester, (1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-three -2,4,6(1H,3H,5H)-trione), tris[(3-mercaptopropoxy)-methyl]isocyanurate.

Examples of the thiol compound having an aromatic ring include 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tri ( Mercaptomethyl)benzene, 1,2,4-tris(decylmethyl)benzene, 1,3,5-tris(decylmethyl)benzene, 1,2,3-tris(decylethyl)benzene, 1, 3,5-tris(decylethyl)benzene, 1,2,4-tris(decylethyl)benzene, 1,2,3,4-tetradecylbenzene.

Among the above thiol compounds, preferred is selected from the group consisting of pentaerythritol tetrakis(3-mercaptopropionate), tris(3-mercaptopropionic acid) trimethylolpropane, and 1,3,5-tris(3-mercaptobutyloxy) Base ethyl)-1,3,5-three -2,4,6(1H,3H,5H)-trione, dipentaerythritol hexa(3-mercaptopropionate) and tris-[(3-mercaptopropoxy)-ethyl]-isocyanuric acid At least one ester is more preferably at least one selected from the group consisting of pentaerythritol tetrakis(3-mercaptopropionate) and dipentaerythritol hexakis(3-mercaptopropionate), and further preferably pentaerythritol tetrakis(3-mercaptopropane) Acid ester).

[Dispersant (D)]

The dispersing agent used in the present invention may, for example, be a polyurethane type or polyamine having a poly(meth)acrylate, a polylactone, a polyalkylene oxide or the like as a main chain or a side chain. Polycarboxylic acids such as polyimine, poly(meth)acrylic acid, polymaleic acid (anhydride) A dispersant which is a polyamine-based dispersant and a part of which is introduced into a quaternary ammonium salt or the like. These dispersing agents may be used singly or in combination of two or more kinds.

As a commercially available dispersant, examples of the polyurethane system include Disperbyk-161, 166, and 167 manufactured by BYK-Chemie Japan Co., Ltd., and Solsperse 55000 and 76500 manufactured by Lubrizol Co., Ltd., Japan; Examples include Disperbyk-106, 110, 111, Solsperse 36000, 41000, EFKA-5060 manufactured by BASF Japan, etc.; as polyamines, Disperbyk-116, 130, Solsperse 24000, 32000, 33000, J200, EFKA -4046, Ajisper PB821, PB822, PB824, PB881, etc. manufactured by Ajinomoto Fine-Techno. Among these, from the viewpoint of dispersibility, a polyamine system is preferred, and EFKA-4046 and Solsperse J200 are more preferred.

[Organic solvent (E)]

Examples of the organic solvent include lower alcohols having 1 to 4 carbon atoms such as ethanol and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as toluene and xylene; and aliphatic hydrocarbons such as cyclohexane; A polyhydric alcohol such as propylene glycol or an ether such as ethylene glycol diethyl ether; or a compound represented by the following formula (2), such as ethyl acetate, eucalyptus oil, higher alcohol, oil or fat, and the like.

Wherein R ⁴ and R ⁵ each independently represent a straight or branched alkyl group having 1 to 4 carbon atoms which may be substituted by an alkoxy group having 1 to 3 carbon atoms; and R ⁶ represents a hydrogen atom or a methyl group; Indicates an integer from 0 to 3]

In the formula (2), examples of the alkyl group having 1 to 4 carbon atoms of R ⁴ and R ⁵ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, and a 3-methoxybutyl group. , isobutyl, second butyl, and tert-butyl. Among these, a methyl group and an ethyl group are preferable.

n is preferably 1 or 2.

The organic solvent is preferably selected from the group consisting of ethylene glycol monoethyl ether acetate and propylene glycol monomethyl ether acetate from the viewpoints of dispersibility of the coloring material and solubility or dispersibility of the dispersing agent (hereinafter, also At least one of a group consisting of "PGMEA (propylene glycol monomethyl ether acetate)", diethylene glycol monobutyl ether acetate, 3-methoxybutyl acetate, and propylene glycol monoethyl ether acetate.

These organic solvents may be used singly 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 solvent resistance. It is considered that during the formation of the coating film by using the colored curable resin composition, drying and hardening, the fluorine compound bleeds out on the surface of the BM, and the penetration of the solvent into the BM is reduced, whereby the elution of the black color material is further suppressed.

The fluorine compound can exert a synergistic effect by using it in combination with a thiol compound, and can obtain remarkable solvent resistance. It is considered that a hydrogen bond is formed between a mercapto group of a thiol compound which is adjacent to the surface of the compound (1) and a fluorine group of the fluorine compound, whereby the fluorine compound is also biased near the surface of the pigment to form a solvent-insoluble property on the surface of the pigment. Film coating to improve solvent resistance.

The fluorine compound may be at least one selected from the group consisting of a surfactant having a fluorocarbon chain, a fluorine-based oligomer, and a compound having a fluorocarbon chain and a polymerizable group.

As a surfactant having a fluorocarbon chain, commercially available products include Fluorinert FC430, FC431 manufactured by Sumitomo 3M Co., Ltd., MEGAFAC F142D, F171, F172, F173, F177, F183, F554 manufactured by DIC Corporation. , R30, Eftop EF301, EF303, EF351, EF352 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., Surflon S-381, S-382, SC-101, SC-105, Daikin Fine Chemical Research, manufactured by AGC Qingmei Chemical Co., Ltd. E5844 manufactured by Institute Co., Ltd., etc.

As a fluorine-based oligomer, commercially available products include Surflon S-611, S-651, and the like manufactured by AGC Seimi Chemical Co., Ltd.

Examples of the compound having a fluorocarbon chain and a polymerizable group include MEGAFAC RS-72-K, RS-75, and RS-76-E manufactured by DIC Corporation.

In order to reduce solvent penetration into the coating film, it is preferred that the solubility of the fluorine compound to the solvent is low.

Since the fluorine compound has a higher molecular weight than the surfactant, it is preferably a fluorine-based oligomer.

The fluorine compound can be simultaneously cured by the reactive group and the component (B), and the polymerization reaction can be further carried out in the vicinity of the surface of the compound (1) by the interaction with the component (C) to further improve the solvent resistance. From the viewpoint of insulating properties, a compound having a fluorocarbon chain and a polymerizable group is preferred.

Further, it is considered that the fluorine compound having a reactive group forms a covalent bond with a thiol compound in addition to the above hydrogen bond by participating in an ene-thiol reaction or chain transfer polymerization which starts from a thiol group. It is fixed near the surface of the pigment to further improve solvent resistance.

Among the fluorine-based oligomers, Surflon S-611 and S-651 are preferred. Among the compounds having a fluorocarbon chain and a polymerizable group, a compound having a fluorocarbon chain and an ethylenically unsaturated bond is preferred, and a fluorocarbon chain, an ethylenically unsaturated bond, and a polyethylene glycol chain are more preferred. As a commercial product, a compound is preferably exemplified by MEGAFAC RS-72-K, RS-75, and RS-76-E.

The fluorine compound used in the present invention may be one type or a mixture of two or more types.

The viscosity of the 30 mass% PGMEA solution of the fluorine compound at 25 ° C is preferably 24 mPa·s or less, more preferably 18 mPa·s or less from the viewpoint of forming a more uniform solvent-resistant film on the surface of the pigment. Further, it is preferably 12 mPa ‧ or less, more preferably 0.1 mPa ‧ s or more, still more preferably 1 mPa ‧ s or more, and still more preferably 3 mPa ‧ s or more

The viscosity is a viscosity measured by an E-type viscometer, and specifically, it can be measured by the method described in the examples.

The colored curable resin composition of the present invention may contain, for example, a photopolymerization initiator, a photoinitiator, an alkali-soluble resin, or the like.

As the photopolymerization initiator, a known polymerization initiator can be used, and for example, 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one, 2 is preferably used. 2-dimethoxy-1,2-diphenylethane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1- Propane-1-one, 1-hydroxy-cyclohexyl-phenyl-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, (4-methylphenyl)[4-( 2-methylpropyl)phenyl]phosphonium hexafluorophosphate, 2-[2-oxo-2-phenylethenyloxyethoxy]ethyl ester and 2-(2-hydroxyethoxy)ethyl a mixture of esters, phenyl glycosylate, benzophenone, and the like. As a commercially available photopolymerization initiator, for example, IRGACURE 369, 907, 651, 2959, 184, 250, 754; DAROCUR MBF, BP, 1173 (manufactured by BASF Japan Co., Ltd.) and the like are preferable. These photopolymerization initiators may be used singly or in combination of two or more.

Further, a photoinitiator may be combined with the photopolymerization initiator.

Examples of the photoinitiating aid include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-di Isoamyl methylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethyl-p-toluidine, 4,4' - bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-di Methoxyquinone, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. These photoinitiating aids may be used singly or in combination of two or more.

The alkali-soluble resin is used to dissolve the unexposed portion in the developer when the color filter is manufactured by photolithography. As the alkali-soluble resin, those generally used for a negative resist can be used as long as they are soluble in an alkaline aqueous solution, that is, dissolved in a 0.05% by mass aqueous solution of tetramethylammonium hydroxide at 20° C. by 1% by mass or more. Anyone can be, and is not particularly limited.

As the alkali-soluble resin used in the present invention, a copolymer of (meth) acrylate and (meth)acrylic acid can be preferably used.

Examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (methyl). At least one of n-butyl acrylate, tert-butyl (meth)acrylate, and benzyl (meth)acrylate. Among these, benzyl (meth)acrylate and methyl (meth)acrylate are preferable. That is, as a copolymer of (meth) acrylate and (meth)acrylic acid, a copolymer of benzyl (meth) acrylate and (meth)acrylic acid, and methyl (meth) acrylate and (a) are more preferable. Copolymer of acrylic acid.

The copolymerization ratio (mol ratio) of the acrylate to (meth)acrylic acid is preferably from 90/10 to 50/50, more preferably from 80/20 to 70/30. The weight average molecular weight of the alkali-soluble resin is preferably from 5,000 to 50,000.

In the present specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. Further, "(meth) acrylate" means at least one selected from the group consisting of acrylates and methacrylates.

The amount of the solid content component in the colored curable resin composition is preferably 10% by mass or more, more preferably 13% by mass or more, further preferably 15% by mass or more, and further preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 25% by mass or less.

The content of the compound (1) in the coloring curable resin composition is preferably 4% by mass or more, more preferably 5% by mass or more, and still more preferably 8% by mass, from the viewpoint of obtaining good light blocking properties. In addition, 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, and more preferably 25% by mass or more based on the amount of the solid content in the colored curable resin composition, from the viewpoint of obtaining a good light-shielding property. Furthermore, it is preferably 40% by mass or more, and is 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 colorant (A) in the coloring curable resin composition is preferably 4% by mass or more, more preferably 5% by mass or more, and still more preferably 8 from the viewpoint of obtaining good light blocking properties. The mass % or more is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less from the viewpoint of obtaining good solvent resistance.

The content of the black colorant (A) is preferably 20% by mass or more, and more preferably 25% by mass, based on the amount of the solid content component in the colored curable resin composition, from the viewpoint of obtaining a good light-shielding property. The above is more preferably 40% by mass or more, and is 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, and further preferably from the viewpoint of obtaining a good film hardness. It is 0.7% by mass or more, more preferably 10% by mass or less, still 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, and more preferably 2.0, based on the amount of the solid content in the colored curable resin composition from the viewpoint of obtaining a good film hardness. The mass% or more is more preferably 3.0% by mass or more, more preferably 30% by mass or less, still more preferably 20% by mass or less, still more preferably 15% by mass or less.

The content of the thiol compound (C) in the coloring curable resin composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and still more preferably 0.3% by mass, from the viewpoint of solvent resistance. In view of the light-shielding property, it is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, further preferably 1% by mass or less, and further preferably 1% by mass or less. 0.7% by mass or less, more preferably 0.5% by mass or less, further preferably 0.4% by mass or less.

Regarding the content of the thiol compound (C), in terms of solvent resistance, relative to The amount of the solid content component in the color curable resin composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 1.5% by mass or more, and further preferably from the viewpoint of light blocking property. It is 30% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, further preferably 5% by mass or less, further preferably 3% by mass or less, and further preferably 2% by mass or less.

The content of the thiol compound (C) in the coloring-curable composition is preferably 1 part by mass or more, and more preferably 2 parts by mass or more from the viewpoint of solvent resistance, from 100 parts by mass of the compound (1). Furthermore, it is preferably 3 parts by mass or more, and more preferably 10 parts by mass or less, more preferably 7 parts by mass or less, still more preferably 5 parts by mass or less, and still more preferably 4, from the viewpoint of light blocking properties. Below the mass.

The mass ratio [(C)/(B)] of the thiol compound (C) to the polyfunctional polymerizable compound (B) in the colored curable resin composition is preferably from the viewpoint of solvent resistance. It is 0.05 or more, more preferably 0.07 or more, further preferably 0.1 or more, further preferably 0.2 or more, further preferably 1 or less, more preferably 0.7 or less, still more preferably 0.5 or less.

The content of the dispersing agent (D) in the colored curable resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably from the viewpoint of good light blocking property and solvent resistance. In addition, from the same viewpoint, it is 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, and more preferably 2.5, based on the amount of the solid content in the colored curable resin composition, from the viewpoint of good light-shielding property and solvent resistance. The mass % or more is further preferably 5% by mass or more, and from the same viewpoint, it is preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less.

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

The content of the fluorine compound (F) in the colored curable resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably from the viewpoint of good insulating properties and solvent resistance. It is 0.08% by mass or more, more preferably 5% by mass or less, more preferably 2% by mass or less, further preferably 1% by mass or less, and still more preferably 0.5% by mass or less.

The content of the fluorine compound (F) is preferably 0.2% by mass or more, and more preferably 0.6%, based on the amount of the solid content in the colored curable resin composition, from the viewpoint of good insulating properties and solvent resistance. The mass% or more is more preferably 1.2% by mass or more, more preferably 10% by mass or less, still more preferably 5% by mass or less, further preferably 3% by mass or less, and still more preferably 1.6% by mass or less.

The content of the fluorine compound (F) in the coloring curable composition is preferably 0.2 part by mass or more, more preferably 0.6 mass, from the viewpoint of solvent resistance and insulating properties with respect to 100 parts by mass of the compound (1). The amount of the color filter is preferably 1.2 parts by mass or more, more preferably 2.5 parts by mass or more, and further preferably 10 parts by mass or less, more preferably 5 parts by mass, from the viewpoint of easy production of the color filter. Hereinafter, it is more preferably 3.5 parts by mass or less.

The mass ratio [(F)/(C)] of the fluorine compound (F) to the thiol compound (C) in the colored curable resin composition is preferably from the viewpoint of solvent resistance and insulation properties. It is preferably 0.05 or more, more preferably 0.07 or more, and further preferably 0.1 or more. Further, from the viewpoint of easy production of the color filter, it is preferably 1 or less, more preferably 0.8 or less, still more preferably 0.7 or less.

The content of the alkali-soluble resin is preferably 5.0% by mass or more, and more preferably 10% by mass based on the amount of the solid content in the colored curable resin composition from the viewpoint of obtaining good developability and film hardness. The above is more preferably 15% by mass or more, further 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 coloring curable resin composition is preferably 5 masses per 100 parts by mass of the component (B) in the coloring curable resin composition from the viewpoint of obtaining a good film hardness. The amount is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, further preferably 70 parts by mass or less, more preferably 60 parts by mass or less, still more preferably 50 parts by mass or less. By setting it as the said range, sufficient heat resistance and chemical resistance can be acquired, and the coating film formation capability can be improved, and hardening failure can be suppressed.

The content of the photopolymerization initiation aid in the coloring curable resin composition is preferably 100 parts by mass based on the component (B) of the coloring curable resin composition, from the viewpoint of obtaining a good film hardness. 1 part by mass or more, more preferably 3 parts by mass or more, further preferably 5 parts by mass or more, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, still more preferably 15 parts by mass or less. By setting it as the said range, sufficient heat resistance and chemical resistance can be acquired, and the coating film formation capability can be improved, and hardening failure can be suppressed.

[Production method]

The method for producing a color-curable resin composition of the present invention preferably has the following steps 1 and 2: Step 1: a compound (1) represented by the formula (1), a thiol compound having three or more mercapto groups ( C) a step of mixing and dispersing the dispersing agent (D) and the organic solvent (E) to obtain a dispersion; and Step 2: dispersing the above-mentioned dispersion and a polyfunctional polymerizable compound having two or more ethylenically unsaturated bonds ( B) The step of mixing.

As the mixing and dispersing machine used in the dispersion of the above step 1, various known dispersing machines can be used. For example, a high-speed stirring and mixing device such as a homomixer, a kneader such as a roll mill, a kneader or an extruder, a high-pressure disperser such as a high-pressure homogenizer, a medium disperser such as a paint shaker or a bead mill, and the like may be mentioned. These devices can also be used in combination with a plurality of types.

Among these, from the viewpoint of uniformly mixing the black colorant in the organic solvent, a high-speed stirring and mixing device such as a homomixer, a paint shaker or a bead mill is preferable. Media disperser. As a commercially available media type dispersing machine, "Ultra Apex Mill" manufactured by Shou Industrial Co., Ltd., "Pico Mill" manufactured by Asada Iron Works Co., Ltd., and the like can be cited.

In the case of using a medium dispersing machine, the material used for the dispersion step is preferably a ceramic such as zirconia or titania, a polymer material such as polyethylene or nylon, or a metal, and the like, in terms of attrition. In other words, zirconia is preferred. Further, the diameter of the medium is preferably 0.003 mm or more, more preferably 0.01 mm or more, and further preferably 0.5 mm or less, more preferably 0.4, from the viewpoint of crushing the aggregated particles in the black coloring material. Below mm.

The dispersing time is preferably 0.3 hours or more, more preferably 1 hour or more from the viewpoint of sufficiently miniaturizing the black color material, and is preferably 50 in terms of the production efficiency of the pigment dispersion. Below the hour, more preferably less than 10 hours.

The mixing method of the step 2 is not particularly limited and can be obtained, for example, by stirring using a roll mixer. The stirring time is preferably 5 minutes or longer, more preferably 15 minutes or longer, and from the viewpoint of production efficiency, it is preferably 10 hours or shorter, more preferably 1 hour or shorter.

The preferred blending amount of each component in the method for producing the colored curable resin composition is such that the final colored curable resin composition is a preferred content of each component in the composition described above.

[Color filter]

The colored curable resin composition of the present invention can be preferably used for the production of a color filter, and more specifically, can be preferably used for the manufacture of a black matrix of a color filter.

Preferably, the method for producing a color filter comprising a black matrix formed by using the colored curable resin composition of the present invention comprises the step (a) of applying the colored curable resin composition of the present invention onto a substrate. Drying, photohardening, developing to obtain a coating film; in step (b), heating the coating film obtained in the above step (a) to 200 to 300 ° C to form a black matrix composed of a cured film; and step (c) Applying organic resin to the above cured film A solvent solution forms a resin film.

After the coating of the above step (a), the organic solvent is dried, and from the viewpoint of smoothness or productivity of the coating film, heating or depressurization is preferred.

In the photocuring, for example, the coating film is irradiated with ultraviolet rays, and the polyfunctional monomer in the colored curable resin composition is subjected to a crosslinking reaction to cure the coating film. The photocuring is carried out in order to leave a pattern on the glass substrate by subsequent development, and it is preferable to provide a mask for preventing ultraviolet rays from being removed by development, so as not to be hardened.

In the above development, for example, the hardened coating film after photohardening is immersed in an alkaline aqueous solution, and further rinsed with water to remove the unhardened portion.

The step (b) is a post-baking step, and by performing this step, a cured film excellent in hardness can be formed.

The resin of the step (c) is, for example, a polyimine. The organic solvent of the step (c) is, for example, N-methyl-2-pyrrolidone.

In the above embodiment, the present invention further discloses the following colored curable resin composition, color filter, and the like.

<1> A colored curable resin composition containing the compound (1) represented by the following formula (1), a polyfunctional polymerizable compound (B) having two or more ethylenically unsaturated bonds, and having three or more a mercapto thiol compound (C), a dispersing agent (D), and an organic solvent (E),

[In the above formula (1), X represents a double bond, and as a geometric isomer, each independently represents an E body or a Z body, and R ¹ independently represents a hydrogen atom, a methyl group, a nitro group, a methoxy group, a bromine atom, or a chlorine atom. An atom, a fluorine atom, a carboxyl group, or a sulfonic acid group, and R ² each independently represents a hydrogen atom, a methyl group, or a phenyl group, and R ³ each independently represents a hydrogen atom, a methyl group, or a chlorine atom].

<2> The colored curable resin composition according to <1>, wherein R ¹ , R ² and R ^{3 of the} compound (1) are preferably a hydrogen atom.

<3> The colored curable resin composition according to <1> or <2>, wherein the content of the compound (1) in the black colorant is preferably 80% by mass or more, more preferably 90% by mass or more, and further Good is 100% by mass.

The colored curable resin composition according to any one of the above aspects, wherein the number of the ethylenically unsaturated bonds contained in the polyfunctional polymerizable compound (B) is preferably three or more. More preferably, it is 4 or more, More preferably 5 or more, More preferably, it is 8 or less, More preferably, it is 7 or less, More preferably, it is 6 or less.

The colored curable resin composition according to any one of <1> to <4> wherein the polyfunctional polymerizable compound (B) is preferably selected from trimethylolpropane tri(meth)acrylate. At least one of pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate, more preferably dipentaerythritol (Meth) acrylate.

(6) The colored curable resin composition according to any one of the above-mentioned, wherein the number of the thiol groups in the thiol compound (C) is three or more, preferably four or more, and further, It is preferably 9 or less, more preferably 8 or less, still more preferably 7 or less, still more preferably 6 or less, still more preferably 5 or less, still more preferably 4 or less, and furthermore Good for 4.

The colored curable resin composition according to any one of <1> to <6> wherein the thiol compound (C) is preferably an aliphatic thiol compound.

<8> The colored curable resin composition according to any one of <1> to <7>, Among them, the thiol compound (C) preferably has a structure derived from a mercaptocarboxylic acid, and more preferably has a structure derived from a β-mercaptocarboxylic acid.

The colored curable resin composition according to any one of the above aspects, wherein the mercapto group in the thiol compound is preferably one or more selected from the group consisting of a primary sulfhydryl group and a secondary fluorenyl group, and more preferably First level thiol.

The colored curable resin composition according to any one of <1> to <9> wherein the thiol compound (C) is preferably selected from the group consisting of pentaerythritol tetrakis(3-mercaptopropionate) and tris(3). - mercaptopropionic acid) trimethylolpropane, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-three -2,4,6(1H,3H,5H)-trione, dipentaerythritol hexa(3-mercaptopropionate) and tris-[(3-mercaptopropoxy)-ethyl]-isocyanuric acid At least one ester is more preferably at least one selected from the group consisting of pentaerythritol tetrakis(3-mercaptopropionate) and dipentaerythritol hexakis(3-mercaptopropionate), and further preferably pentaerythritol tetrakis(3-mercaptopropane) Acid ester).

The colored curable resin composition according to any one of <1> to <10> wherein the dispersing agent (D) preferably has a poly(meth)acrylate, a polylactone, a polyalkylene oxide. Polycarboxylates such as polyurethanes, polyamines, polyimines, poly(meth)acrylic acid, polymaleic acid (anhydrides), etc., which are main chains or side chains, The amine-based dispersant and a dispersant obtained by introducing a part of a quaternary ammonium salt or the like into a part thereof are more preferably a polyamine-based dispersant.

The colored curable resin composition according to any one of <1> to <11> wherein the organic solvent (E) is preferably selected from the group consisting of ethylene glycol monoethyl ether acetate and propylene glycol monomethyl ether acetate. At least one of a group consisting of ester (PGMEA), diethylene glycol monobutyl ether acetate, 3-methoxybutyl acetate, and propylene glycol monoethyl ether acetate.

The colored curable resin composition according to any one of <1> to <12>, which further preferably contains a fluorine compound (F).

<14> The colored curable resin composition according to <13>, wherein the fluorine compound (F) is preferably selected from the group consisting of a surfactant having a fluorocarbon chain, a fluorine-based oligomer, and having a fluorocarbon chain and polymerizability. At least one of the compounds of the group, more preferably a fluorocarbon chain and a polymerizable group Further, the compound is preferably a compound having a fluorocarbon chain and an ethylenically unsaturated bond, and more preferably a compound having a fluorocarbon chain, an ethylenically unsaturated bond, and a polyethylene glycol chain.

<15> The colored curable resin composition according to <13> or <14>, wherein the 30% by mass of the PGMEA solution of the fluorine compound (F) has a viscosity at 25 ° C of preferably 24 mPa ‧ or less, more preferably 18 mPa ‧ s or less is further preferably 12 mPa ‧ s or less, more preferably 0.1 mPa ‧ s or more, still more preferably 1 mPa ‧ s or more, and still more preferably 3 mPa ‧ s or more

The colored curable resin composition according to any one of <1> to <15>, which further preferably contains a photopolymerization initiator.

<17> The colored curable composition according to <16>, which further preferably contains a photoinitiating aid.

The colored curable resin composition according to any one of <1> to <17>, which further preferably contains an alkali-soluble resin.

The colored curable resin composition according to any one of the above aspects, wherein the amount of the solid content component in the colored curable resin composition is preferably 10% by mass or more, more preferably 13% by mass. % or more is further preferably 15% by mass or more, more preferably 40% by mass or less, still more preferably 30% by mass or less, and still more preferably 25% by mass or less.

The colored curable resin composition according to any one of the above aspects, wherein the content of the compound (1) in the colored curable resin composition is preferably 4% by mass or more, more preferably 5 mass% or more, more preferably 8% by mass or more, further preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less.

The colored curable resin composition according to any one of the above aspects, wherein the content of the compound (1) is preferably 20 based on the amount of the solid content in the colored curable resin composition. The mass% or more is more preferably 25% by mass or more, further preferably 40% by mass or more, more preferably 80% by mass or less, still more preferably 70% by mass or less, and still more preferably 60% by mass or less.

The colored curable resin composition according to any one of the above aspects, wherein the content of the black colorant (A) in the colored curable resin composition is preferably 4% by mass or more, and more preferably It is preferably 5% by mass or more, more preferably 8% by mass or more, further preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less.

The colored curable resin composition according to any one of <1> to <22>, wherein the content of the black colorant (A) is preferably the amount of the solid content in the colored curable resin composition. It is 20% by mass or more, more preferably 25% by mass or more, further preferably 40% by mass or more, more preferably 80% by mass or less, still more preferably 70% by mass or less, and still more preferably 60% by mass or less.

The colored curable resin composition according to any one of the above aspects, wherein the content of the polyfunctional polymerizable compound (B) in the colored curable resin composition is preferably 0.3% by mass or more. The amount is more preferably 0.5% by mass or more, further preferably 0.7% by mass or more, more preferably 10% by mass or less, still more preferably 5% by mass or less, still more preferably 3% by mass or less.

The colored curable resin composition according to any one of the above aspects, wherein the content of the polyfunctional polymerizable compound (B) is relative to the amount of the solid content in the colored curable resin composition. It is preferably 1.0% by mass or more, more preferably 2.0% by mass or more, still more preferably 3.0% by mass or more, further preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass. the following.

The colored curable resin composition according to any one of the above aspects, wherein the content of the thiol compound (C) in the colored curable resin composition is preferably 0.1% by mass or more. It is preferably 0.2% by mass or more, more preferably 0.3% by mass or more, further preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, and further preferably 1% by mass. The amount is more preferably 0.7% by mass or less, further preferably 0.5% by mass or less, and further preferably 0.4% by mass or less.

<27> The colored curable resin composition as described in any one of <1> to <26> The content of the thiol compound (C) is preferably 0.5% by mass or more, more preferably 1% by mass or more, and still more preferably 1.5% by mass or more based on the amount of the solid content component in the colored curable resin composition. Further, it is preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, further preferably 5% by mass or less, further preferably 3% by mass or less, and further preferably 3% by mass or less. 2% by mass or less.

The colored curable resin composition according to any one of <1> to <27> wherein the content of the thiol compound (C) in the coloring curable composition is 100 parts by mass based on the compound (1). It is preferably 1 part by mass or more, more preferably 2 parts by mass or more, further preferably 3 parts by mass or more, more preferably 10 parts by mass or less, still more preferably 7 parts by mass or less, still more preferably 5 parts by mass or less. Further, it is preferably 4 parts by mass or less.

The colored curable resin composition according to any one of <1> to <28> wherein the thiol compound (C) in the colored curable resin composition is relative to the polyfunctional polymerizable compound (B) The mass ratio [(C)/(B)] is preferably 0.05 or more, more preferably 0.07 or more, still more preferably 0.1 or more, still more preferably 0.2 or more, further preferably 1 or less, more preferably 0.7 or less. Further, it is preferably 0.5 or less.

The colored curable resin composition according to any one of the above aspects, wherein the content of the dispersing agent (D) in the colored curable resin composition is preferably 0.1% by mass or more, more preferably It is 0.5% by mass or more, more preferably 1% by mass or more, further preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less.

The colored curable resin composition according to any one of the above aspects, wherein the content of the dispersing agent (D) is preferably the amount of the solid content in the colored curable resin composition. 0.5% by mass or more, more preferably 2.5% by mass or more, further preferably 5% by mass or more, more preferably 40% by mass or less, still more preferably 30% by mass or less, still more preferably 20% by mass or less.

The colored curable resin composition according to any one of the above aspects, wherein the content of the organic solvent (E) in the colored curable resin composition is preferably 60. The amount is at least 70% by mass, more preferably 75% by mass or more, further preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less.

The colored curable resin composition according to any one of the above aspects, wherein the content of the fluorine compound (F) in the colored curable resin composition is preferably 0.01% by mass or more, more preferably It is 0.05% by mass or more, more preferably 0.08% by mass or more, further preferably 5% by mass or less, more preferably 2% by mass or less, further preferably 1% by mass or less, and still more preferably 0.5% by mass or less. .

The colored curable resin composition according to any one of the above aspects, wherein the content of the fluorine compound (F) is preferably the amount of the solid content in the colored curable resin composition. 0.2% by mass or more, more preferably 0.6% by mass or more, further preferably 1.2% by mass or more, further preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, and further More preferably, it is 1.6% by mass or less.

The colored curable resin composition according to any one of the above aspects, wherein the content of the fluorine compound (F) in the coloring curable composition is preferably 100 parts by mass based on 100 parts by mass of the compound (1). It is 0.2 parts by mass or more, more preferably 0.6 parts by mass or more, further preferably 1.2 parts by mass or more, more preferably 2.5 parts by mass or more, still more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less. Further, it is preferably 3.5 parts by mass or less.

The colored curable resin composition according to any one of <1> to <35>, wherein the mass ratio of the fluorine compound (F) to the thiol compound (C) in the colored curable resin composition is [ (F)/(C)] is preferably 0.05 or more, more preferably 0.07 or more, further preferably 0.1 or more, further preferably 1 or less, more preferably 0.8 or less, still more preferably 0.7 or less.

The colored curable resin composition according to any one of the above aspects, wherein the content of the alkali-soluble resin is preferably 5.0 by mass based on the amount of the solid content component in the colored curable resin composition. More preferably, it is 10% by mass or more, more preferably 15% by mass or more, further preferably 50% by mass or less, more preferably 40% by mass or less, more preferably Good is 35 mass% or less.

The colored curable resin composition according to any one of the above aspects, wherein the content of the photopolymerization initiator in the colored curable resin composition is relative to that of the colored curable resin composition. 100 parts by mass of the component (B) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 20 parts by mass or more, more preferably 70 parts by mass or less, still more preferably 60 parts by mass or less. Further, it is preferably 50 parts by mass or less.

The colored curable resin composition according to any one of the above aspects, wherein the content of the photopolymerization initiation aid in the coloring curable resin composition is relative to the coloring curable resin composition. 100 parts by mass of the component (B) is preferably 1 part by mass or more, more preferably 3 parts by mass or more, further preferably 5 parts by mass or more, more preferably 30 parts by mass or less, still more preferably 20 parts by mass. Hereinafter, it is more preferably 15 parts by mass or less.

The colored curable resin composition according to any one of <1> to <39>, which is preferably a black matrix for forming a color filter.

<41> A method for producing a color-curable resin composition, comprising the following steps 1 and 2: Step 1: a compound (1) represented by the following formula (1), a thiol having three or more mercapto groups a step of mixing and dispersing the compound (C), the dispersing agent (D) and the organic solvent (E) to obtain a dispersion; and Step 2: dispersing the above-mentioned dispersion and polyfunctional polymerizable having two or more ethylenically unsaturated bonds Step of mixing compound (B) [Chemical 6]

[In the above formula (1), X represents a double bond, and as a geometric isomer, each independently represents an E body or a Z body, and R ¹ independently represents a hydrogen atom, a methyl group, a nitro group, a methoxy group, a bromine atom, or a chlorine atom. An atom, a fluorine atom, a carboxyl group, or a sulfonic acid group, and R ² each independently represents a hydrogen atom, a methyl group, or a phenyl group, and R ³ each independently represents a hydrogen atom, a methyl group, or a chlorine atom].

<42> A color filter comprising a black matrix formed by using the color-curable resin composition according to any one of <1> to <40>.

<43> A method of producing a color filter comprising a black matrix, comprising: step (a), applying the color-curable resin composition according to any one of <1> to <40> on a substrate And drying, photohardening, and developing to obtain a coating film; in step (b), heating the coating film obtained in the above step (a) to 200 to 300 ° C to form a black matrix composed of a cured film; and a step (c) An organic solvent solution of a resin is applied onto the cured film to form a resin film.

The use of the color-curable resin composition according to any one of the items <1> to <40>, which is a black matrix for producing a color filter.

The use of the color-curable resin composition according to any one of the items <1> to <40>, which is used for producing a color filter.

[Examples]

Preparation of a coated substrate, measurement of optical density (hereinafter referred to as "OD (optical density)"), evaluation of solvent resistance, measurement of surface resistivity, evaluation of electrical insulating properties, weight average molecular weight, and solid content And the determination of viscosity by the following The law is carried out.

(1) Production of coated substrate

The colored curable resin composition was applied onto the glass substrate by a spin coater, allowed to stand on a water platform for 5 minutes, and dried on a hot plate at 120 ° C for 10 minutes. Further, it was treated in a clean oven at 230 ° C for 20 minutes to obtain a substrate (also referred to as a "coating substrate") having a coating film on one side.

(2) Measurement of OD (shading evaluation) and evaluation of solvent resistance

The OD (pre-treatment OD) of the coating film substrate was measured by a tabletop transmission density meter ("Model 361T" manufactured by X-Rite Co., Ltd., measuring wavelength: 550 nm). The larger the OD before treatment, the better the light blocking property.

Next, 50 μL of N-methyl-2-pyrrolidone droplets were formed on a coating film of the coated substrate using a micro syringe. After standing for 5 minutes, air was blown to remove droplets, and the OD (treated OD) of the portion where the above droplets were formed was measured. The OD difference was obtained by the following formula. The closer the OD difference is to 0, the better the solvent resistance.

OD difference = OD before processing - pre-processing OD

(3) Measurement of surface resistivity and evaluation of electrical insulation

After the coating substrate was allowed to stand in an environment of 25 ° C and 45% RH for 6 hours, the resistance value measuring chamber (manufactured by Kawaguchi Electric Co., Ltd.) connected to an insulation resistor ("4329A" manufactured by Yokogawa Hewlett Packard Co., Ltd.) was used. "Model P-601", measurement voltage: 100 V), surface resistivity Ps (Ω / □) was measured, and electrical insulation was evaluated. The greater the value of the surface resistivity, the better the electrical insulation.

(4) Determination of weight average molecular weight

The sample was diluted with N,N-dimethylformamide to prepare a solution having a solid content of 0.3% by mass of the sample, and 0.1 mL of the solution was used as a measurement solution. A solution obtained by dissolving phosphoric acid and lithium bromide in a concentration of 60 mmol/L and 50 mmol/L in a concentration of 60 mmol/L and 50 mmol/L, respectively, as a solution, by gel permeation chromatography (hereinafter, Also known as "GPC (Gel Permeation Chromatography)") [Device: "HLC-8120GPC" manufactured by Tosoh Co., Ltd., column: "TSK-GEL, α-M" × 2 manufactured by Tosoh Co., Ltd., flow rate: 1 mL / Min], using polystyrene as a standard substance for measurement.

(5) Determination of solid content

A glass rod and 10 g of dry anhydrous sodium sulfate were placed in a petri dish, and 2 g of the sample was weighed therein, mixed with a glass rod, and dried by a vacuum dryer (pressure: 8 kPa) at 105 ° C for 2 hours. The mass after drying was weighed, and the value obtained by the following formula was taken as the solid content component of the sample.

Solid content (% by mass) = [[mass after drying - (quality of culture dish + glass rod + anhydrous sodium sulfate)] / mass of sample] × 100

(6) Method for measuring viscosity

The viscosity of the fluorine compound was determined by the following conditions.

[condition]

Viscometer: E-type viscometer

Rotor: Conical, radius 24mm, angle 1° 34'

Number of revolutions: 100r/min

Measuring temperature: 25 ° C, Measurement time: 1min

Sample: 30% by mass PGMEA solution

Synthesis Example 1 Synthesis of Black Colorant

2,5-dihydroxybenzene-1,4-diacetic acid (Wako Pure Chemicals) in a 4-liter four-necked flask equipped with a stirring device, a thermometer, a nitrogen gas blowing tube, a Dean-Stark tube, and a Dyna tube Industrial Co., Ltd.) 150 g, blush (manufactured by Tokyo Chemical Industry Co., Ltd.) 150 g, 35 g of p-toluenesulfonic acid monohydrate, and 3,750 g of toluene were heated to 110 ° C, and stirred for 7 hours while dehydrating, and further superheated 10 hour. The mixture was cooled to room temperature. The black suspension was filtered using a filter paper No. 2 (Advantec Toyo Co., Ltd.). The filtrate residue was washed with 5 L of methanol, and dried at 60 ° C / 104 Pa to obtain 236 g of a black substance of the following formula (a).

The black substance was dissolved in dimethylformamide and subjected to ESI/MS (Electrospray Ionization/Mass Spectrometry) by liquid chromatography mass spectrometry to confirm the molecular weight of 448.07.

Production Example 1 (Preparation of Black Colorant Dispersion 1)

10.0 g of the black coloring material obtained in Synthesis Example 1 of the pigment, 0.25 g of pentaerythritol tetrakis(3-mercaptopropionate) as the compound (C), and "Solsperse J-200" manufactured by Lubrizol Co., Ltd., Japan as a dispersing agent 2.25g, propylene glycol monomethyl ether acetate (PGMEA) 37.5g, and 100 g of 0.3 mm zirconia particles ("YTZ ball" manufactured by NIKKATO) was placed in a 250 mL polyethylene container, and stirred for 3 hours by a paint shaker, and then the zirconium oxide particles were removed by filtration to obtain a black colorant dispersion 1.

Production Examples 2 to 12, Comparative Production Examples 1 to 6 (Preparation of Black Colorant Dispersions 2 to 18)

Black colorant dispersions 2 to 18 were obtained by the same method as in Production Example 1, except that the components described in Table 1 were replaced. Further, the compounds used for the preparation are as follows.

A-1: Black colorant obtained in Synthesis Example 1.

A-2: Carbon black, "Raven1060" manufactured by Columbian Carbon

A-3: aniline black, "No. 2 superblack" manufactured by Toda Industry Co., Ltd.

C-1: pentaerythritol tetrakis(3-mercaptopropionate)

C-2: tris(3-mercaptopropionic acid) trimethylolpropane

C-3: 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-three -2,4,6(1H,3H,5H)-trione

C-4: bis(2-mercaptoacetic acid) ethylene glycol ester

C-5: dipentaerythritol hexa(3-mercaptopropionate)

C-6: tris-[(3-mercaptopropoxy)-ethyl]-isocyanurate

Synthesis Example 2 [Synthesis of alkali-soluble resin (copolymer of benzyl methacrylate and methacrylic acid)]

Separable with a mixer, reflux condenser, nitrogen inlet tube and thermometer 3.6 g of methacrylic acid (hereinafter referred to as "MAA (methacrylic acid)") and benzyl methacrylate (hereinafter also referred to as "BZMA (benzyl methacrylate))) were added to the flask, 36.4 g, 3-mercaptopropyl propyl 0.56 g of acid and 40 g of PGMEA were replaced with nitrogen while stirring.

While stirring, the temperature inside the flask was raised to 78 ° C, and it took 3 hours to add dropwise MAA 14.4 g, BzMA 145.6 g, 3-mercaptopropionic acid 2.2 g, PGMEA 160 g, and 2,2'-azobis (2,4- Dimethyl valeronitrile (a mixture of "V-65" (hereinafter also referred to as "V-65")) manufactured by Wako Pure Chemical Industries Co., Ltd. (2.0 g), after the addition, V- 65 2.0 g mixed solution with PGMEA 10.0 g. After stirring at 78 ° C for 1 hour, a mixed solution of 1.0 g of V-65 and 10.0 g of PGMEA was added. Further, the mixture was stirred at 78 ° C for 1 hour, and 100 g of PGMEA was added thereto, followed by cooling 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 Transparent Corrosion Solution)

211.0 g of a copolymer 1 of a solid content of 40.0% by mass of the solid content obtained in Synthesis Example 2, 33.2 g of dipentaerythritol hexaacrylate (DPHA), and 256.6 g of PGMEA were uniformly mixed to obtain a transparent resist liquid.

Example 1 (Preparation of colored curable resin composition 1)

5.0 g of the black colorant dispersion 1 obtained in Production Example 1, 5.0 g of the transparent resist liquid obtained in Preparation Example 1, and 2.1 g of PGMEA were placed in a sample bottle, and after being fastened, a roll type mixer was used. The color-curable resin composition 1 having the composition shown in Table 2 was obtained by uniformly mixing for 20 minutes. Using the obtained color-curable resin composition, a coating film substrate was prepared by the above method, and various evaluations were performed. The results are shown in Table 2.

Examples 2 to 12 and Comparative Examples 1 to 6 (preparation of colored curable resin compositions 2 to 18)

The colored curable resin compositions 2 to 18 were obtained by the same method as in Example 1 except that the components were replaced by the components described in Table 2. Furthermore, for the preparation The composition is as follows. Using the obtained colored curable resin composition, a coating film substrate was produced by the above method, and various evaluations were performed. The results are shown in Table 2.

Fluorine compound (F)

F-1: "Surflon S-611" manufactured by AGC Qingmei Chemical Co., Ltd. (a non-ionic fluorine-based surfactant containing polyethylene glycol chain, viscosity*: 19.70 mPa‧s)

F-2: "Surflon S-651" manufactured by AGC Qingmei Chemical Co., Ltd. (a non-ionic fluorine-based surfactant containing polyethylene glycol chain, viscosity *: 3.61 mPa‧s)

F-3: "MEGAFAC RS-72-K" manufactured by DIC Corporation (30% by mass PGMEA solution containing a polyethylene glycol chain and a polymerizable nonionic fluorine-based oligomer, viscosity: 9.70 mPa‧s)

* The viscosity of F-1 and F-2 was measured by a 30% by mass solution of PGMEA.

[Industrial availability]

According to the colored curable resin composition of the present invention, a color filter including a black matrix excellent in electrical insulating properties, light blocking properties, and solvent resistance can be provided.

Claims (15)

A colored curable resin composition containing the compound (1) represented by the following formula (1), a polyfunctional polymerizable compound (B) having two or more ethylenically unsaturated bonds, and sulfur having three or more mercapto groups. The alcohol compound (C), the dispersing agent (D), and the organic solvent (E), wherein the content of the thiol compound (C) in the coloring curable resin composition is 1 part by mass or more based on 100 parts by mass of the compound (1). And 10 parts by mass or less, [In the above formula (1), X represents a double bond, and as a geometric isomer, each independently represents an E body or a Z body, and R ¹ independently represents a hydrogen atom, a methyl group, a nitro group, a methoxy group, a bromine atom, or a chlorine atom. An atom, a fluorine atom, a carboxyl group, or a sulfonic acid group, and R ² each independently represents a hydrogen atom, a methyl group, or a phenyl group, and R ³ each independently represents a hydrogen atom, a methyl group, or a chlorine atom]. The colored curable resin composition of claim 1, wherein the mass ratio of the thiol compound (C) to the polyfunctional polymerizable compound (B) in the colored curable resin composition is [(C)/(B)] 0.1 or more and 2 or less. The colored curable resin composition of claim 1 or 2, wherein the thiol compound (C) is an aliphatic thiol compound. The colored curable resin composition according to claim 1 or 2, wherein the thiol compound (C) has 4 or more and 6 or less sulfhydryl groups. The colored curable resin composition of claim 1 or 2, wherein the mercapto group in the thiol compound (C) is a primary mercapto group. The colored curable resin composition of claim 1 or 2, which further contains a fluorine compound (F). The colored curable resin composition of claim 6, wherein the fluorine compound (F) is at least one selected from the group consisting of a surfactant having a fluorocarbon chain, a fluorine-based oligomer, and a compound having a fluorocarbon chain and a polymerizable group. Kind. The colored curable resin composition of claim 6, wherein the fluorine compound (F) is a compound having a fluorocarbon chain and a polymerizable group. The colored curable resin composition of claim 6, wherein the content of the fluorine compound (F) based on 100 parts by mass of the compound (1) is 0.2 parts by mass or more and 10 parts by mass or less. The colored curable resin composition according to claim 1 or 2, wherein R ¹ , R ² and R ³ of the compound (1) are a hydrogen atom. The colored curable resin composition of claim 1 or 2, which is used for forming a black matrix of a color filter. A color filter comprising a black matrix formed using the color hardening resin composition according to any one of claims 1 to 11. A method for producing a color-curable resin composition, comprising the following steps 1 and 2: Step 1: a compound (1) represented by the following formula (1), a thiol compound having three or more mercapto groups (C) a step of mixing and dispersing the dispersing agent (D) and the organic solvent (E) to obtain a dispersion; and Step 2: dispersing the above-mentioned dispersion and a polyfunctional polymerizable compound having two or more ethylenically unsaturated bonds (B) Mixing step [In the above formula (1), X represents a double bond, and as a geometric isomer, each independently represents an E body or a Z body, and R ¹ independently represents a hydrogen atom, a methyl group, a nitro group, a methoxy group, a bromine atom, or a chlorine atom. An atom, a fluorine atom, a carboxyl group, or a sulfonic acid group, and R ² each independently represents a hydrogen atom, a methyl group, or a phenyl group, and R ³ each independently represents a hydrogen atom, a methyl group, or a chlorine atom]. The use of the colored curable resin composition according to any one of claims 1 to 10, which is a black matrix for producing a color filter. Use of the colored curable resin composition according to any one of claims 1 to 10 for producing a color filter.