WO2015016294A1

WO2015016294A1 - Colored curable resin composition

Info

Publication number: WO2015016294A1
Application number: PCT/JP2014/070153
Authority: WO
Inventors: 史博高沢; 昭人井樋
Original assignee: 花王株式会社
Priority date: 2013-07-31
Filing date: 2014-07-31
Publication date: 2015-02-05
Also published as: JPWO2015016294A1; JP6471092B2; CN105431777A; TWI634161B; TW201512312A; KR20160039183A

Abstract

　The present invention addresses the problem of providing a colored curable resin composition for manufacturing a black matrix having exceptional electrical insulation properties, light shielding properties, and solvent resistance, as well as a color filter provided with the black matrix formed using the same, and a method for manufacturing the colored curable resin composition. [1] A colored curable resin composition containing a compound (1) represented by formula (1), a polyfunctional polymerizable compound (B) having two or more unsaturated ethylene bonds, a thiol compound (C) having three or more mercapto groups, a dispersant (D), and an organic solvent (E); [2] a color filter provided with a black matrix formed by using the colored curable resin composition in [1]; and a method for manufacturing the colored curable resin composition, the method having a step 1 and a step 2 as below. Step 1: A step for obtaining a dispersion by mixing and dispersing the compound (1) represented by formula (1), the thiol compound (C) having three or more mercapto groups, the dispersant (D), and the organic solvent (E). Step 2: A step for mixing the dispersion and the polyfunctional polymerizable compound (B) having two or more unsaturated ethylene bonds.

Description

Colored curable resin composition

The present invention relates to a color curable resin composition used for producing a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like, a color filter including a black matrix formed using the same, and a color The present invention relates to a method for producing a curable resin composition.

A grid-like black pattern called a black matrix (hereinafter also referred to as “BM”) having a light shielding property is formed in the gaps between the red, green, and blue filter segments of the color filter for the purpose of improving contrast. It is common.
The BM is required to have excellent light shielding properties in order to improve the image quality of the liquid crystal display. In particular, in order to cope with higher definition and higher brightness in recent years, a BM is formed on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device from a conventional method of forming a BM on a color filter substrate. The BOA (Black Matrix on Array) method has been studied. This BOA method eliminates the need for a pasting process for aligning with the element, greatly increases the pixel aperture ratio (aperture ratio), and shortens the manufacturing process. Since 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, when a BM is to be formed on the array substrate side, the BM itself is in direct contact with the liquid crystal. Therefore, if the insulation of the BM itself is low, a display failure of the liquid crystal display is caused.
Moreover, since the mask alignment performed at the time of BM formation is performed using an infrared camera, a certain level of light transmittance in the near infrared region is also required. Therefore, carbon black, which has been mainly used as a conventional BM material, not only exhibits a high dielectric constant and poor insulation, but also has a low light transmittance in the near-infrared region, making alignment difficult. It is difficult to use for a BOA type liquid crystal panel.
As a method for solving such a problem, a method of providing light shielding properties with a specific organic pigment (see Patent Document 1) is disclosed.

Special table 2012-515233

That is, the present invention relates to the following [1] to [3].
[1] Compound (1) represented by the following formula (1), polyfunctional polymerizable compound (B) having two or more ethylenically unsaturated bonds, and thiol compound (C) having three or more mercapto groups And a colored curable resin composition containing a dispersant (D) and an organic solvent (E).

[In the above formula (1), X represents a double bond, and each independently represents an E-form or a Z-form as a geometric isomer, and each R ¹ independently represents a hydrogen atom, a methyl group, a nitro group, or a methoxy group. , a bromine atom, a chlorine atom, a fluorine atom, a carboxy group, or a sulfonic acid group, R ² each independently represent a hydrogen atom, a methyl group, or a phenyl group, R ³ each independently represents a hydrogen atom Represents 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 colored curable resin composition, comprising the following step 1 and step 2.
Step 1: A compound (1) represented by the formula (1), a thiol compound (C) having three or more mercapto groups, a dispersant (D) and an organic solvent (E) are mixed and dispersed to obtain a dispersion. Step of obtaining Step 2: Step of mixing the dispersion and a polyfunctional polymerizable compound (B) having two or more ethylenically unsaturated bonds

In addition, since BM is immersed in a solvent such as N-methyl-2-pyrrolidone (hereinafter, also simply referred to as “NMP”) that dissolves the polyimide precursor at the time of polyimide film formation, BM is required to have solvent resistance. 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 having excellent light shielding properties, insulating properties, and solvent resistance. The present invention relates to a colored curable resin composition for producing a black matrix having excellent electrical insulation properties, light shielding properties, and solvent resistance, a color filter including a black matrix formed using the same, and colored curing An object is to provide a method for producing a conductive resin composition.

The present inventors use a composition containing a compound (1) represented by the following formula (1) as a black color material, a specific polyfunctional polymerizable compound, and a thiol compound having three or more mercapto groups. Thus, it was found that a colored curable resin composition having high electrical insulation, excellent light shielding properties, and good solvent resistance can be obtained.

[Indicate the above formula (1), X double bond, E-isomer or Z isomer independently as geometric isomers, R ¹ is each independently a hydrogen atom, a methyl group, a nitro group, a methoxy group , A bromine atom, a chlorine atom, a fluorine atom, a carboxy group, or a 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. Represents 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 colored curable resin composition, comprising the following step 1 and step 2.
Step 1: A compound (1) represented by the formula (1), a thiol compound (C) having three or more mercapto groups, a dispersant (D) and an organic solvent (E) are mixed and dispersed to obtain a dispersion. Step of obtaining Step 2: Step of mixing the dispersion and a polyfunctional polymerizable compound (B) having two or more ethylenically unsaturated bonds

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

The colored curable resin composition of the present invention includes 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 simply referred to as “component (B)”), thiol compound (C) having 3 or more mercapto groups (hereinafter also simply referred to as “component (C)”), and dispersant (D) (hereinafter referred to as “component (B)”). And an organic solvent (E) (hereinafter also simply referred to as “(E) component”).

According to the present invention, it is possible to obtain a colored curable resin composition capable of producing a black matrix having excellent electrical insulation and light shielding properties and excellent solvent resistance. The reason why such an effect is obtained is not clear, but is considered as follows.
By selecting the compound (1) as the black color material, excellent electrical insulation and light shielding properties can be obtained. On the other hand, it tends to be inferior in solvent resistance by using the black color material, but by using a specific component (B) and a specific component (C) in combination, the electrical insulation and light shielding properties described above are used. High solvent resistance can be obtained while maintaining First, the (C) component is unevenly distributed in the vicinity of the surface of the compound (1) due to the interaction between the mercapto group of the thiol compound of the (C) component and the lactam moiety of the compound (1). And since (C) component has three or more mercapto groups, (C) component itself is efficient as a crosslinking agent, promoting polymerization, accompanied by ene-thiol reaction and chain transfer reaction with (B) component. It functions well and improves the crosslink density near the surface of compound (1). Therefore, it is presumed that good curing characteristics are obtained and the solvent resistance is excellent. However, these are estimations, and the present invention is not limited to these mechanisms.

[Compound (1) / Black color material (A)]
The composition of this invention contains the compound (1) represented by Formula (1) from an electrical insulating property and a light-shielding viewpoint.

In the above formula (1), X represents a double bond, and each independently represents an E isomer or a Z isomer as a geometric isomer, and each R ¹ independently represents a hydrogen atom (—H), a methyl group (—CH ₃ ), nitro group (—NO ₂ group), methoxy group (—OCH ₃ ), bromine atom (—Br), chlorine atom (—Cl), fluorine atom (—F), carboxy group (—COOH), or sulfone Represents an acid group (—SO ₃ H), 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. . 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. Said compound can be used individually or in combination of 2 or more types.
R ^1, R ^2, and R ³ of the compound (1) is preferably a hydrogen atom.
The said compound (1) can be manufactured by the method described in international publication WO2000 / 24736, international publication WO2010 / 081624, for example.

The composition of the present invention may contain a black color material other than the compound (1) as long as the effects of the present invention are not impaired. Examples of other black color materials include carbon black and titanium black.
In the present specification, the compound (1) and other black color materials are collectively referred to simply as “black color material (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 still more preferably 100% by mass.
Further, from the viewpoint of enhancing the affinity between the black color material and the organic solvent, and improving the dispersibility and storage stability, the surface of the compound (1) is previously coated with a resin, a polymer, a derivative of the compound (1), or the like. A black color material that has been treated can also be used.

[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.
A polyfunctional (meth) acrylate compound is preferably used as the polyfunctional polymerizable compound.
The number of ethylenically unsaturated bonds contained in one molecule of the polyfunctional polymerizable compound is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, from the viewpoint of solvent resistance. , Preferably 8 or less, more preferably 7 or less, and even 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, diglycidyl phthalate 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, condensates of dimethylene ether bis (meth) acrylamide 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 (Hereinafter also referred to as “DPHA”), and more preferably DPHA.
In the present specification, “(meth) acrylate” means at least one selected from acrylate and methacrylate. “(Meth) acrylamide” means at least one selected from acrylamide and methacrylamide.

[Thiol Compound (C)]
The thiol compound used in the present invention has three or more mercapto groups from the viewpoint of solvent resistance. When the number of mercapto groups is less than 3, the crosslink density becomes low, so that the colored curable resin composition after curing is swollen by a solvent (for example, N-methyl-2-pyrololidone (hereinafter also referred to as “NMP”)) The elution of the coloring material cannot be suppressed.

From the viewpoint of solvent resistance, the number of mercapto groups in one molecule of the thiol compound is 3 or more, preferably 4 or more, and from the same viewpoint, preferably 9 or less, more preferably It is 8 or less, more preferably 7 or less, even more preferably 6 or less, even more preferably 5 or less, even more preferably 4 or less, and even more preferably 4.
Examples of the thiol compound include an aliphatic thiol compound, a thiol compound having a cyclic structure such as a heterocyclic ring or an aromatic ring. From the viewpoint of solvent resistance and ease of designing the number of mercapto groups of the thiol compound, the aliphatic thiol compound Is preferred.
Examples of the mercapto group in the thiol compound include primary, secondary and tertiary mercapto groups. From the viewpoint of solvent resistance, preferably one or more selected from primary mercapto groups and secondary mercapto groups, and more. A primary mercapto group is preferred.
Further, from the viewpoint of solvent resistance, the thiol compound preferably has a structure derived from mercaptocarboxylic acid, 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, 1,2,3-tris (3-mercaptopropyl). Thio) propane, trimethylolpropane tris (2-mercaptoacetate), glycerin tris (2-mercaptoacetate), pentaerythritol tetrakis (2-mercaptoacetate), dipentaerythritol pentakis (2-mercaptoacetate), Dipentaerythritol hexakis (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercapto) Ropioneto), trimethylolpropane tris (3-mercapto butyrate), pentaerythritol tetrakis (3-mercapto butyrate), dipentaerythritol hexakis (3-mercapto butyrate), and the like.
Examples of the thiol compound having a heterocyclic ring include tris [(3-mercaptopropionyloxy) -ethyl] isocyanurate, tris [(3-mercaptobutyryloxy) -ethyl] isocyanurate (1,3,5-tris (3 -Mercaptobutyryloxyethyl) -1,3,5-triasian-2,4,6 (1H, 3H, 5H) -trione), tris [(3-mercaptopropionyloxy) -methyl] isocyanurate It is done.
Examples of thiol compounds having an aromatic ring include 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl). Benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,3,5-tris (mercapto) And ethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, and 1,2,3,4-tetramercaptobenzene.

Among the above thiol compounds, preferably pentaerythritol tetrakis (3-mercaptopropionate), tris (3-mercaptopropionic acid) trimethylolpropane, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1 , 3,5-triasian-2,4,6 (1H, 3H, 5H) -trione, dipentaerythritol hexakis (3-mercaptopropionate) and tris-[(3-mercaptopropionyloxy) -ethyl] -At least one selected from isocyanurates, more preferably at least one selected from pentaerythritol tetrakis (3-mercaptopropionate) and dipentaerythritol hexakis (3-mercaptopropionate), More preferably pentaerythrito A Rutetorakisu (3-mercaptopropionate).

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

Commercially available dispersants include, for example, Dispersbyk-161, 166, 167 manufactured by Big Chemie Japan, Solsperse 55000, 76500 manufactured by Nippon Lubrizol, etc .; Dispersbyk-106, 110, 111 as polycarboxylic acids , Solsperse 36000, 41000, EFKA-5060 manufactured by BASF Japan, etc .; Disperbyk-116, 130, Solsperse 24000, 32000, 33000, J200, EFKA-4046, Ajimoto Fine Techno Co., Ajisper PB821, PB822 , PB824, PB881, and the like. Among these, polyamines are preferable from the viewpoint of dispersibility, and EFKA-4046 and Solsperse J200 are more preferable.

[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; aliphatic hydrocarbons such as cyclohexane; propylene glycol and the like In addition to ethers such as ethylene glycol diethyl ether, ethyl acetate, silicone oil, higher alcohols, fats and the like, and a compound represented by the following formula (2) are exemplified.

[Wherein, R ⁴ and R ⁵ each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms, in which hydrogen may be substituted with an alkoxy group having 1 to 3 carbon atoms, R ⁶ represents a hydrogen atom or a methyl group, and n represents an integer of 0 to 3. ]

In the formula (2), the alkyl group having 1 to 4 carbon atoms of R ⁴ and R ⁵ includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 3-methoxybutyl group, and an isobutyl group. , Sec-butyl group, and tert-butyl group. In these, a methyl group and an ethyl group are preferable.
n is preferably 1 or 2.
Examples of the organic solvent include ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (hereinafter also referred to as “PGMEA”), diethylene glycol monobutyl ether acetate from the viewpoints of dispersibility of the colorant and solubility or dispersibility of the dispersant. More preferred is at least one selected from the group consisting of 3-methoxybutyl acetate and propylene glycol monoethyl ether acetate.
Said organic solvent can be used individually or in combination of 2 or more types.

[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. In the process of forming a coating film using a colored curable resin composition, drying and curing, the fluorine compound bleeds out to the surface of the BM and reduces the infiltration of the solvent into the BM, thereby elution of the black color material. It is thought to further suppress.
By using a fluorine compound in combination with a thiol compound, a synergistic effect can be exhibited and remarkable solvent resistance can be obtained. A hydrogen bond is formed between the mercapto group of the thiol compound that is unevenly distributed near the surface of the compound (1) and the fluoro group of the fluorine compound, whereby the fluorine compound is also unevenly distributed near the pigment surface and is insoluble in the pigment surface. It is thought that the solvent resistance is improved by forming a film.

Examples of the fluorine compound include at least one selected from a surfactant having a fluorocarbon chain, a fluorine-based oligomer, and a compound having a fluorocarbon chain and a polymerizable group.
As surfactants having a fluorocarbon chain, commercially available products such as Fluorinert FC430 and FC431 manufactured by Sumitomo 3M Limited, MegaFac manufactured by DIC Corporation F142D, F171, F172, F173, F177, F183, F554, R30, Mitsubishi Materials EFTOP EF301, EF303, EF351, EF352 manufactured by Denka Kasei Co., Ltd., Surflon S-381, S-382, SC-101, SC-105 manufactured by AGC Seimi Chemical Co., E5844 manufactured by Daikin Fine Chemical Laboratory Co., Ltd. Is mentioned.
Examples of the fluorine-based oligomer include Surflon S-611 and S-651 manufactured by AGC Seimi Chemical Co., Ltd. as commercially available products.
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 the penetration of the solvent into the coating film, it is preferable that the solubility of the fluorine compound in 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 cured at the same time as the component (B) by the reactive group, and further, the reaction with the component (C) causes a polymerization reaction near the surface of the compound (1) to further improve the solvent resistance and insulation. From the viewpoint, a compound having a fluorocarbon chain and a polymerizable group is preferable.
In addition, the fluorine compound having a reactive group is involved in the ene-thiol reaction and chain transfer polymerization generated from the thiol group as a starting point, and forms a covalent bond with the thiol compound in addition to the hydrogen bond. It is considered that the solvent resistance is further improved.

Of the fluorinated 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 preferable, and a compound having a fluorocarbon chain, an ethylenically unsaturated bond, and a polyethylene glycol chain is more preferable. As commercially available products, preferably MegaFac RS-72-K, RS-75, and RS-76-E are mentioned.
The fluorine compound used in the present invention may be one type or a mixture of two or more types.

The viscosity at 25 ° C. of the 30% by mass PGMEA solution of the fluorine compound is preferably 24 mPa · s or less, more preferably 18 mPa · s or less, and still more preferably 12 mPa · s, from the viewpoint of forming a uniform solvent-resistant film on the pigment surface. s or less, preferably 0.1 mPa · s or more, more preferably 1 mPa · s or more, and further preferably 3 mPa · s or more.
The viscosity is a viscosity measured by an E-type viscometer, and can be specifically 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 photoinitiation assistant, an alkali-soluble resin, and the like.

As the photopolymerization initiator, a known polymerization initiator can be used. For example, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2,2-dimethoxy-1 , 2-diphenylethane-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 -Phenylacetoxyethoxy] ethyl ester and 2- (2-hydroxyethoxy) ethyl ester, phenylglycosyl , Benzophenone, and the like are preferable. As a commercially available photopolymerization initiator, for example, IRGACURE 369, 907, 651, 2959, 184, 250, 754; DAROCUR MBF, BP, 1173 (manufactured by BASF Japan) and the like are preferable. These photopolymerization initiators can be used alone or in combination of two or more.

Moreover, you may combine a photoinitiator adjuvant with this photoinitiator.
Examples of the photoinitiator include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoic acid. 2-ethylhexyl, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 9,10-dimethoxyanthracene, Examples include 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. These photoinitiation assistants can be used alone or in combination of two or more.

The alkali-soluble resin is used for dissolving an unexposed portion in a developer when a color filter is produced by a photolithography method. As the alkali-soluble resin, those generally used for negative resists can be used, and those having solubility in an alkaline aqueous solution, that is, 1% by mass in a 0.05% by mass tetramethylammonium hydroxide aqueous solution at 20 ° C. There is no particular limitation 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 Examples include at least one selected from benzyl (meth) acrylate. 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 a copolymer is more preferable.
The copolymerization ratio (molar ratio) of acrylic acid ester and (meth) acrylic acid is preferably 90/10 to 50/50, and more preferably 80/20 to 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. “(Meth) acrylate” means at least one selected from acrylate and methacrylate.

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, and preferably 40% by mass or less, more preferably 30%. It is at most 25% by mass, more preferably at most 25% by mass.
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 further preferably 8% by mass or more from the viewpoint of obtaining good light shielding 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, more preferably 25% by mass or more, and further preferably from the solid content in the colored curable resin composition from the viewpoint of obtaining good light-shielding properties. From the viewpoint of obtaining good solvent resistance, it is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass or less.
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, and still more preferably 8% by mass or more, from the viewpoint of obtaining good light shielding properties. From the viewpoint of obtaining good solvent resistance, it is preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less.
The content of the black color material (A) is preferably 20% by mass or more, more preferably 25% by mass or more, more preferably 25% by mass or more, based on the solid content in the colored curable resin composition, from the viewpoint of obtaining good light shielding properties. Preferably, it is 40% by mass or more, and from the viewpoint of obtaining good solvent resistance, it is preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 60% by mass or less.

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, further from the viewpoint of obtaining good film hardness. Preferably it is 0.7 mass% or more, Preferably it is 10 mass% or less, More preferably, it is 5 mass% or less, More preferably, it is 3 mass% or less.
From the viewpoint of obtaining good film hardness, the content of the polyfunctional polymerizable compound (B) is preferably 1.0% by mass or more, more preferably 2.% by weight, based on the solid content in the colored curable resin composition. It is 0 mass% or more, More preferably, it is 3.0 mass% or more, Preferably it is 30 mass% or less, More preferably, it is 20 mass% or less, More preferably, it is 15 mass% or less.

From the viewpoint of solvent resistance, the content of the thiol compound (C) in the colored 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%. From the viewpoint of light shielding properties, it is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, still more preferably 1% by mass or less, and still more preferably 0.00%. It is 7 mass% or less, More preferably, it is 0.5 mass% or less, More preferably, it is 0.4 mass% or less.
From the viewpoint of solvent resistance, 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 based on the solid content in the colored curable resin composition. Is 1.5% by mass or more, and from the viewpoint of light shielding properties, it is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, still more preferably 5% by mass or less, Preferably it is 3 mass% or less, More preferably, it is 2 mass% or less.
The content of the thiol compound (C) with respect to 100 parts by mass of the compound (1) in the colored curable composition is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and still more preferably from the viewpoint of solvent resistance. From the viewpoint of light shielding properties, it is 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 further preferably 4 parts by mass or less.
The mass ratio [(C) / (B)] of the thiol compound (C) to the polyfunctional polymerizable compound (B) in the colored curable resin composition is preferably 0.05 or more from the viewpoint of solvent resistance. More preferably 0.07 or more, still more preferably 0.1 or more, still more preferably 0.2 or more, and preferably 1 or less, more preferably 0.7 or less, still more preferably 0.5 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, more preferably from the viewpoint of good light shielding properties and solvent resistance. Preferably, it is 1% by mass or more, and from the same viewpoint, it is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less.
The content of the dispersant (D) is preferably 0.5% by mass or more, more preferably 2. 5% by mass, based on the solid content in the colored curable resin composition, from the viewpoints of good light shielding properties and solvent resistance. From the same viewpoint, it is preferably 40% by mass or less, more preferably 30% by mass or less, and further 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 further preferably 75% by mass or more, from the viewpoint of good light shielding properties. Moreover, it is preferably 95% by mass or less, more preferably 90% by mass or less, and still 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, more preferably from the viewpoint of good insulation and solvent resistance. Preferably it is 0.08 mass% or more, Preferably it is 5 mass% or less, More preferably, it is 2 mass% or less, More preferably, it is 1 mass% or less, More preferably, it is 0.5 mass% or less.
The content of the fluorine compound (F) is preferably 0.2% by mass or more, and more preferably 0.2% by mass or more with respect to the solid content in the colored curable resin composition, from the viewpoint of good insulation and solvent resistance. 6 mass% or more, more preferably 1.2 mass% or more, preferably 10 mass% or less, more preferably 5 mass% or less, still more preferably 3 mass% or less, and even more preferably 1.6 mass%. % Or less.
The content of the fluorine compound (F) with respect to 100 parts by mass of the compound (1) in the colored curable composition is preferably 0.2 parts by mass or more, more preferably 0.6 from the viewpoints of solvent resistance and insulation. It is preferably not less than 1.2 parts by mass, more preferably not less than 1.2 parts by mass, and even more preferably not less than 2.5 parts by mass. From the viewpoint of easy production of the color filter, it is preferably not more than 10 parts by mass, more preferably 5 parts by mass. Part or less, more preferably 3.5 parts by weight 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 0.05 or more from the viewpoint of solvent resistance and insulation. More preferably, it is 0.07 or more, more preferably 0.1 or more, and 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. is there.

The content of the alkali-soluble resin is preferably 5.0% by mass or more, 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 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. As mentioned above, More preferably, it is 10 mass parts or more, More preferably, it is 20 mass parts or more, Preferably it is 70 mass parts or less, More preferably, it is 60 mass parts or less, More preferably, it is 50 mass parts 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 hardening failure can be suppressed.
The content of the photopolymerization initiation assistant 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 good film hardness. Part or more, more preferably 3 parts by weight or more, still more preferably 5 parts by weight or more, and preferably 30 parts by weight or less, more preferably 20 parts by weight or less, still more preferably 15 parts by weight 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 hardening failure 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 1 and process 2.
Step 1: A compound (1) represented by the formula (1), a thiol compound (C) having three or more mercapto groups, a dispersant (D) and an organic solvent (E) are mixed and dispersed to obtain a dispersion. Step of obtaining Step 2: Step of mixing the dispersion and a polyfunctional polymerizable compound (B) having two or more ethylenically unsaturated bonds

Various known dispersers can be used as the mixing disperser used in the dispersion in Step 1 above. Examples thereof include high-speed stirring and mixing devices such as homomixers, kneaders such as roll mills, kneaders and extruders, high-pressure dispersers such as high-pressure homogenizers, media-type dispersers such as paint shakers and bead mills. These devices can be used in combination.
Among these, from the viewpoint of uniformly mixing the black color material in the organic solvent, a high-speed stirring and mixing device such as a homomixer, and a media type dispersing machine such as a paint shaker or a bead mill are preferable. Commercially available media type dispersers include “Ultra Apex Mill” manufactured by Kotobuki Industries Co., Ltd., “Picomill” manufactured by Asada Tekko Co., Ltd., and the like.
In the case of using a media type disperser, the material of the media used in the dispersion step is preferably a ceramic material such as zirconia or titania, a polymer material such as polyethylene or nylon, a metal, or the like, and zirconia is preferred from the viewpoint of wear. Further, the diameter of the media is preferably 0.003 mm or more, more preferably 0.01 mm or more, and preferably 0.5 mm or less, more preferably, from the viewpoint of crushing the aggregated particles in the black color material. Is 0.4 mm or less.
The dispersion time is preferably 0.3 hours or more from the viewpoint of sufficiently miniaturizing the black color material, more preferably 1 hour or more, and preferably 50 hours or less from the viewpoint of the production efficiency of the pigment dispersion. Less than the time is more preferable.

Although there is no restriction | limiting in particular in the mixing method of the process 2, For example, it can obtain by stirring with a roller type stirrer. The stirring time is preferably 5 minutes or longer, more preferably 15 minutes or longer, from the viewpoint of production efficiency, preferably 10 hours or shorter, more preferably 1 hour or shorter.
The preferable blending amount of each component in the method for producing the colored curable resin composition is such that the finally obtained colored curable resin composition is a preferable content of each component in the composition shown above. is there.

[Color filter]
The colored curable resin composition of the present invention is preferably used for producing a color filter, and more specifically, preferably used for producing a black matrix of a color filter.
The manufacturing method of the color filter which comprises the black matrix formed 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 forming a black matrix comprising a cured film by heating the coating film obtained in the step (a) to 200 to 300 ° C., and on the cured film It is preferable to have a step (c) of applying a resin organic solvent solution to form a resin film.

After the application of the step (a), it is preferable to dry the organic solvent and to heat or reduce the pressure from the viewpoint of the smoothness and productivity of the coating film.
In the photocuring, for example, the coating film is irradiated with ultraviolet rays, and the polyfunctional monomer in the colored curable resin composition undergoes a crosslinking reaction to cure the coating film. Photocuring is performed to leave a pattern on the glass substrate in the subsequent development, and it is preferable not to cure the portion removed by development by placing a photomask for preventing ultraviolet rays.
In the above development, for example, the photocured cured coating film is immersed in an alkaline aqueous solution and further rinsed with water to remove uncured portions.
Step (b) is a post-baking step, and by performing this step, a cured film having excellent hardness can be formed.
The resin in step (c) is, for example, polyimide. The organic solvent in step (c) is, for example, N-methyl-2-pyrrolidone.

In relation to the above-described embodiment, the present invention further discloses the following colored curable resin composition, color filter, and production methods thereof.

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

[In the above formula (1), X represents a double bond, and each independently represents an E-form or a Z-form as a geometric isomer, and each R ¹ independently represents a hydrogen atom, a methyl group, a nitro group, or a methoxy group. , A bromine atom, a chlorine atom, a fluorine atom, a carboxy group, or a 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. Represents 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 hydrogen atoms.
<3> The content of the compound (1) in the black color material is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 100% by mass, described in <1> or <2>. Colored curable resin composition.
<4> The number of ethylenically unsaturated bonds contained in the polyfunctional polymerizable compound (B) is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, and preferably The colored curable resin composition according to any one of <1> to <3>, which is 8 or less, more preferably 7 or less, and still more preferably 6 or less.
<5> The polyfunctional polymerizable compound (B) is preferably trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and The colored curable resin composition according to any one of <1> to <4>, which is at least one selected from dipentaerythritol hexa (meth) acrylate, more preferably dipentaerythritol hexa (meth) acrylate. .

<6> The number of mercapto groups in the thiol compound (C) is 3 or more, preferably 4 or more, preferably 9 or less, more preferably 8 or less, and even more preferably 7 Any one of <1> to <5>, more preferably 6 or less, even more preferably 5 or less, even more preferably 4 or less, and even more preferably 4 or less. The colored curable resin composition described in 1.
<7> 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 coloring according to any one of <1> to <7>, wherein the thiol compound (C) preferably has a structure derived from mercaptocarboxylic acid, more preferably a structure derived from β-mercaptocarboxylic acid. Curable resin composition.
<9> The mercapto group in the thiol compound is preferably one or more selected from primary mercapto groups and secondary mercapto groups, more preferably primary mercapto groups, and any one of <1> to <8> The colored curable resin composition as described.
<10> The thiol compound (C) is preferably pentaerythritol tetrakis (3-mercaptopropionate), tris (3-mercaptopropionic acid) trimethylolpropane, 1,3,5-tris (3-mercaptobutyryloxy) Ethyl) -1,3,5-triasian-2,4,6 (1H, 3H, 5H) -trione, dipentaerythritol hexakis (3-mercaptopropionate) and tris-[(3-mercaptopropionyloxy ) -Ethyl] -isocyanurate, more preferably at least one selected from pentaerythritol tetrakis (3-mercaptopropionate) and dipentaerythritol hexakis (3-mercaptopropionate). Seed, more preferably pentaerythri A Rutetorakisu (3-mercaptopropionate), <1> to colored curable resin composition according to any one of <9>.

<11> The dispersant (D) preferably has a poly (meth) acrylate, polylactone, polyalkylene oxide or the like as a main chain or a side chain, polyurethane-based, polyamide-based, polyimide-based, poly (meth) acrylic acid, A polycarboxylic acid-based dispersant such as poly (anhydride) maleic acid, a polyamine-based dispersant, and a dispersant into which a quaternary ammonium salt or the like is introduced, and more preferably a polyamine-based dispersant, < The colored curable resin composition according to any one of 1> to <10>.
<12> The organic solvent (E) is preferably selected from the group consisting of ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (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 <11>, which is at least one selected.
<13> The colored curable resin composition according to any one of <1> to <12>, preferably further containing a fluorine compound (F).
<14> The fluorine compound (F) is preferably at least one selected from a surfactant having a fluorocarbon chain, a fluorine-based oligomer, and a compound having a fluorocarbon chain and a polymerizable group, more preferably a fluorocarbon chain and It is a compound having a polymerizable group, more preferably a compound having a fluorocarbon chain and an ethylenically unsaturated bond, and still more preferably a compound having a fluorocarbon chain, an ethylenically unsaturated bond, and a polyethylene glycol chain. The colored curable resin composition according to 13>.
<15> The viscosity at 25 ° C. of the 30% by mass PGMEA solution of the fluorine compound (F) is preferably 24 mPa · s or less, more preferably 18 mPa · s or less, still more preferably 12 mPa · s or less, and preferably The colored curable resin composition according to <13> or <14>, which is 0.1 mPa · s or more, more preferably 1 mPa · s or more, and further preferably 3 mPa · s or more.
<16> The colored curable resin composition according to any one of <1> to <15>, preferably further containing a photopolymerization initiator.
<17> The colored curable composition according to <16>, preferably further containing a photoinitiation aid.
<18> The colored curable resin composition according to any one of <1> to <17>, preferably further containing an alkali-soluble resin.

<19> 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, and preferably 40% by mass or less. The colored curable resin composition according to any one of <1> to <18>, preferably 30% by mass or less, more preferably 25% by mass or less.
<20> 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, still more preferably 8% by mass or more, and preferably 30%. The colored curable resin composition according to any one of <1> to <19>, which is not more than mass%, more preferably not more than 20 mass%, still more preferably not more than 15 mass%.
<21> The content of the compound (1) is preferably 20% by mass or more, more preferably 25% by mass or more, and further preferably 40% by mass or more with respect to the solid content in the colored curable resin composition. The colored curable resin composition according to any one of <1> to <20>, which is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass or less.
<22> 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, and still more preferably 8% by mass or more. The colored curable resin composition according to any one of <1> to <21>, wherein is 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.
<23> The content of the black color material (A) is preferably 20% by mass or more, more preferably 25% by mass or more, and further preferably 40% by mass or more, based on the solid content in the colored curable resin composition. The colored curable resin composition according to any one of <1> to <22>, which is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass or less.
<24> 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 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, and the colored curable resin composition according to any one of <1> to <23> object.
<25> The content of the polyfunctional polymerizable compound (B) is preferably 1.0% by mass or more, more preferably 2.0% by mass or more, further based on the solid content in the colored curable resin composition. Preferably, the content is 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, according to any one of <1> to <24>. Colored curable resin composition.
<26> The content of the thiol compound (C) in the colored curable resin composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and further preferably 0.3% by mass or more. And preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, still more preferably 1% by mass or less, still more preferably 0.7% by mass or less, still more preferably 0.8% by mass. The colored curable resin composition according to any one of <1> to <25>, which is 5% by mass or less, more preferably 0.4% by mass or less.
<27> 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 with respect to the solid content in the colored curable resin composition. More preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, still more preferably 5% by mass or less, still more preferably 3% by mass or less, still more preferably. The colored curable resin composition according to any one of <1> to <26>, which is 2% by mass or less.
<28> The content of the thiol compound (C) with respect to 100 parts by mass of the compound (1) in the colored curable composition is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and further preferably 3 parts by mass or more. Preferably, it is 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 parts by mass or less, according to any one of <1> to <27>. Colored curable resin composition.
<29> The mass ratio [(C) / (B)] of the thiol compound (C) to the polyfunctional polymerizable compound (B) in the colored curable resin composition is preferably 0.05 or more, more preferably 0. 0.07 or more, more preferably 0.1 or more, even more preferably 0.2 or more, and preferably 1 or less, more preferably 0.7 or less, and even more preferably 0.5 or less, <1 > The colored curable resin composition according to any one of <28>.
<30> 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, and further preferably 1% by mass or more. The colored curable resin composition according to any one of <1> to <29>, which is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less.
<31> The content of the dispersant (D) is preferably 0.5% by mass or more, more preferably 2.5% by mass or more, and still more preferably 5% with respect to the solid content in the colored curable resin composition. The colored curable resin according to any one of <1> to <30>, which is not less than 40% by weight, preferably not more than 40% by weight, more preferably not more than 30% by weight, and still more preferably not more than 20% by weight. Composition.
<32> 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, still more preferably 75% by mass or more, and preferably The colored curable resin composition according to any one of <1> to <31>, which is 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less.
<33> 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 0.08% by mass or more. Any one of <1> to <32>, preferably 5% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and still more preferably 0.5% by mass or less. The colored curable resin composition described in 1.
<34> The content of the fluorine compound (F) is preferably 0.2% by mass or more, more preferably 0.6% by mass or more, and still more preferably 1% with respect to the solid content in the colored curable resin composition. 2 mass% or more, preferably 10 mass% or less, more preferably 5 mass% or less, still more preferably 3 mass% or less, still more preferably 1.6 mass% or less, <1> to The colored curable resin composition according to any one of <33>.
<35> The content of the fluorine compound (F) with respect to 100 parts by mass of the compound (1) in the colored curable composition is preferably 0.2 parts by mass or more, more preferably 0.6 parts by mass or more, and still more preferably. 1.2 parts by mass or more, still more preferably 2.5 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3.5 parts by mass or less. The colored curable resin composition according to any one of 1> to <34>.
<36> The mass ratio [(F) / (C)] of the fluorine compound (F) to the thiol compound (C) in the colored curable resin composition is preferably 0.05 or more, more preferably 0.07 or more. The coloring according to any one of <1> to <35>, more preferably 0.1 or more, and preferably 1 or less, more preferably 0.8 or less, and still more preferably 0.7 or less. Curable resin composition.
<37> The content of the alkali-soluble resin is preferably 5.0% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, based on the solid content in the colored curable resin composition. The colored curable resin composition according to any one of <1> to <36>, which is preferably 50% by mass or less, more preferably 40% by mass or less, and more preferably 35% by mass or less.
<38> The content of the photopolymerization initiator in the colored curable resin composition is preferably 5 parts by mass or more, more preferably 10 parts per 100 parts by mass of the component (B) in the colored curable resin composition. Any one of <1> to <37>, which is at least 20 parts by mass, more preferably at least 20 parts by mass, preferably at most 70 parts by mass, more preferably at most 60 parts by mass, and even more preferably at most 50 parts by mass. A colored curable resin composition according to claim 1.
<39> The content of the photopolymerization initiation assistant in the colored curable resin composition is preferably 1 part by mass or more, more preferably 100 parts by mass of the component (B) in the colored curable resin composition. 3 parts by mass or more, more preferably 5 parts by mass or more, preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 15 parts by mass or less, from <1> to <38> The colored curable resin composition according to any one of the above.
<40> The colored curable resin composition according to any one of <1> to <39>, which is preferably used for forming a black matrix of a color filter.

<41> A method for producing a colored curable resin composition, comprising the following step 1 and step 2.
Step 1: A compound (1) represented by the following formula (1), a thiol compound (C) having three or more mercapto groups, a dispersant (D), and an organic solvent (E) are mixed and dispersed to obtain a dispersion. Step 2: Step of mixing the dispersion and a polyfunctional polymerizable compound (B) having two or more ethylenically unsaturated bonds

[In the above formula (1), X represents a double bond, and each independently represents an E-form or a Z-form as a geometric isomer, and each R ¹ independently represents a hydrogen atom, a methyl group, a nitro group, or a methoxy group. , A bromine atom, a chlorine atom, a fluorine atom, a carboxy group, or a 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. Represents a methyl group or a chlorine atom. ]
<42> A color filter comprising a black matrix formed using the colored curable resin composition according to any one of <1> to <40>.
<43> A step (a) of applying a colored curable resin composition according to any one of <1> to <40> onto a substrate, drying, photocuring, and developing to obtain a coating film, and the step (a) (B) forming a black matrix comprising a cured film by heating the coating film obtained at 200 to 300 ° C., and forming a resin film by applying an organic solvent solution of a resin on the cured film A method for producing a color filter comprising a black matrix, comprising (c).
<44> Use of the colored curable resin composition according to any one of <1> to <40> for producing a black matrix of a color filter.
<45> Use of the colored curable resin composition according to any one of <1> to <40> for producing a color filter.

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, solid content and viscosity are as follows: The method was performed.

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

(2) OD measurement (light-shielding evaluation) and solvent resistance evaluation Using a tabletop transmission densitometer (X-Rite “Model 361T”, measurement wavelength 550 nm), the OD of the coating film substrate (OD before processing) was measured. It was measured. The greater the pre-treatment OD, the better the light shielding property.
Next, 50 μL of N-methyl-2-pyrrolidone droplets were formed on the coating film of the coating film 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 formula. The closer the OD difference is to 0, the better the solvent resistance.
OD difference = OD after processing-OD before processing

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

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

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

(6) Method for measuring viscosity The viscosity of the fluorine compound was measured under the following conditions.
[conditions]
Viscometer: E type viscometer Rotor: Cone type, radius 24mm, angle 1 ° 34 '
Rotation speed: 100r / min
Measurement temperature: 25 ° C.
Measurement time: 1 min
Sample: 30% by mass PGMEA solution

Synthesis Example 1 Synthesis of black color material 2,5-dihydroxybenzene-1,4-diacetic acid (sum) was added to a 5 L four-necked flask equipped with a stirrer, thermometer, nitrogen blowing tube, Dean-Stark tube and Dimroth tube. A mixed liquid of 115 g (manufactured by Kojun Pharmaceutical Co., 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. for 7 hours while dehydrating Stir and heat for an additional 10 hours. The mixture was cooled to room temperature, and the black suspension was filtered with filter paper No. 2 (Advantech Toyo Co., Ltd.). This filtration 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).
This black substance was dissolved in dimethylformamide, and ESI / MS measurement by liquid chromatography mass spectrometry was performed to confirm that the molecular weight was 448.07.

Production Example 1 (Preparation of black color material dispersion 1)
10.0 g of the black color material obtained in Synthesis Example 1 as the pigment, 0.25 g of pentaerythritol tetrakis (3-mercaptopropionate) as the compound (C), and “Solsperth J-200” manufactured by Lubrizol Japan 2.25 g, 37.5 g of propylene glycol monomethyl ether acetate (PGMEA), and 100 g of zirconia beads having a diameter of 0.3 mm (“YTZ ball” manufactured by Nikkato) were placed in a 250 mL plastic container, and stirred for 3 hours in a paint shaker. The zirconia beads were removed by filtration to obtain a black color material dispersion 1.

Production Examples 2 to 12 and Comparative Production Examples 1 to 6 (Preparation of black color material dispersions 2 to 18)
Black color material dispersions 2 to 18 were obtained in the same manner as in Production Example 1, except that the formulation shown in Table 1 was used. In addition, the compound used for preparation is as follows.

A-1: Black color material obtained in Synthesis Example 1 A-2: Carbon black; “Raven 1060” manufactured by Colombian Carbon
A-3: Aniline black; “No. 2 superblack” manufactured by Toda Kogyo Co., Ltd.
C-1: Pentaerythritol tetrakis (3-mercaptopropionate)
C-2: Tris (3-mercaptopropionic acid) trimethylolpropane C-3: 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 ( 1H, 3H, 5H) -trione C-4: bis (2-mercaptoacetic acid) ethylene glycol C-5: dipentaerythritol hexakis (3-mercaptopropionate)
C-6: Tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate

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 performed while stirring.
While stirring the flask, the temperature was raised to 78 ° C., and MAA 14.4 g, BzMA 145.6 g, 3-mercaptopropionic acid 2.2 g, PGMEA 160 g, and 2,2′-azobis (2,4-dimethylvaleronitrile). ) (“V-65” manufactured by Wako Pure Chemical Industries, Ltd. (hereinafter also referred to as “V-65”)) A solution prepared by mixing 2.0 g was added dropwise over 3 hours. A mixed solution of 0.0 g and 10.0 g of PGMEA was added. The mixture was stirred at 78 ° C. for 1 hour, and 1.0 g of V-65, 10.0 g of PGMEA and a mixed solution were added. The mixture was further stirred at 78 ° C. for 1 hour, 100 g of PGMEA was added, and the mixture was 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 is prepared by uniformly mixing 211.0 g of the copolymer 1 solution having a solid content of 40.0% by mass obtained in Synthesis Example 2, 33.2 g of dipentaerythritol hexaacrylate (DPHA), and 256.6 g of PGMEA. A liquid was obtained.

Example 1 (Preparation of colored curable resin composition 1)
After putting 5.0 g of the black color material dispersion 1 obtained in Production Example 1 and 5.0 g of the clear resist solution obtained in Preparation Example 1 and 2.1 g of PGMEA into a sample bottle and sealing them, a roller type stirrer Were mixed uniformly 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 substrate was prepared according to the above-described method, and various evaluations were performed. The results are shown in Table 2.

Examples 2 to 12, Comparative Examples 1 to 6 (Preparation of colored curable resin compositions 2 to 18)
Colored curable resin compositions 2 to 18 were obtained in the same manner as in Example 1 except that the formulation was changed so as to obtain the composition shown in Table 2. In addition, the compound used for preparation is as follows. Using the obtained colored curable resin composition, a coated substrate was prepared according to the above-described method, and various evaluations were performed. The results are shown in Table 2.

Fluorine compound (F)
F-1: “Surflon S-611” manufactured by AGC Seimi Chemical Co., Ltd. (polyethylene glycol chain-containing nonionic fluorosurfactant, viscosity *: 19.70 mPa · s)
F-2: “Surflon S-651” manufactured by AGC Seimi Chemical Co., Ltd. (polyethylene glycol chain-containing nonionic fluorosurfactant, viscosity *: 3.61 mPa · s)
F-3: “Megafac RS-72-K” manufactured by DIC (30 mass% PGMEA solution of nonionic fluorine-containing oligomer containing a polyethylene glycol chain and a polymerizable group, viscosity: 9.70 mPa · s)
* Viscosities of F-1 and F-2 were measured as 30% by weight PGMEA solution.

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

Claims

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

[In the above formula (1), X represents a double bond, and each independently represents an E-form or a Z-form as a geometric isomer, and each R 1 independently represents a hydrogen atom, a methyl group, a nitro group, or a methoxy group. , A bromine atom, a chlorine atom, a fluorine atom, a carboxy group, or a 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. Represents a methyl group or a chlorine atom. ]
The mass ratio [(C) / (B)] of the thiol compound (C) to the polyfunctional polymerizable compound (B) in the colored curable resin composition is 0.1 or more and 2 or less. Colored curable resin composition.
The colored curable resin composition according to claim 1 or 2, wherein the content of the thiol compound (C) with respect to 100 parts by mass of the compound (1) in the colored curable composition is 1 part by mass or more and 10 parts by mass or less. .
The colored curable resin composition according to any one of claims 1 to 3, wherein the thiol compound (C) is an aliphatic thiol compound.
The colored curable resin composition according to any one of claims 1 to 4, wherein the thiol compound (C) has 4 to 6 mercapto groups.
The colored curable resin composition according to any one of claims 1 to 5, wherein the mercapto group in the thiol compound (C) is a primary mercapto group.
The colored curable resin composition according to any one of claims 1 to 6, further comprising a fluorine compound (F).
The colored curable resin composition according to claim 7, wherein the fluorine compound (F) is at least one selected from a surfactant having a fluorocarbon chain, a fluorine-based oligomer, and a compound having a fluorocarbon chain and a polymerizable group. object.
The colored curable resin composition according to claim 7 or 8, wherein the fluorine compound (F) is a compound having a fluorocarbon chain and a polymerizable group.
The colored curable resin composition according to any one of claims 7 to 9, wherein the content of the fluorine compound (F) is from 0.2 parts by mass to 10 parts by mass with respect to 100 parts by mass of the compound (1).
The colored curable resin composition according to any one of claims 1 to 10, wherein R 1 , R 2 and R 3 of the compound (1) are hydrogen atoms.
The colored curable resin composition according to any one of claims 1 to 11, which is used for forming a black matrix of a color filter.
A color filter comprising a black matrix formed using the colored curable resin composition according to any one of claims 1 to 11.
The manufacturing method of the colored curable resin composition which has the following process 1 and process 2. FIG.
Step 1: A compound (1) represented by the following formula (1), a thiol compound (C) having three or more mercapto groups, a dispersant (D), and an organic solvent (E) are mixed and dispersed to obtain a dispersion. Step 2: Step of mixing the dispersion and a polyfunctional polymerizable compound (B) having two or more ethylenically unsaturated bonds

[In the above formula (1), X represents a double bond, and each independently represents an E-form or a Z-form as a geometric isomer, and each R 1 independently represents a hydrogen atom, a methyl group, a nitro group, or a methoxy group. , a bromine atom, a chlorine atom, a fluorine atom, a carboxy group, or a sulfonic acid group, R 2 each independently represent a hydrogen atom, a methyl group, or a phenyl group, R 3 each independently represents a hydrogen atom Represents a methyl group or a chlorine atom. ]
Use of the colored curable resin composition according to any one of claims 1 to 11 for producing a black matrix of a color filter.
Use of the colored curable resin composition according to any one of claims 1 to 11 for producing a color filter.