KR102642067B1 - Colored curable resin composition, color filter and display apparatus comprizing the same - Google Patents

Abstract

A colored curable product comprising a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), wherein the colorant (A) includes C.I. Pigment Blue 16, a red colorant, and/or a purple colorant. Resin composition.

Description

Colored curable resin composition, color filter, and display device comprising the same {COLORED CURABLE RESIN COMPOSITION, COLOR FILTER AND DISPLAY APPARATUS COMPRIZING THE SAME}

The present invention relates to a colored curable resin composition, a color filter, and a display device containing the same.

Recently, the demand for liquid crystal display devices with a wide color gamut that can be displayed is increasing, such as the recommendation Rec.ITU-R BT.2020, which stipulates video formats with a wide color gamut. Development is underway to expand the color reproduction range. As part of this, color filters with darker colors are required.

A method of deepening the color of a color filter includes a method of increasing the colorant concentration in the color filter. However, if the colorant concentration is increased, the performance as a colored curable resin composition deteriorates, such as deterioration of the pattern shape. On the other hand, by using a colorant with high coloring power, it becomes possible to produce a pattern of a dark color filter. However, when a colorant with high coloring power is used, the brightness may be lowered. In addition, there is also a method of obtaining a dark color filter by making the color filter a thick film. However, when thickened, when applied to a liquid crystal display device, color mixing of light occurs between adjacent pixels.

Japanese Patent Publication No. 2012-088423 is a photosensitive resin composition capable of improving the phase difference in the oblique direction of the blue colored layer, and includes C. I. Pigment Blue 15:6, C. I. Pigment Blue 16, C. I. Pigment Blue 60, and C. I. A blue photosensitive resin composition containing at least one type of Pigment Blue 80 is proposed.

The present invention provides the colored curable resin composition, color filter, and display device shown below.

[1] Containing a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D),

The colorant (A) is a colored curable resin composition containing C.I. Pigment Blue 16, a red colorant, and/or a purple colorant.

[2] The colored curable resin composition according to [1], wherein the red colorant and/or the purple colorant is a dye.

[3] The colored curable resin composition according to [1] or [2], wherein the red colorant and/or the purple colorant is a compound having a xanthene skeleton.

[4] The colored curable resin composition according to any one of [1] to [3], wherein the colorant (A) contains C.I. Pigment Blue 16 and a red colorant.

[5] A color filter formed from the colored curable resin composition according to any one of [1] to [4] above.

[6] A display device comprising the color filter described in [5] above.

<Colored curable resin composition>

The colored curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and the colorant (A) is C.I. Pigment Blue 16, a red colorant, and /or contains a purple colorant.

C. I. According to a colored curable resin composition containing a specific combination of Pigment Blue 16 and a red colorant and/or a purple colorant, it is possible to obtain a dark color filter while using a thin film and an appropriate colorant concentration.

In addition, the compounds exemplified as each component in this specification can be used individually or in combination of multiple types, unless otherwise specified.

[1] Colorant (A)

In the colored curable resin composition of the present invention, the colorant (A) contains C.I. Pigment Blue 16, a red colorant, and/or a purple colorant.

Since the colored curable resin composition of the present invention contains the colorant (A), at an appropriate colorant concentration, it is possible to obtain a thin colored coating film that has both deep color reproduction and good pattern developability. Therefore, the colored curable resin composition is useful as a material for colored patterns.

The red colorant and the purple colorant may be a pigment or a dye. The colorant (A) may contain one or more types of red colorant and/or purple colorant in addition to C.I. Pigment Blue 16, and a pigment and dye may be used in combination.

Pigments for red colorants and purple colorants include compounds classified as red pigments in the color index (published by The Society of Dyers and Colourists), for example, C.I. Pigment Red 9, 97, 105, Red pigments such as 122, 123, 144, 149, 166, 168, 175, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, and violet pigments Compounds classified as pigments, for example, violet pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38, etc. can be mentioned. Two or more types of pigments may be used together.

As the dye in the red colorant and purple colorant, one or two or more types of conventionally known dyes can be used. Among these, the dye preferably contains a compound having a xanthene skeleton (hereinafter also referred to as “xanthene dye”) from the viewpoint of obtaining a dark color filter, and more preferably consists of the compound.

In addition, from the viewpoint of obtaining a dark color filter, the red colorant and/or the purple colorant are preferably composed of one or two or more types of dyes, using the formula (1):

It is more preferable that it is a compound represented by (hereinafter also referred to as “xanthene dye (1)”). Xanthene dye (1) may be used individually or in combination of two or more types.

In formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁸ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, or R ¹ and R ² and R ³ and R ⁴ Each becomes one to form a ring containing a nitrogen atom. The hydrogen atom contained in the aromatic hydrocarbon group is a halogen atom, -R ⁸ , -OH, -OR ⁸ , -SO ₃ -, -SO ₃ H, -SO ₃ ^{-M +} , -CO ₂ H, -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ may be substituted. Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

R ⁵ is -OH, -SO ₃ -, -SO ₃ H, -SO ₃ ^{-M +} , -CO ₂ H, -CO ₂ ^{-M +} , -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO It represents ₂ NR ⁹ R ¹⁰ .

m represents an integer from 0 to 5. When m is an integer of 2 or more, a plurality of R ⁵ may be the same or different from each other.

R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. M ⁺ represents ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ . X represents a halogen atom. Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. a represents 0 or 1.

R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, and -CH ₂ - contained in the saturated hydrocarbon group may be -S-, -O-, -CO- or It may be substituted with -NR ¹¹ -. R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. When there is a plurality of R ¹¹ , all or part of them may be the same.

R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with -OH or a halogen atom, and the saturated aliphatic group may be substituted with -OH or a halogen atom. -CH ₂ - contained in the hydrocarbon group may be substituted with -S-, -O-, -CO-, -NH- or -NR ⁸ -, and R ⁹ and R ¹⁰ are bonded to each other and contain a nitrogen atom. It may form a heterocyclic ring of 3 to 10 atoms. Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

In R ¹ to R ⁴ in formula (1), examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms include phenyl group, toluyl group, xylyl group, mesityl group, propylphenyl group and butylphenyl group.

In R ¹ to R ⁴ in formula (1), the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms is -SO ₃ -, -SO ₃ H, -SO ₃ ^{-M +} and -SO ₂ NR ⁹ R ¹⁰ as substituents. It is preferable to have at least one type selected from the group consisting of, and it is more preferable to have at least one type selected from the group consisting of -SO ₃ ^{-M +} and -SO ₂ NR ⁹ R ¹⁰ . In this case, -SO ₃ ^{-M +} is preferably -SO ₃ ^-+ N(R ¹¹ ) ₄ . If R ¹ to R ⁴ are these groups, it is advantageous in forming a color filter with excellent heat resistance.

Examples of the ring formed by R ¹ and R ² becoming one and the ring formed by R ³ and R ⁴ becoming one include the following groups.

For R ⁸ to R ¹¹ in formula (1), the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms includes methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, Alkyl groups having 1 to 20 carbon atoms such as neopentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, and icosyl group; Cycloalkyl groups having 3 to 20 carbon atoms, such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and tricyclodecyl group, can be mentioned.

With respect to the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms for R ⁸ , aromatic hydrocarbon groups having 6 to 10 carbon atoms in which a hydrogen atom may be substituted include phenyl group, toluyl group, xylyl group, mesityl group, propylphenyl group, butylphenyl group, etc. can be mentioned. Examples of groups in which -CH ₂ - contained in R ⁸ are substituted with -S-, -O-, -CO-, or -NR ¹¹ - include the following groups.

Examples of the alkyl group having 1 to 6 carbon atoms for R ⁶ and R ⁷ in formula (1) include those having 1 to 6 carbon atoms among the alkyl groups exemplified above.

Examples of the group represented by -SO ₂ NR ⁹ R ¹⁰ include groups represented by the following formula.

In the above formula, X ¹ represents a halogen atom. The halogen atom for X ¹ includes a fluorine atom, a chlorine atom, and a bromine atom.

Examples of the aralkyl group having 7 to 10 carbon atoms for R ¹¹ in formula (1) include benzyl group, phenylethyl group, and phenylbutyl group.

M ⁺ is ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and is preferably ⁺ N(R ¹¹ ) ₄ . ⁺ N(R ¹¹ ) ₄ It is preferable that at least two of the four R ¹¹ groups are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. Moreover, the total carbon number of four R ¹¹ is preferably 20 to 80, and more preferably 20 to 60.

The xanthene dye (1) is more preferably of formula (2):

It is preferable that it is a compound represented by .

In formula (2), R ²¹ to R ²⁴ each independently represent a hydrogen atom, -R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group is -SO ₃ - , -SO ₃ ^{-M a +} , -SO ₃ H, -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ may be substituted. X represents a halogen atom. Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

a1 represents 0 or 1. m1 represents an integer from 0 to 5. When m1 is an integer of 2 or more, a plurality of R ²⁵ may be the same or different from each other. M ^a+ represents ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ .

R ²⁵ represents -SO ₃ -, -SO ₃ ^{-M a+} , -SO ₃ H, or SO ₂ NHR ²⁶ . R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. The four R ^27s each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms for R ²¹ to R ²⁴ in formula (2) include the same groups as those exemplified as the aromatic hydrocarbon group for R ¹ to R ⁴ . Among them, R ²¹ and R ²³ are hydrogen atoms, and R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and when the hydrogen atom contained in the aromatic hydrocarbon group is substituted, the group to be substituted is -SO ₃ -, -SO ₃ ^{-M +} , -SO ₃ H, -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ is preferred. In addition, R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group is -SO ₃ ^{-M +} or -SO It is more preferable that it may be substituted with ₂ NHR ²⁶ . If R ²¹ to R ²⁴ are these groups, it is advantageous in forming a color filter with excellent heat resistance.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms for R ²⁶ and R ²⁷ in formula (2) include the same groups as those exemplified as the saturated hydrocarbon group for R ⁸ to R ¹¹ . -R ²⁶ in R ²¹ to R ²⁴ in formula (2) is preferably each independently a hydrogen atom, a methyl group, or an ethyl group.

R ²⁶ in -SO ₃ R ²⁶ and -SO ₂ NHR ²⁶ in formula (2) is preferably a branched alkyl group having 3 to 20 carbon atoms, and more preferably a branched alkyl group having 6 to 12 carbon atoms. , 2-ethylhexyl group is more preferred.

M ^a+ is ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ , and is preferably ⁺ N(R ²⁷ ) ₄ . ⁺ N(R ²⁷ ) ₄ It is preferable that at least two of the four R ²⁷ groups are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. Moreover, the total carbon number of four R ²⁷ is preferably 20 to 80, and more preferably 20 to 60.

The xanthene dye (1) preferably includes compounds represented by formulas (1-1) to (1-16). In addition, in each formula, Ra represents a 2-ethylhexyl group.

Among these compounds, the sulfonamide of C.I. Acid Red 289 or the quaternary ammonium salt of C.I. Acid Red 289 is more preferable. Examples of such compounds include compounds represented by formulas (1-1) to (1-8), (1-11), and (1-12), respectively.

The compounds represented by formula (1-1) to formula (1-16) are obtained by adding a pigment produced by the method described in the upper right column to the lower left column on page 3 of Japanese Patent Application Laid-Open No. 3-78702, in the same manner as above, with chlorine. It can also be produced by reacting it with an amine after conversion.

Other preferred xanthene dyes (1) include one or more of the compounds represented by formulas (1-17) to (1-31).

Compounds represented by formulas (1-17) to (1-31) can be produced according to the methods described in the upper right column to the lower left column of page 3 of Japanese Patent Application Laid-Open No. 3-78702.

As such a method, for example, there is a method of reacting the compound represented by formula (1a), the compound represented by formula (1b), and the compound represented by formula (1c). In formulas (1b) and (1c), R ¹ to R ⁴ each have the same meaning as above.

The xanthene dye (1) is a commercially available xanthene dye (e.g., “Chugai Aminol Fast Pink R-H/C” manufactured by Chugai Chemical Co., Ltd., “Rhodamin 6G” manufactured by Taoka Chemical Industry Co., Ltd.). You can use it. It can also be synthesized using a commercially available xanthene dye as a starting material, with reference to Japanese Patent Publication No. 2010-32999.

Specific examples of xanthene dye (1) include C.I. Acid Red 51 (hereinafter, description of C.I. Acid Red will be omitted and only the number will be described. The same applies to others), 52, 87, 92, 94. , 289, 388, etc. C.I. acid red dyes; C.I. Acid Violet dyes such as C.I. Acid Violet 9, 30, and 102; C. I. Basic Red dyes such as C. I. Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, 10 (Rhodamine B), 11; C. I. Basic Violet dyes such as C. I. Basic Violet 10, 11, and 25; C.I. Solvent Red dyes such as C.I. Solvent Red 218; C. I. Mordant Red dyes such as C. I. Mordant Red 27; C. I. Reactive Red dyes such as C. I. Reactive Red 36 (Rose Bengal B); Sulforhodamine G; Xanthene dye described in Japanese Patent Application Publication No. 2010-32999; and xanthene dyes described in Japanese Patent No. 4492760; etc. can be mentioned.

The content ratio of C.I. Pigment Blue 16 and the sum of the red colorant and the purple colorant in the colorant (A) (C.I. Pigment Blue 16/sum of the red colorant and the purple colorant) is usually 0.8 to 20 on a weight basis. and from the viewpoint of obtaining a dark color filter, it is preferably 1 to 15, more preferably 1.1 to 10, and still more preferably 1.2 to 8.

The colorant (A) may include colorants other than C.I. Pigment Blue 16, a red colorant, and a purple colorant. The other colorant may be a pigment, a dye, or both of these. As for other colorants, only one type may be used, or two or more types may be used in combination. Other pigments include organic pigments, inorganic pigments, and compounds classified as pigments in the Color Index (published by The Society of Dyers and Colourists).

As other dyes, known dyes can be used and include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of dyes include compounds classified as having colors other than pigments in the Color Index (published by The Society of Dyers and Colourists), and known dyes described in Dyeing Notes (Shiki Sens). Additionally, according to their chemical structures, azo dyes, cyanine dyes, triphenylmethane dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squaryllium dyes, and acridine dyes. , styryl dye, coumarin dye, quinoline dye, nitro dye, etc. Among these, organic solvent-soluble dyes are preferred.

The colorant (A) may contain a blue colorant (blue pigment and/or blue dye) other than C.I. Pigment Blue 16. Other blue pigments include C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60, etc.

As blue dye,

C. I. Solvent Blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98 , 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139, etc. C.I. solvent blue dyes;

C. I. Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90: 1, 91, 92, 93, 93: 1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234 , C.I. acid blue dyes such as 236, 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324:1, 335, 340;

C. I. Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84 , 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153 , 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 1 96 , 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 2 46 , 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293, etc. C.I. Direct blue dyes;

C. I. dispers blue dyes such as C. I. dispers blue 1, 14, 56, 60;

C. I. Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66 , 67, 68, 81, 83, 88, 89, etc. C. I. basic blue dye;

C. I. Mordant Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84 C. I. Mordant blue dye; etc. can be mentioned.

However, from the viewpoint of expanding the displayable color gamut, the higher the total content of C.I. Pigment Blue 16, the red colorant, and the purple colorant in the colorant (A), the more preferable it is. Specifically, the total content of C.I. Pigment Blue 16, the red colorant, and the purple colorant in the colorant (A) is preferably 50 to 100% by weight, more preferably 50 to 100% by weight, based on 100% by weight of the colorant (A). is 70 to 100% by weight, more preferably 80 to 100% by weight, and particularly preferably 90 to 100% by weight.

The content of C.I. Pigment Blue 16 in the colorant (A) is usually 20 to 95% by weight based on 100% by weight of the colorant (A), and is preferably 40 to 90% from the viewpoint of obtaining a dark color filter. % by weight, more preferably 50 to 85% by weight.

The content of the red colorant and the purple colorant in the colorant (A) is usually 5 to 80% by weight based on 100% by weight of the colorant (A), and is preferably 1 to 60% from the viewpoint of obtaining a dark color filter. % by weight, more preferably 15 to 50% by weight.

The total content of the colorant (A) in the colored curable resin composition is usually 10 to 50% by weight based on 100% by weight of solid content of the colored curable resin composition, but from the viewpoint of obtaining a dark color filter, it is preferably 30% by weight. It is % by weight or more, more preferably 15 to 40 % by weight, and even more preferably 20 to 35 % by weight. From the viewpoint of ease of forming a resist pattern, the total content is preferably 45% by weight or less, based on 100% by weight of solid content of the colored curable resin composition.

According to the present invention, it is possible to form a color filter that fits the color gamut of Rec.ITU-R BT.2020. In addition, in this specification, "solid content of colored curable resin composition" refers to all components other than the solvent (E) among the components contained in colored curable resin composition.

The various pigments used in the preparation of the colored curable resin composition are preferably in the state of a dispersion liquid uniformly dispersed in a solvent. Additionally, the pigment preferably has a uniform particle size. The dispersion liquid can be obtained by mixing a pigment and a solvent. If necessary, a pigment dispersant may be mixed. By containing a pigment dispersant and performing dispersion treatment, a pigment dispersion in which the pigment is uniformly dispersed in the solvent can be obtained.

As the pigment dispersant, commercially available surfactants can be used, including silicone-based, fluorine-based, ester-based (including polyester-based), cationic, anionic, nonionic, amphoteric, polyester-based, polyamine-based, and acrylic-based. and surfactants such as these. Specific examples of surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol diester, sorbitan fatty acid ester, fatty acid modified polyester, tertiary amine modified polyurethane, polyethylene imine, etc., and KP under the brand name. (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by BASF Japan Co., Ltd.), Azispur (registered trademark) ( Ajinomoto Fine Techno Co., Ltd.), Disperbyk (manufactured by Big Chemistry Co., Ltd.), etc. can be mentioned. As for the pigment dispersant, only 1 type may be used, and 2 or more types may be used together.

When using a pigment dispersant, the amount used is preferably 100 parts by weight or less, and more preferably 5 to 50 parts by weight, based on 100 parts by weight of the pigment. If the amount of the pigment dispersant used is within the above range, a pigment dispersion liquid in a uniformly dispersed state tends to be easily obtained.

The solvent constituting the pigment dispersion is not particularly limited, and includes solvents similar to the solvent (E) described later that may be contained in the colored curable resin composition. Among them, the solvent is propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxypropionate ethyl, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3 -Methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, etc. are preferred, and propylene glycol monomethyl ether acetate and propylene glycol. Monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 3-ethoxy ethyl propionate, etc. are preferable.

The amount of solvent used is not particularly limited, but the concentration of solid content in the pigment dispersion is preferably 3 to 20% by weight, more preferably 5 to 18% by weight.

Various pigments used in the preparation of colored curable resin compositions may be treated with rosin, surface treatment using pigment derivatives or pigment dispersants into which acidic or basic groups are introduced, grafting treatment on the pigment surface with polymer compounds, etc., as necessary, with sulfuric acid. Atomization treatment by an atomization method, etc., a washing treatment with an organic solvent or water to remove impurities, or a removal treatment by an ion exchange method of ionic impurities, etc. may be performed.

[2] Resin (B)

The colored curable resin composition of the present invention contains one or two or more types of resin (B). Resin (B) is preferably an alkali-soluble resin. Alkali solubility refers to the property of dissolving in a developer solution, which is an aqueous solution of an alkaline compound. Resins (B) include the following resins [K1] to [K6].

Resin [K1]: At least one (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter sometimes referred to as “(a)”) and a cyclic resin having 2 to 4 carbon atoms. A copolymer of monomer (b) (hereinafter sometimes referred to as “(b)”) having an ether structure and an ethylenically unsaturated bond.

Resin [K2]: (a) and (b), and monomer (c) copolymerizable with (a) (however, it is different from (a) and (b)) [hereinafter sometimes referred to as “(c)” 〕copolymer of.

Resin [K3]: Copolymer of (a) and (c).

Resin [K4]: Resin obtained by reacting (b) with the copolymer of (a) and (c).

Resin [K5]: Resin obtained by reacting (a) with the copolymer of (b) and (c).

Resin [K6]: Resin obtained by reacting (a) with the copolymer of (b) and (c) and further reacting a carboxylic acid anhydride.

(a), specifically,

Unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hepto-2-ene, 5,6-dicarboxybicyclo[2.2.1]hepto-2- N, 5-carboxy-5-methylbicyclo[2.2.1]hepto-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hepto-2-ene, 5-carboxy-6-methylbi Bicyclo unsaturated compounds containing a carboxyl group such as cyclo[2.2.1]hepto-2-ene and 5-carboxy-6-ethylbicyclo[2.2.1]hepto-2-ene;

Maleic acid anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride , unsaturated dicarboxylic acid anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo[2.2.1]hepto-2-ene anhydride (hymic acid anhydride);

Unsaturated mono[(meth)acryloyloxyalkyl of divalent or higher polyvalent carboxylic acids such as mono[2-(meth)acryloyloxyethyl] succinic acid, mono[2-(meth)acryloyloxyethyl] phthalate, etc. 〕Ester;

and unsaturated (meth)acrylic acids containing a hydroxy group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)(meth)acrylic acid.

Among them, from the viewpoint of copolymerization reactivity and solubility in aqueous alkaline solution, (a) is preferably (meth)acrylic acid, maleic anhydride, etc.

In addition, in this specification, "(meth)acryl" represents at least one type selected from the group consisting of acrylic and methacryl. The same applies to expressions such as “(meth)acryloyl” and “(meth)acrylate.”

(b) is an ethylenically unsaturated bond with a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one member selected from the group consisting of an oxilane ring, an oxetane ring, and a tetrahydrofuran ring (oxolane ring)) refers to a polymerizable compound having . (b) is preferably a monomer having a cyclic ether structure of 2 to 4 carbon atoms and a (meth)acryloyloxy group.

Examples of (b) include monomer (b1) having an oxylanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), a monomer having an oxetanyl group and an ethylenically unsaturated bond ( b2) [hereinafter sometimes referred to as “(b2)”], monomer (b3) [hereinafter sometimes referred to as “(b3)”], etc. having a tetrahydrofuryl group and an ethylenically unsaturated bond. .

(b1) is a monomer (b1-1) having a structure obtained by epoxidizing an unsaturated aliphatic hydrocarbon (hereinafter sometimes referred to as “(b1-1)”), a monomer having a structure obtained by epoxidizing an unsaturated alicyclic hydrocarbon. (b1-2) [hereinafter sometimes referred to as “(b1-2)”].

(b1-1) includes glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, and o-vinylbenzyl. Glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α -Methyl-p-vinylbenzylglycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxy) Methyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene, etc. You can.

Examples of (b1-2) include vinylcyclohexenemonoxide, 1,2-epoxy4-vinylcyclohexane (e.g., Celoxide 2000; manufactured by Daicel Chemical Industry Co., Ltd.), and 3,4-epoxycyclohexylmethyl. (meth)acrylate (e.g., Cyclomer A400; manufactured by Daicel Chemical Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer M100; manufactured by Daicel Chemical Co., Ltd.) (manufactured by Co., Ltd.), a compound represented by the following formula (I), a compound represented by the following formula (II), etc.

In formulas (I) and formulas (II), R ^a and R ^b independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group. do. X ¹ and X ² independently represent a single bond, *-R ^c -, *-R ^c -O-, *-R ^c -S-, or *-R ^c -NH-. R ^c represents an alkanediyl group having 1 to 6 carbon atoms. * represents a bond with O.

Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group.

Alkyl groups in which hydrogen atoms are substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1- Examples include hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, and 4-hydroxybutyl group. .

R ^a and R ^b are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

Alkanediyl groups constituting R ^c include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, and pentane-1,5-diyl group. Diyl group, hexane-1,6-diyl group, etc. can be mentioned.

_X ^{1 and} _{_ _} , more preferably a single bond, *-CH ₂ CH ₂ -O- group.

Specific examples of the compound represented by formula (I) include compounds represented by formulas (I-1) to formula (I-15). Preferably, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), formula (I-11) to formula (I- 15), and more preferably, it is formula (I-1), formula (I-7), formula (I-9), and formula (I-15).

Specific examples of the compound represented by formula (II) include compounds represented by the following formula (II-1) to the following formula (II-15). Preferably, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), formula (II-11) to formula (II- 15), and more preferably, it is formula (II-1), formula (II-7), formula (II-9), and formula (II-15).

The compound represented by formula (I) and the compound represented by formula (II) can each be used individually. They can be mixed in any ratio. When mixing, the mixing ratio is Formula (I):Formula (II) [molar ratio], preferably 5:95 to 95:5, more preferably 10:90 to 90:10, even more preferably It is 20:80 ~ 80:20.

The monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond is preferably a monomer having an oxetanyl group and a (meth)acryloyloxy group. Preferred examples of (b2) include 3-methyl-3-(meth)acryloyloxymethyloxetane, 3-ethyl-3-(meth)acryloyloxymethyloxetane, 3-methyl-3-(meth) ) Acryloyloxyethyloxetane, 3-ethyl-3-(meth)acryloyloxyethyloxetane.

The monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond is preferably a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group. Preferred examples of (b3) include tetrahydrofurfuryl acrylate (Viscott V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

A specific example of (c) is,

Methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate , dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate Rate, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl(meth)acrylate [In the technical field, it is called “dicyclofentanyl (meth)acrylate” as a common name. It is also sometimes called “tricyclodecyl (meth)acrylate”], tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth)acrylate [in the technical field, it is called “dicyclo” as a common name. It is called ‘pentenyl (meth)acrylate’, dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, (meth)acrylic acid esters such as propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate;

Hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate;

Bicyclo[2.2.1]hepto-2-ene, 5-methylbicyclo[2.2.1]hepto-2-ene, 5-ethylbicyclo[2.2.1]hepto-2-ene, 5-hydroxybi Cyclo[2.2.1]hepto-2-ene, 5-hydroxymethylbicyclo[2.2.1]hepto-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hepto-2 -N, 5-methoxybicyclo[2.2.1]hepto-2-ene, 5-ethoxybicyclo[2.2.1]hepto-2-ene, 5,6-dihydroxybicyclo[2.2.1]hepto -2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hepto-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hepto- 2-ene, 5,6-dimethoxybicyclo[2.2.1]hepto-2-ene, 5,6-diethoxybicyclo[2.2.1]hepto-2-ene, 5-hydroxy-5-methyl Bicyclo[2.2.1]hepto-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hepto-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1] Hepto-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hepto-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hepto-2-ene, 5-phenoc Cycarbonylbicyclo[2.2.1]hepto-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hepto-2-ene, 5,6-bis(cyclohexyl oxide Bicyclo unsaturated compounds such as cycarbonyl)bicyclo[2.2.1]hepto-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl Dicarbonylimide derivatives such as -6-maleimide caproate, N-succinimidyl-3-maleimide propionate, and N-(9-acridinyl)maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, acetic acid. Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc. can be mentioned.

Among them, from the viewpoint of copolymerization reactivity and heat resistance, (c) is benzyl (meth)acrylate, tricyclodecyl (meth)acrylate, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, and N-benzyl. Maleimide, bicyclo[2.2.1]hepto-2-ene, etc. are preferred. Furthermore, benzyl (meth)acrylate and tricyclodecyl (meth)acrylate are more preferable for (c) because of their excellent developability during pattern formation.

In the resin [K1], the ratio of structural units derived from each is preferably within the following range among all structural units constituting the resin [K1].

(a) Structural unit derived from ; 2 to 50 mol% (more preferably 10 to 45 mol%),

Structural units derived from (b), especially structural units derived from (b1); 50 to 98 mol% (more preferably 55 to 90 mol%).

If the ratio of the structural units of the resin [K1] is within the above range, the storage stability, developability, and solvent resistance of the resulting pattern tend to be excellent.

Resin [K1] was prepared by referring to the method described in the document “Experimental Methods for Polymer Synthesis” (written by Takayuki Otsu, Chemistry Co., Ltd., 1st edition, 1st printing, published on March 1, 1972) and the cited literature described in this document. It can be manufactured.

Specifically, a method includes pouring a predetermined amount of (a) and (b) (particularly (b1)), a polymerization initiator, a solvent, etc. into a reaction vessel, followed by stirring, heating, and keeping warm in a deoxygenated atmosphere. In addition, the polymerization initiator and solvent used here are not particularly limited, and any of those commonly used in the field can be used. Polymerization initiators include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.). You can. The solvent may be any solvent that dissolves each monomer, and solvents such as solvent (E) described later can be used as a solvent for the colored curable resin composition.

In addition, the obtained copolymer may be used as a solution after the reaction, a concentrated or diluted solution, or a solid (powder) taken out by a method such as reprecipitation. In particular, by using the solvent (E) described later as a solvent during this polymerization, the solution after the reaction can be used as is, and the manufacturing process can be simplified.

In the resin [K2], the ratio of structural units derived from each is preferably within the following range among all structural units constituting the resin [K2].

(a) Structural unit derived from ; 4 to 45 mol% (more preferably 10 to 30 mol%),

Structural units derived from (b), especially structural units derived from (b1); 2 to 95 mol% (more preferably 5 to 80 mol%),

(c) structural unit derived from; 1 to 65 mol% (more preferably 5 to 60 mol%).

When the ratio of the structural units of the resin [K2] is within the above range, storage stability, developability, solvent resistance of the resulting pattern, heat resistance, and mechanical strength tend to be excellent.

Resin [K2] can be produced in the same manner as the method described as the production method for resin [K1]. Specifically, a method of injecting a predetermined amount of (a), (b) (particularly (b1)), and (c), a polymerization initiator, and a solvent into a reaction vessel, followed by stirring, heating, and keeping warm in a deoxygenated atmosphere. You can. The obtained copolymer may be used as a solution after the reaction, a concentrated or diluted solution, or a solid (powder) taken out by a method such as reprecipitation.

In resin [K3], the ratio of structural units derived from each is preferably within the following range among all structural units constituting resin [K3].

(a) Structural unit derived from ; 2 to 55 mol% (more preferably 10 to 50 mol%),

(c) structural unit derived from; 45 to 98 mol% (more preferably 50 to 90 mol%).

Resin [K3] can be produced in the same manner as the method described as the production method for Resin [K1].

Resin [K4] is obtained by obtaining a copolymer of (a) and (c), and forming the cyclic ether structure of 2 to 4 carbon atoms possessed by (b), particularly the oxilane ring possessed by (b1) into the carboxyl ring possessed by (a). It can be prepared by addition to acids and/or carboxylic acid anhydrides. Specifically, first, the copolymers of (a) and (c) are produced in the same manner as the method described as the production method of resin [K1]. In this case, the ratio of structural units derived from each is preferably within the following range among all structural units constituting the copolymers (a) and (c).

(a) Structural unit derived from ; 5 to 50 mol% (more preferably 10 to 45 mol%),

(c) structural unit derived from ; 50 to 95 mol% (more preferably 55 to 90 mol%).

Next, a portion of the carboxylic acid and/or carboxylic acid anhydride derived from (a) in the above copolymer contains a cyclic ether structure having 2 to 4 carbon atoms of (b), particularly an oxilane ring of (b1). react. Specifically, following the production of the copolymers of (a) and (c), the atmosphere in the flask was replaced from nitrogen to air, and (b) (particularly (b1)), carboxylic acid or carboxylic acid anhydride and the ring A reaction catalyst with an ether-type ether structure (e.g., tris(dimethylaminomethyl)phenol, etc.) and a polymerization inhibitor (e.g., hydroquinone, etc.) are placed in a flask and reacted at 60 to 130° C. for 1 to 10 hours. You can obtain resin [K4].

The amount of (b) used, especially the amount of (b1) used, is preferably 5 to 80 moles, more preferably 10 to 75 moles, per 100 moles of (a). By setting it within this range, the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity tends to become good. Since the reactivity of the cyclic ether structure is high and unreacted (b) rarely remains, (b) used in resin [K4] is preferably (b1), and (b1-1) is more preferable. .

The amount of the reaction catalyst used is preferably 0.001 to 5% by weight based on the total amount of (a), (b) (particularly (b1)) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5% by weight based on the total amount of (a), (b), and (c).

Reaction conditions such as injection method, reaction temperature and time can be adjusted appropriately taking into account the manufacturing equipment and the amount of heat generated by polymerization. In addition, like the polymerization conditions, the injection method and reaction temperature can be adjusted appropriately by taking into consideration the manufacturing equipment and the amount of heat generated by polymerization.

Resin [K5] is prepared in the same manner as the above-described production method for resin [K1] in the first step to obtain a copolymer of (b) (particularly (b1)) and (c). Similarly to the above, the obtained copolymer may be used as a solution after the reaction, a concentrated or diluted solution, or a solid (powder) taken out by a method such as reprecipitation.

The ratio of the structural units derived from (b) (particularly (b1)) and (c) is preferably within the following range with respect to the total number of moles of all structural units constituting the above copolymer.

Structural units derived from (b), especially structural units derived from (b1); 5 to 95 mol% (more preferably 10 to 90 mol%),

(c) structural unit derived from ; 5 to 95 mol% (more preferably 10 to 90 mol%).

Furthermore, under the same conditions as the method for producing resin [K4], the cyclic ether structure derived from (b) possessed by the copolymer of (b) (particularly (b1)) and (c) is added to the cyclic ether structure derived from (b) possessed by (a). Resin [K5] can be obtained by reacting a boxylic acid or carboxylic acid anhydride. The amount of (a) reacted with the above copolymer is preferably 5 to 80 moles per 100 moles of (b) (particularly (b1)). Since the reactivity of the cyclic ether structure is high and unreacted (b) rarely remains, (b) used in resin [K5] is preferably (b1), and (b1-1) is more preferable. .

Resin [K6] is a resin obtained by reacting resin [K5] with a carboxylic acid anhydride. A carboxylic acid anhydride is reacted with a hydroxy group generated by the reaction of a cyclic ether structure with a carboxylic acid or carboxylic acid anhydride.

Carboxylic acid anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, and 1,2,3. , 6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hepto-2-ene anhydride (hymic acid anhydride), etc.

Among resins [K1] to [K6], the resin preferable as resin (B) is [K1] or [K2]. Resin (B) may consist of one type of resin or may contain two or more types of resin.

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. If the molecular weight is within the above range, the solubility of the unexposed portion in the developer is high, and the residual film rate and hardness of the resulting pattern tend to be high as well. The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, more preferably 1.2 to 4.

The solution acid value of the resin (B) is preferably 5 to 180 mg-KOH/g, more preferably 10 to 100 mg-KOH/g, and still more preferably 12 to 50 mg-KOH/g. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be obtained, for example, by titration using an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, and even more preferably 15 to 30% by weight, based on 100% by weight of solid content of the colored curable resin composition. . When the content of the resin (B) is within the above range, the solubility of the unexposed portion in the developing solution tends to be high.

[3] Polymerizable compound (C)

The polymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by active radicals generated from the polymerization initiator (D) by irradiation of light, etc., and examples thereof include compounds having a polymerizable ethylenically unsaturated bond. . The weight average molecular weight of the polymerizable compound (C) is preferably 3,000 or less.

Among them, the polymerizable compound (C) is preferably a photopolymerizable compound having three or more ethylenically unsaturated bonds, such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tri(meth)acrylate. Erythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth) Acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, ethylene glycol modified pentaerythritol tetra. (meth)acrylate, ethylene glycol-modified dipentaerythritol hexa(meth)acrylate, propylene glycol-modified pentaerythritol tetra(meth)acrylate, propylene glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified Pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, etc. can be mentioned. Among them, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are preferable.

The colored curable resin composition of the present invention may contain one or two or more types of polymerizable compounds (C). The content of the polymerizable compound (C) is preferably 20 to 150 parts by weight, more preferably 80 to 120 parts by weight, based on 100 parts by weight of the resin (B) in the colored curable resin composition.

[4] Polymerization initiator (D)

The polymerization initiator (D) is not particularly limited as long as it is a compound that can initiate polymerization by generating active radicals, acids, etc. under the action of light or heat, and any known polymerization initiator can be used.

Examples of the polymerization initiator (D) include oxime-based compounds such as O-acyloxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds. Two or more types of polymerization initiators (D) may be used in combination, taking into account sensitivity, ability to form precise pattern shapes, etc. The polymerization initiator (D) preferably contains an oxime-based compound such as an O-acyloxime compound from the viewpoint of sensitivity and advantage in precisely creating a pattern shape with a desired line width.

An O-acyloxime compound is a compound having a structure represented by formula (d). Hereinafter, * represents a bond.

O-acyloxime compounds include, for example, a compound represented by formula (d1) (hereinafter sometimes referred to as “compound (d1)”), a compound represented by formula (d2) (hereinafter referred to as “compound (d2)”) It is preferable that it is at least one type selected from the group consisting of) and a compound represented by formula (d3) (hereinafter sometimes referred to as “compound (d3)”).

In formulas (d1) to (d3),

R ^d1 is an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, a heterocyclic group having 3 to 36 carbon atoms which may have a substituent, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or an aromatic hydrocarbon group and its alkyl group. represents a group that may have a substituent in combination with an alkanediyl group derived from, and the methylene group (-CH ₂ -) contained in the alkyl group is -O-, -CO-, -S-, -SO ₂ - or -NR ^d5 - may be substituted,

R ^d2 represents an aromatic hydrocarbon group with 6 to 18 carbon atoms, a heterocyclic group with 3 to 36 carbon atoms, or an alkyl group with 1 to 10 carbon atoms,

R ^d3 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, or a heterocyclic group having 3 to 36 carbon atoms which may have a substituent,

R ^d4 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, which may have a substituent, or an aliphatic hydrocarbon group having 1 to 15 carbon atoms, which may have a substituent, and the methylene group (-CH ₂ -) contained in the aliphatic hydrocarbon group is - It may be substituted with O-, -CO- or -S-, and the methine group (-CH<) contained in the aliphatic hydrocarbon group may be substituted with _-PO3 <, and the hydrogen atom contained in the aliphatic hydrocarbon group may be It may be substituted with an OH group,

R ^d5 represents an alkyl group having 1 to 10 carbon atoms, and the methylene group (-CH ₂ -) contained in the alkyl group may be substituted with -O- or -CO-.

The carbon number of the aromatic hydrocarbon group represented by R ^d1 is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, anthryl group, phenanthryl group, biphenyl group, terphenyl group, etc., with phenyl group and naphthyl group being preferable, and phenyl group being more preferable.

The aromatic hydrocarbon group represented by R ^d1 may have one or two or more substituents. The substituent is preferably substituted at the α-position or γ-position of the aromatic hydrocarbon group, and is more preferably substituted at the γ-position. The substituents include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, and pentadecyl group. Alkyl groups having 1 to 15 carbon atoms, such as; Halogen atoms such as fluorine atom, chlorine atom, iodine atom, and bromine atom; etc. can be mentioned.

The carbon number of the alkyl group as the substituent is preferably 1 to 10, and more preferably 1 to 7. The alkyl group as the substituent may be linear, branched, or cyclic, or may be a combination of a chain group and a cyclic group. The methylene group (-CH ₂ -) included in the alkyl group as the substituent may be substituted with -O- or -S-. Additionally, the hydrogen atom contained in the alkyl group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom, or a bromine atom, and is preferably substituted with a fluorine atom.

In the aromatic hydrocarbon group represented by R ^d1 , examples of the alkyl group as a substituent include groups represented by the formula below. In the formula, * represents a binding hand.

For R ^d1 , examples of the aromatic hydrocarbon group that may have a substituent include groups represented by the formula below. In the formula, * represents a binding hand.

For R ^d1 , the aromatic hydrocarbon group that may have a substituent is preferably a group represented by the formula below.

In the formula, R ^d6 represents an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, and the hydrogen atom contained in R ^d6 may be substituted with a halogen atom. m2 represents an integer from 1 to 5.

Examples of the alkyl group represented by R ^d6 include the same groups as the alkyl groups exemplified as substituents of the aromatic hydrocarbon group represented by R ^d1 . The number of carbon atoms of R ^d6 is preferably 2 to 7, and more preferably 2 to 5. Additionally, the alkyl group represented by R ^d6 may be linear, branched, or cyclic, and is preferably chain.

Halogen atoms that may be replacing the hydrogen atom contained in R ^d6 include a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom, and fluorine is particularly preferable. Additionally, it is preferable that 2 or more and 10 or less hydrogen atoms contained in R ^d6 are substituted with halogen atoms, and 3 or more but 6 or less hydrogen atoms are preferably substituted with halogen atoms. The position of substitution of the R ^d6 O- group is preferably the ortho position or the para position, and the para position is particularly preferable. Moreover, it is preferable that m2 is 1-2, and it is especially preferable that it is 1.

The number of carbon atoms of the heterocyclic group represented by R ^d1 is preferably 3 to 20, more preferably 3 to 10, and still more preferably 3 to 5. Examples of the heterocyclic group include pyrrolyl group, furyl group, thienyl group, indolyl group, benzofuryl group, and carbazolyl group.

The heterocyclic group represented by R ^d1 may have one or two or more substituents. Examples of the substituent include the same groups as those exemplified as substituents that the aromatic hydrocarbon group represented by R ^d1 may have.

The alkyl group represented by R ^d1 preferably has 1 to 12 carbon atoms. The alkyl group represented by R ^d1 includes methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, and Pentadecyl group, etc. can be mentioned. These alkyl groups may be linear, branched, or cyclic, and may be a combination of a chain group and a cyclic group. In addition, in the alkyl group represented by R ^d1 , the methylene group (-CH ₂ -) may be substituted by -O-, -CO-, -S-, -SO ₂ - or -NR ^d5 -, and the hydrogen atom may be substituted by -O-, -CO-, -S-, -SO 2 - or -NR d5 - , may be substituted with an OH group or SH group.

R ^d5 represents an alkyl group with 1 to 10 carbon atoms, preferably an alkyl group with 1 to 5 carbon atoms, and more preferably an alkyl group with 1 to 3 carbon atoms. The alkyl group may be chain-shaped (linear or branched), cyclic, straight-chain, branched-chain, or cyclic, or may be a combination of a chain group and a cyclic group. It can also be a contribution. Additionally, in the alkyl group of R ^d5 , the methylene group (-CH ₂ -) may be substituted with -O- or -CO-.

For R ^d1 , specific examples of the alkyl group that may have a substituent include groups represented by the following formula. * indicates a binding hand.

Moreover, in R ^d1 , the carbon number of the group combining an aromatic hydrocarbon group and an alkanediyl group is preferably 7 to 33, more preferably 7 to 18, and still more preferably 7 to 12. The combined group may have one or two or more substituents, and the substituents include the same groups as those exemplified as the substituents that an aromatic hydrocarbon group and an alkyl group may have. The group represented by R ^d1 which is a combination of an aromatic hydrocarbon group and an alkanediyl group includes an aralkyl group, and specifically, a group represented by the following formula. In the formula, * represents a binding hand.

Among them, R ^d1 is preferably an aromatic hydrocarbon group that may have a substituent or an alkyl group that may have a substituent, and more preferably an aromatic hydrocarbon group that may have a substituent.

The carbon number of the aromatic hydrocarbon group represented by R ^d2 is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, anthryl group, phenanthryl group, biphenyl group, and terphenyl group.

The number of carbon atoms of the heterocyclic group represented by R ^d2 is preferably 3 to 20, more preferably 3 to 10, and still more preferably 3 to 5. Examples of the heterocyclic group include pyrrolyl group, furyl group, thienyl group, indolyl group, benzofuryl group, and carbazolyl group.

The number of carbon atoms of the alkyl group represented by R ^d2 is preferably 1 to 7, more preferably 1 to 5, and still more preferably 1 to 3. Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group. The alkyl group may be linear, branched, or cyclic, or may be a combination of a chain group and a cyclic group.

R ^d2 is preferably a chain alkyl group, more preferably a chain alkyl group having 1 to 5 carbon atoms, even more preferably a chain alkyl group having 1 to 3 carbon atoms, and a methyl group is particularly preferable.

The carbon number of the aromatic hydrocarbon group represented by R ^d3 is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, anthryl group, phenanthryl group, biphenyl group, and terphenyl group, and phenyl group and naphthyl group are more preferable.

The aromatic hydrocarbon group represented by R ^d3 may have one or two or more substituents. The substituent is preferably substituted at the α-position or γ-position of the aromatic hydrocarbon group. The substituent is preferably an aliphatic hydrocarbon group having 1 to 15 carbon atoms, and specifically, carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. Alkyl groups of 1 to 15; alkenyl groups having 1 to 15 carbon atoms such as ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, nonenyl group, and decenyl group; etc. can be mentioned.

In R ^d3 , the aliphatic hydrocarbon group that the aromatic hydrocarbon group may have more preferably has 1 to 7 carbon atoms, and the aliphatic hydrocarbon group may be linear, branched, or cyclic, and may be chain. A combination of a cyclic group and a cyclic group can also be used. In addition, the methylene group (-CH ₂ -) contained in the aliphatic hydrocarbon group may be substituted with -O-, -CO-, or -S-, and the methine group (-CH<) may be substituted with -N< You can stay.

In R ^d3 , examples of the aliphatic hydrocarbon group that the aromatic hydrocarbon group may have include groups represented by the formula below. In the formula, * represents a binding hand.

For R ^d , examples of the aromatic hydrocarbon group that may have a substituent include groups represented by the formula below. In the formula, * represents a binding hand.

The carbon number of the heterocyclic group represented by R ^d3 is preferably 3 to 20, more preferably 3 to 10, and still more preferably 3 to 5. Examples of the heterocyclic group include pyrrolyl group, furyl group, thienyl group, indolyl group, benzofuryl group, and carbazolyl group. The heterocyclic group represented by R ^d3 may have one or two or more substituents, and examples of the substituent include the same groups as those exemplified as the substituents that the aromatic hydrocarbon group represented by R ^d1 may have.

Among them, R ^d3 is preferably an aromatic hydrocarbon group having a substituent, and the substituent is preferably a chain alkyl group having 1 to 7 carbon atoms (more preferably 1 to 3 carbon atoms), and the number of substituents is 2. It is preferable that there are more than 5 or less.

The carbon number of the aromatic hydrocarbon group represented by R ^d4 is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, anthryl group, phenanthryl group, biphenyl group, and terphenyl group, with phenyl group and naphthyl group being more preferable, and phenyl group being still more preferable. The aromatic hydrocarbon group represented by R ^d4 may have one or two or more substituents. The substituent includes the same group as the substituent that the aromatic hydrocarbon group of R ^d1 may have.

The aliphatic hydrocarbon group represented by R ^d4 preferably has 1 to 13 carbon atoms, more preferably 2 to 10 carbon atoms, and still more preferably 4 to 9 carbon atoms. The aliphatic hydrocarbon group represented by R ^d4 includes methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, and tetradecyl group. and alkyl groups such as pentadecyl group; Ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, butadecenyl group and pentadecenyl group. Alkenyl groups such as groups; etc. can be mentioned. These aliphatic hydrocarbon groups may be chain-shaped (linear or branched-chain), cyclic, or may be a combination of a chain group and a cyclic group. In addition, in the aliphatic hydrocarbon group of R ^d4 , the methylene group (-CH ₂ -) may be substituted with -O-, -CO-, or -S-, and the methine group (-CH <) may be -PO ₃ < may be substituted, and the hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an OH group.

Examples of the aliphatic hydrocarbon group that may have a substituent represented by R ^d4 include groups represented by the following formula. In the formula, * represents a binding hand.

R ^d4 is preferably a chain aliphatic hydrocarbon group that may have a substituent, more preferably a chain alkyl group without a substituent, and even more preferably a branched alkyl group without a substituent.

Examples of the compound (d1) include the compound represented by (d1), specifically, the compound having each substituent described in (d1-1) to the compound having each substituent described in (d1-67). In Tables 1 to 7, * represents a bond.

Among them, compounds having each of the substituents described in (d1-3) to compounds having each of the substituents described in (d1-6), compounds having each of the substituents described in (d1-18) to each of the compounds described in (d1-52) A compound having a substituent, a compound having each substituent described in (d1-55), a compound having each substituent described in (d1-56), a compound having each substituent described in (d1-60), (d1-61) Compounds having each of the substituents described are preferred,

More preferably, the compound having each substituent described in (d1-3) to the compound having each substituent described in (d1-6), the compound having each substituent described in (d1-18) to (d1-41). It is a compound having each substituent described,

More preferably, it is a compound having each substituent described in (d1-24), a compound having each substituent described in (d1-36) to a compound having each substituent described in (d1-40), and particularly preferably (d1 It is a compound having each substituent described in -24).

Compound (d1) can be produced, for example, by the production method described in Japanese Patent Publication No. 2014-500852.

Compound (d2) is,

R ^d1 is an alkyl group having 1 to 15 carbon atoms which may have a substituent,

R ^d2 is an alkyl group having 1 to 10 carbon atoms,

R ^d3 is an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent,

Compounds where R ^d4 is an aliphatic hydrocarbon group having 1 to 15 carbon atoms which may have a substituent are preferred,

More preferably,

R ^d1 represents a methyl group, an ethyl group, or a propyl group,

R ^d2 represents a methyl group, an ethyl group, or a propyl group,

R ^d3 represents a phenyl group substituted with a methyl group,

A compound where R ^d4 is a methyl group, ethyl group, or propyl group,

More preferably,

It is a compound in which R ^d1 and R ^d2 are methyl groups, R ^d3 is o-tolyl group, and R ^d4 is ethyl group.

Compound (d3) is,

R ^d1 is an alkyl group having 1 to 15 carbon atoms which may have a substituent,

Compounds in which R ^d2 is an aromatic hydrocarbon group having 6 to 18 carbon atoms are preferred,

More preferably,

It is a compound in which R ^d1 is a hexyl group and R ^d2 is a phenyl group.

Such O-acyloxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl) Octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9- Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3, 3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2- Methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole- 3-yl]-3-cyclopentylpropan-1-one-2-imine, etc. are mentioned. You may use commercially available products such as Irgacure OXE01, OXE02, OXE03 (manufactured by BASF), and N-1919 (manufactured by ADEKA). With these O-acyloxime compounds, a color filter with excellent litho performance tends to be obtained.

An alkylphenone compound is a compound having a structure represented by formula (d4) or a structure represented by formula (d5). Among these structures, the benzene ring may have a substituent.

Compounds having a structure represented by formula (d4) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morph Polinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butane-1- You can lift your whole back. Commercially available products such as Irgacure 369, 907, and 379 (manufactured by BASF) may be used.

Compounds having a structure represented by formula (d5) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxy ethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, oligomer of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α -diethoxyacetophenone, benzyldimethylketal, etc. can be mentioned.

From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by the formula (d4).

Biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole and 2,2'-bis(2,3-dichlorophenyl). -4,4',5,5'-tetraphenylbiimidazole (see Japanese Patent Application Publication No. 6-75372, Japanese Patent Application Publication No. 6-75373, etc.), 2,2'-bis (2-chloro Phenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole , 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4 ',5,5'-tetra(trialkoxyphenyl)biimidazole (Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62-174204, etc., reference), 4,4',5,5'- and imidazole compounds in which the phenyl group at the position is substituted by a carboalkoxy group (see Japanese Patent Application Laid-Open No. 7-10913, etc.). Among them, compounds represented by the following formulas or mixtures thereof are preferable.

Triazine compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-( 4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine Romethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl) ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2 ,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)- and 6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

Furthermore, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, o-benzoylmethylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphor quinone; Examples include 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with the polymerization initiation auxiliary agent (D1) (especially amines) described later.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by weight, more preferably 5 to 25 parts by weight, based on 100 parts by weight of the total amount of the resin (B) and the polymerizable compound (C). Preferably it is 10 to 20 parts by weight. When the content of the polymerization initiator (D) is within the above range, the sensitivity increases and the exposure time tends to be shortened, so the productivity of the color filter tends to improve.

[5] Polymerization initiation aid (D1)

The polymerization initiation aid (D1) is a compound or a sensitizer used to promote polymerization of a polymerizable compound whose polymerization has been initiated by a polymerization initiator. When a polymerization initiation aid (D1) is included, it is used in combination with a polymerization initiator (D).

Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds. Among them, thioxanthone compounds are preferable. You may use two or more types of polymerization initiation aids (D1) in combination.

Amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and 4-dimethyl benzoate. Aminobenzoic acid 2-ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4, Examples include 4'-bis(ethylmethylamino)benzophenone, and among these, 4,4'-bis(diethylamino)benzophenone is preferable. You may use a commercial product such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.).

Alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10- Dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc. can be mentioned.

Thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxyl. City Oak Santon, etc. may be mentioned.

Carboxylic acid compounds include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, Examples include chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

The content of the polymerization initiation aid (D1) is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the total amount of the resin (B) and the polymerizable compound (C). If the content of the polymerization initiation auxiliary agent (D1) is within the above range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to improve.

[6] Thiol compound (T)

The colored curable resin composition of the present invention may contain one type or two or more types of thiol compounds (T). The thiol compound (T) is particularly preferably used when the polymerization initiator (D) is an oxime-based compound such as an O-acyloxime compound, and/or a biimidazole compound. The thiol compound (T) is a compound having at least one sulfanyl group (-SH) in the molecule. The thiol compound (T) is preferably a compound having one sulfanyl group in the molecule.

Compounds having one sulfanyl group in the molecule include 2-sulfanyloxazole, 2-sulfanylthiazole, 2-sulfanylbenzimidazole, 2-sulfanylbenzothiazole, 2-sulfanylbenzoxazole, 2-sulfanylnicotinic acid, 2-sulfanylpyridine, 2-sulfanylpyridin-3-ol, 2-sulfanylpyridine-N-oxide, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4- Amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino-2-sulfanylpyrimidine, 6-amino-5-nitroso-2-thiouracil, 4,5-diamino-6-hydroxy -2-sulfanylpyrimidine, 4,6-diamino-2-sulfanylpyrimidine, 2,4-diamino-6-sulfanylpyrimidine, 4,6-dihydroxy-2-sulfanylpyrimidine , 4,6-dimethyl-2-sulfanylpyrimidine, 4-hydroxy-2-sulfanyl-6-methylpyrimidine, 4-hydroxy-2-sulfanyl-6-propylpyrimidine, 2-sulfanyl -4-methylpyrimidine, 2-sulfanylpyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazole-2-thiol, 2-sulfanylimidazole, 2-sulfanyl-1-methylimidazole, 4-amino-3-hydrazino-5-sulfanyl-1,2,4-triazole, 3-amino-5-sul Panyl-1,2,4-triazole, 2-methyl-4H-1,2,4-triazole-3-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol, 3 -Sulfanyl 1H-1,2,4-triazole-3-thiol, 2-amino-5-sulfanyl-1,3,4-thiadiazole, 5-amino-1,3,4-thiadiazole -2-thiol, 2,5-disulfanyl-1,3,4-thiadiazole, (furan-2-yl)methanethiol, 2-sulfanyl-5-thiazolidone, 2-sulfanylthiazoline, 2-sulfanyl-4(3H)-quinazolinone, 1-phenyl-1H-tetrazole-5-thiol, 2-quinolinethiol, 2-sulfanyl-5-methylbenzimidazole, 2-sulfanyl-5 -Nitrobenzimidazole, 6-amino-2-sulfanylbenzothiazole, 5-chloro-2-sulfanylbenzothiazole, 6-ethoxy-2-sulfanylbenzothiazole, 6-nitro-2-sul Panylbenzothiazole, 2-sulfanylnaphthoimidazole, 2-sulfanylnaphthooxazole, 3-sulfanyl-1,2,4-triazole, 4-amino-6-sulfanylpyrazolo[2,4 -d]pyridine, 2-amino-6-purinethiol, 6-sulfanylpurine, and 4-sulfanyl-1H-pyrazolo[2,4-d]pyrimidine.

Compounds having two or more sulfanyl groups in the molecule include hexanedithiol, decanedithiol, 1,4-bis(methylsulfanyl)benzene, butanediolbis(3-sulfanylpropionate), butanediolbis(3- Sulfanyl acetate), Ethylene glycol bis (3-sulfanyl acetate), Trimethylol propane tris (3-sulfanyl acetate), Butanediol bis (3-sulfanyl propionate), Trimethylol propane tris (3-sulfanyl propionate) cypionate), trimethylolpropane tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl acetate), trishydroxyethyl tris ( 3-sulfanylpropionate), pentaerythritol tetrakis (3-sulfanylbutyrate), and 1,4-bis(3-sulfanylbutyloxy)butane.

The content of the thiol compound (T) is preferably 0.5 to 50 parts by weight, more preferably 5 to 45 parts by weight, and even more preferably 10 to 40 parts by weight, based on 100 parts by weight of the polymerization initiator (D). When the content of the thiol compound (T) is within the above range, sensitivity tends to increase and developability tends to improve.

[7] Solvent (E)

The colored curable resin composition of the present invention preferably contains one or two or more solvents (E). Solvents (E) include ester solvents (solvents containing -COO-), ether solvents other than ester solvents (solvents containing -O-), and ether ester solvents (solvents containing -COO- and -O-). , ketone solvents (solvents containing -CO-) other than ester solvents, alcohol solvents, aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, and ethyl butyrate. , butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran , 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetol and methylaniline. A brush, etc. may be mentioned.

Ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, and 3-ethoxypropionic acid. Methyl, 3-ethoxyethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2 -Methyl propionate, 2-ethoxy-2-methyl ethyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and dipropylene glycol methyl ether acetate.

Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, Cyclopentanone, cyclohexanone, and isophorone can be mentioned.

Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin. Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene. Amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

The solvent (E) preferably contains an organic solvent having a boiling point of 120°C or more and 180°C or less at 1 atm from the viewpoint of coatability and drying properties. Among them, the solvent (E) is propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl. Contains at least one member selected from the group consisting of ether, 3-methoxybutylacetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, and N,N-dimethylformamide. It is preferable to use propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, and 3-ethoxyethyl propionate. It is more preferable to include at least one type selected from the group consisting of.

Content of the solvent (E) is preferably 70 to 95% by weight, more preferably 75 to 92% by weight in the colored curable resin composition. In other words, the solid content of the colored curable resin composition is preferably 5 to 30% by weight, more preferably 8 to 25% by weight. When the content of the solvent (E) is in the above range, the flatness during application becomes good and the color density is not insufficient when a color filter is formed, so the display characteristics tend to be good.

〔8〕Leveling agent (F)

The colored curable resin composition of this invention may contain 1 type, or 2 or more types of leveling agents (F). Examples of the leveling agent (F) include silicone-based surfactants (not having a fluorine atom), fluorine-based surfactants, and silicone-based surfactants having a fluorine atom. These may have a polymerizable group in the side chain.

Silicone-based surfactants (not having a fluorine atom) include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, Copper SH7PA, Copper DC11PA, Copper SH21PA, Copper SH28PA, Copper SH29PA, Copper SH30PA, Copper SH8400 (Product Name: Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324. , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan Joint Stock Company) etc. can be mentioned.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Fluorad (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megapak (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (manufactured by DIC Co., Ltd.), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Material Electronics Co., Ltd.), Suplon (registered trademark) S381 , S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemical Laboratories Co., Ltd.).

Silicone-based surfactants having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megapak (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Co., Ltd.) can be mentioned.

The content of the leveling agent (F) in the colored curable resin composition is usually 0.001% by weight or more and 0.2% by weight or less, preferably 0.002% by weight or more and 0.1% by weight or less, more preferably 0.005% by weight or more and 0.05% by weight. It is as follows. In addition, this content does not include the content of the pigment dispersant.

〔9〕Antioxidant (G)

From the viewpoint of improving the heat resistance and light resistance of the colorant (A), it is preferable that the colored curable resin composition contains an antioxidant. The antioxidant is not particularly limited as long as it is an antioxidant commonly used industrially, and phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, etc. can be used. Two or more types of antioxidants may be used.

As a phenolic antioxidant, Irganox 1010 (Irganox 1010: pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Co., Ltd. ), Irganox 1076 (Irganox 1076: octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, manufactured by BASF Co., Ltd.), Irganox 1330 (Irganox 1330) : 3,3',3",5,5',5"-hexa-t-butyl-a,a',a"-(mesitylene-2,4,6-triyl)tri-p-cresol, BASF Co., Ltd. manufacture), Irganox 3114 (Irganox 3114: 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2 , 4,6(1H,3H,5H)-trione, manufactured by BASF Co., Ltd.), Irganox 3790 (Irganox 3790: 1,3,5-tris ((4-t-butyl-3-hydroxy- 2,6-xylyl)methyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Co., Ltd.), Irganox 1035 (Irganox 1035: Thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Co., Ltd., Irganox 1135 (Irganox 1135: benzenepropanoic acid, 3, 5-bis(1,1-dimethylethyl)-4-hydroxy, C7-C9 side chain alkyl ester, manufactured by BASF Co., Ltd., Irganox 1520L (Irganox 1520L: 4,6-bis(octylthiomethyl) -o-cresol, manufactured by BASF Corporation), Irganox 3125 (Irganox 3125, manufactured by BASF Corporation), Irganox 565 (Irganox 565: 2,4-bis(n-octylthio)-6-( 4-Hydroxy3',5'-di-t-butylanilino)-1,3,5-triazine, manufactured by BASF Co., Ltd., Adeka Stab AO-80 (Adeka Stab AO-80) : 3,9-bis(2-(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetra Oxaspiro(5,5)undecane, manufactured by ADEKA Co., Ltd.), Sumilizer BHT (Sumilizer BHT, manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GA-80 (Sumilizer GA-80, manufactured by Sumitomo Chemical Co., Ltd.) , Sumilizer GS (manufactured by Sumitomo Chemical Co., Ltd.), Cyanox 1790 (manufactured by Cytech Co., Ltd.), and Vitamin E (manufactured by Eisai Co., Ltd.).

Phosphorus-based antioxidants include Irgafos 168 (Irgafos 168: Tris(2,4-di-t-butylphenyl)phosphite, manufactured by BASF Corporation), Irgafos 12 (Irgafos 12: Tris[2-[ [2,4,8,10-tetra-t-butyldibenzo[d,f][1,3,2]dioxaphosphin-6-yl]oxy]ethyl]amine, manufactured by BASF Co., Ltd.), Irgafos 38 (Irgafos 38: Bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl)ethyl ester phosphorous acid, manufactured by BASF Co., Ltd., Adeka Stab 329K (manufactured by ADEKA Co., Ltd.) ), Adeka Stab PEP36 (manufactured by ADEKA Co., Ltd.), Adeka Stab PEP-8 (manufactured by ADEKA Co., Ltd.), Sandstab P-EPQ (manufactured by Clariant Co., Ltd.), Weston 618 (Weston 618, manufactured by GE Co., Ltd.) ), Weston 619G (Weston 619G, manufactured by GE), Ultranox 626 (Ultranox 626, manufactured by GE), and Sumilizer GP (Sumilizer GP: 6-[3-(3-t-butyl-4-hydroxy- 5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f][1.3.2]dioxaphosphepine) (manufactured by Sumitomo Chemical Co., Ltd.), etc. there is.

Sulfur-based antioxidants include dialkylthiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl, or distearyl, and polyols such as tetrakis[methylene(3-dodecylthio)propionate]methane. β-alkyl mercaptopropionic acid ester compounds, etc. can be mentioned.

[10] Other ingredients

The colored curable resin composition of the present invention may, if necessary, contain one or two or more additives such as fillers, polymer compounds other than resin (B), adhesion promoter, ultraviolet absorber, anti-agglomeration agent, organic acid, organic amine compound, and curing agent. It may contain.

Fillers include glass, silica, alumina, etc. Polymer compounds other than resin (B) include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate.

Adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-( 2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane and 3-mercaptopropyltri Methoxysilane, etc. can be mentioned.

Examples of the ultraviolet absorber include benzotriazole-based compounds such as 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole; Benzophenone-based compounds such as 2-hydroxy-4-octyloxybenzophenone; Benzoate-based compounds such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; Triazine-based compounds such as 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol; etc. can be mentioned. Examples of the anti-agglomeration agent include sodium polyacrylate.

Organic acids are used for adjusting developability, etc., specifically,

Aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, and capuric acid;

Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, Aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, and mesaconic acid;

Aliphatic tricarboxylic acids such as tricarbalylic acid, aconitic acid, and camphoronic acid;

Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemellitic acid, and mesitylenic acid;

Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid;

Aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, mellophanic acid, and pyromellitic acid; etc. can be mentioned.

As organic amine compounds,

n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n- Monoalkylamines such as nonylamine, n-decylamine, n-undecylamine, and n-dodecylamine;

Monocycloalkylamines such as cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, and 4-methylcyclohexylamine;

Methylethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine , dialkylamines such as di-tert-butylamine, di-n-pentylamine, and di-n-hexylamine;

Monoalkyl monocycloalkylamine such as methylcyclohexylamine and ethylcyclohexylamine;

Dicycloalkylamine such as dicyclohexylamine;

Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl-n-propylamine, diethyl-n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine , trialkylamines such as triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-tert-butylamine, tri-n-pentylamine, and tri-n-hexylamine. ;

Dialkyl monocycloalkylamines such as dimethylcyclohexylamine and diethylcyclohexylamine;

Monoalkyldicycloalkylamine such as methyldicyclohexylamine, ethyldicyclohexylamine, and tricyclohexylamine;

Monoalkanes such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, and 6-amino-1-hexanol Allamine;

Monocycloalkanolamines such as 4-amino-1-cyclohexanol;

Dialkanolamines such as diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n-pentanolamine, and di-n-hexanolamine;

Dicycloalkanolamines such as di(4-cyclohexanol)amine;

Trialanolamines such as triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, triisobutanolamine, tri-n-pentanolamine, and tri-n-hexanolamine;

Tricycloalkanolamines such as tri(4-cyclohexanol)amine;

3-Amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethylamino-1,2 -Aminoalkanediols such as propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, and 2-diethylamino-1,3-propanediol;

Aminocycloalkanediols such as 4-amino-1,2-cyclohexanediol and 4-amino-1,3-cyclohexanediol;

Amino group-containing cycloalkanone methanol, such as 1-aminocyclopentanone methanol and 4-aminocyclopentanone methanol;

1-Aminocyclohexanonemethanol, 4-aminocyclohexanonemethanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol, 4-diethylaminocyclohexanemethanol, etc. Amino group-containing cycloalkane methanol;

β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1 -Aminocarboxylic acids such as aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, and 4-aminocyclohexanecarboxylic acid;

Aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, p-n-propylaniline, p-isopropylaniline, p-n-butylaniline, p-tert-butylaniline, 1-naphthylamine , aromatic amines such as 2-naphthylamine, N,N-dimethylaniline, N,N-diethylaniline, and p-methyl-N,N-dimethylaniline;

Aminobenzyl alcohol such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, and p-diethylaminobenzyl alcohol;

Aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, and p-diethylaminophenol;

Aminobenzoic acids such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, and p-diethylaminobenzoic acid; etc. can be mentioned.

Examples of the curing agent include compounds that can crosslink the resin (B) by reacting with carboxyl groups in the resin (B) when heated, compounds that can polymerize alone to cure the colored pattern, and epoxy compounds and jade. A cetane compound, etc. can be mentioned.

Epoxy compounds include bisphenol A-based epoxy resins, hydrogenated bisphenol A-based epoxy resins, bisphenol F-based epoxy resins, hydrogenated bisphenol F-based epoxy resins, novolak-type epoxy resins, other aromatic epoxy resins, alicyclic-based epoxy resins, and heterocyclic epoxy resins. Epoxy resins such as type epoxy resins, glycidyl ester resins, glycidylamine resins, and epoxidized oils, brominated derivatives of these epoxy resins, and aliphatic, alicyclic, or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof. , epoxidized products of (co)polymers of butadiene, epoxidized products of (co)polymers of isoprene, (co)polymers of glycidyl (meth)acrylate, and triglycidyl isocyanurate. Commercially available epoxy resins include ortho-cresol novolak-type epoxy resin and “Sumiepoxy (registered trademark) ESCN-195XL-80” (manufactured by Sumitomo Chemical Co., Ltd.).

Examples of the oxetane compound include carbonate bisoxetane, xylylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.

When the colored curable resin composition of the present invention contains an epoxy compound, an oxetane compound, etc. as a curing agent, it may contain a compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. Examples of the compound include polyhydric carboxylic acid, polyhydric carboxylic acid anhydride, and acid generator.

As polycarboxylic acid,

Aromatic polyvalent carboxylic acids such as 3,4-dimethylphthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid, and 3,3',4,4'-benzophenonetetracarboxylic acid Boxylic acid;

Aliphatic polyhydric carboxylic acids such as 1,2,3,4-butanetetracarboxylic acid;

Hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentane Alicyclic polyhydric carboxylic acids such as tetracarboxylic acid and 1,2,4,5-cyclohexanetetracarboxylic acid; etc. can be mentioned.

As polyhydric carboxylic acid anhydride,

Aromatic polyhydric carboxylic acid anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic acid anhydride, and 3,3',4,4'-benzophenone tetracarboxylic dianhydride;

Aliphatic polyvalent carboxylic acid anhydrides such as itaconic acid anhydride, succinic anhydride, citraconic acid anhydride, dodecenylsuccinic anhydride, tricarbalylic anhydride, maleic anhydride, and 1,2,3,4-butanetetracarboxylic acid dianhydride. ;

Hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic anhydride, Cyclopentanetetracarboxylic acid 2 Alicyclic polyhydric carboxylic acid anhydrides such as anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, hymic acid anhydride, and nadic acid anhydride;

Carboxylic acid anhydrides containing ester groups, such as ethylene glycol bistrimellitate acid and glyceroltristrimellitate anhydride; etc. can be mentioned.

As the carboxylic acid anhydride, you may use a commercially available epoxy resin curing agent. As an epoxy resin hardener, the brand name is “Adeka Hardener (registered trademark) EH-700” (manufactured by ADEKA Co., Ltd.), the brand name is “Rikacid (registered trademark) HH” (manufactured by Shin-Nippon Rika Co., Ltd.), and the brand name is “MH.” -700” (manufactured by Shin Nippon Rika Co., Ltd.).

As an acid generator, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4- Acetoxyphenyl·methyl·benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyl iodonium p-toluenesulfonate, diphenyl iodine Examples include onium salts such as nium hexafluoroantimonate, nitrobenzyl tosylate, and benzoin tosylate.

<Method for producing colored curable resin composition>

The colored curable resin composition of the present invention includes a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and, if necessary, a solvent (E), a thiol compound (T), and a leveling agent. It can be prepared by mixing (F), polymerization initiation auxiliary (D1), antioxidant (G), and other components.

＜Color filter and its manufacturing method, color filter, and display device＞

The colored curable resin composition of the present invention is useful as a material for a color filter. A color filter formed from the colored curable resin composition of the present invention also falls within the scope of the present invention. The color filter may form a colored pattern.

Methods for producing a colored pattern from the colored curable resin composition of the present invention include photolithographic methods, inkjet methods, and printing methods. Among them, the photolithographic method is preferable. The photolithographic method is a method of applying a colored curable resin composition to a substrate, drying it to form a colored composition layer, exposing the colored composition layer to light through a photomask, and developing the colored composition layer. In the photolithography method, a colored coating film, which is a cured product of the colored composition layer, can be formed by not using a photomask during exposure and/or not developing. A colored pattern or colored coating film formed from the colored curable resin composition of the present invention is a color filter of the present invention.

The color filter of the present invention is typically used as a blue pixel.

The substrate may be a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, or soda lime glass coated with silica on the surface, a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, or silicon. Aluminum, silver, silver/copper/palladium alloy thin films, etc. are used. Other color filter layers, resin layers, transistors, circuits, etc. may be formed on these substrates.

The formation of each color pixel by the photolithographic method can be performed using known or customary equipment and conditions, and can be produced, for example, as follows. First, the colored curable resin composition is applied onto a substrate and dried to remove volatile components such as solvents by heat drying (prebake) and/or reduced pressure drying to obtain a smooth colored composition layer. Application methods include spin coat method, slit coat method, and slit and spin coat method.

The temperature when performing heat drying is preferably 30 to 120°C, and more preferably 50 to 110°C. Additionally, the heating time is preferably 10 seconds to 5 minutes, and more preferably 30 seconds to 3 minutes. When performing reduced-pressure drying, it is preferable to carry out it in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa. The film thickness of the coloring composition layer is not particularly limited and may be appropriately selected depending on the film thickness of the target color filter.

According to the present invention, a dark color color filter can be formed even if it is a thin film.

Next, the coloring composition layer is exposed through a photomask for forming the desired coloring pattern. The pattern on the photomask is not particularly limited, and a pattern depending on the intended use is used. The light source used for exposure is preferably a light source that generates light with a wavelength of 250 to 450 nm. For example, light below 350 nm can be cut using a filter that cuts this wavelength range, or light around 436 nm, 408 nm, and 365 nm can be cut using a band-pass filter that extracts these wavelength ranges. So it can be taken out selectively. Specifically, light sources include mercury lamps, light-emitting diodes, metal halide lamps, and halogen lamps.

For exposure, it is preferable to use an exposure device such as a mask aligner or stepper because it can irradiate parallel light uniformly over the entire exposure surface or precisely align the photomask and the substrate on which the coloring composition layer is formed. .

By developing the colored composition layer after exposure by contacting it with a developing solution, a colored pattern is formed on the substrate. By development, the unexposed portion of the coloring composition layer is dissolved in the developing solution and removed. The developing solution is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by weight, more preferably 0.03 to 5% by weight. Additionally, the developer may contain a surfactant. The development method may be any of the paddle method, dipping method, and spray method. Additionally, the substrate may be tilted at an arbitrary angle during development. After development, it is preferable to wash with water.

Additionally, it is preferable to post-bake the obtained colored pattern. The post-bake temperature is preferably 150 to 250°C, and more preferably 160 to 235°C. The post-bake time is preferably 1 to 120 minutes, and more preferably 10 to 60 minutes.

The film thickness of the obtained colored coating film is preferably as thin as possible since it affects adjacent pixels. Particularly in the case of thick film, when a liquid crystal panel is manufactured, light from the light source may leak through pixels of two or more colors, and there is a risk that the vividness of colors may be lost when the panel is viewed at an angle. The film thickness of the colored coating film after post-baking is preferably 3 μm or less, and more preferably 2.8 μm or less. The lower limit of the film thickness of the colored coating film is not particularly limited, but is usually 1 μm or more, and may be 1.5 μm or more.

As described above, according to the present invention, a dark color color filter can be formed even if it is a thin film. Additionally, the colored coating film is excellent as a material for a color filter because it can exhibit excellent developability.

The higher the brightness of the colored coating film, the more preferable it is, preferably 38.5 or more, more preferably 39 or more. The upper limit is not particularly limited, but is usually 70 or less.

The color filter according to the present invention is useful as a color filter used in display devices (liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

Example

Hereinafter, the present invention will be described in more detail by showing examples and comparative examples, but the present invention is not limited to these examples. In the examples, % and parts indicating content or usage amount are based on weight, unless otherwise specified.

<Synthesis Example 1: Preparation of xanthene dye>

20 parts of the compound represented by the above formula (1a) and 200 parts of N-propyl-2,6-dimethylaniline (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under light-shielding conditions, and the resulting solution was stirred at 110°C for 6 hours.

The obtained reaction solution was cooled to room temperature, added to a mixed solution of 800 parts of water and 50 parts of 35% by weight hydrochloric acid, and stirred at room temperature for 1 hour, whereupon crystals precipitated. The precipitated crystals were collected as a residue from suction filtration and then dried to obtain the compound represented by the above formula (1-24). Hereinafter, the compound is referred to as “xanthene dye (A-3).”

<Synthesis Example 2: Preparation of resin (B)>

Nitrogen was flowed at 0.02 L/min into a flask equipped with a reflux condenser, dropping funnel, and stirrer to create a nitrogen atmosphere, 200 parts of 3-methoxy-1-butanol and 105 parts of 3-methoxybutyl acetate were added, and the mixture was stirred at 70°C. It was heated until. Next, 60 parts of methacrylic acid, 240 parts of 3,4-epoxytricyclo[5.2.1.0 ^2.6 ] decyl acrylate were dissolved in 140 parts of 3-methoxybutylacetate to prepare a solution, and the solution was poured into a dropping funnel. It was added dropwise into a flask kept at 70°C over 4 hours. Meanwhile, a mixed solution of 30 parts of 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 225 parts of 3-methoxybutylacetate was added dropwise into the flask over 4 hours using another dropping funnel. After the dropwise addition was completed, the temperature was maintained at the same temperature for 4 hours, and then cooled to room temperature to obtain a resin solution with a solid content of 32.6% by weight and an acid value of 110 mg-KOH/g (solid content conversion). The weight average molecular weight Mw of the resin (B) contained in the obtained resin solution was 13,400, and the dispersion degree was 2.50.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained resin (B) were measured using GPC method under the following conditions. The ratio (Mw/Mn) of the weight average molecular weight and number average molecular weight in terms of polystyrene obtained under the following conditions was used as the molecular weight distribution.

Device ; HLC-8120GPC (manufactured by Tosoh Co., Ltd.),

column ; TSK-GELG2000HXL,

column temperature; 40℃,

solvent; THF,

flow rate; 1.0 mL/min,

Solid content concentration of test liquid; 0.001 to 0.01% by weight,

injection volume; 50㎕,

detector; R.I.,

Standard materials for calibration; TSK STANDARD POLYSTYRENE

F-40, F-4, F-288, A-2500, A-500

(manufactured by Tosoh Co., Ltd.).

<Synthesis Example 3: Preparation of pigment dispersion (A1)>

C. I. Pigment Blue 16 12.1 parts

5.4 parts of acrylic pigment dispersant, and

Propylene glycol monomethyl ether acetate 82.5 parts

was mixed and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion (A1) containing C.I. Pigment Blue 16.

<Synthesis Example 4: Preparation of pigment dispersion (A2)>

C. I. Pigment Blue 15:6 12.0 parts

2.0 parts of acrylic pigment dispersant, and

Propylene glycol monomethyl ether acetate 86.0 parts

was mixed and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion (A2) containing C.I. Pigment Blue 15:6.

<Examples 1 to 3 and Comparative Examples 1 to 3>

(1) Preparation of colored curable resin composition

A resin solution containing the xanthene dye (A-3) obtained in Synthesis Example 1, the resin (B) obtained in Synthesis Example 2, the pigment dispersion liquid (A1) obtained in Synthesis Example 3, or the pigment dispersion liquid obtained in Synthesis Example 4. (A2), polymerizable compound (C-1), polymerization initiator (D-1), polymerization initiator (D-2), polymerization initiator (D-3), and leveling agent (E-1) are listed in Table 8. It was mixed so that the compounding amount described was obtained, and a colored curable resin composition was obtained.

In addition, in preparing the colored curable resin composition, propylene glycol monomethyl ether acetate was mixed so that the solid content of the colored curable resin composition was 20% by weight. The unit of the compounding amount of each component in Table 8 is "part by weight", and the compounding amount is converted to solid content. The details of each ingredient are as follows.

[1] Colorant (A-1): C.I. Pigment Blue 16,

[2] Colorant (A-2): C.I. Pigment Blue 15:6,

[3] Colorant (A-3): Compound represented by formula (1-24) (xanthene dye (A-3)),

[4] Resin (B): Resin (B) contained in the resin solution obtained in Synthesis Example 2,

[5] Polymerizable compound (C-1): Pentaerythritol triacrylate (trade name “A-TMM-3LM-N” manufactured by Shinnakamura Chemical Industry Co., Ltd.),

[6] Polymerization initiator (D-1): Formula below

A compound represented by .

[7] Polymerization initiator (D-2): 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'- Biimidazole (brand name “TCDM” manufactured by CHEMBRIDGE INTERNATIONAL CORPORATION),

[8] Polymerization initiator (D-3): 2-mercaptobenzothiazole (trade name “Sanceller M” manufactured by Sanshin Chemical Industry Co., Ltd.),

[9] Leveling agent (F): Polyether-modified silicone oil (trade name “Toray Silicone SH8400” manufactured by Toray Dow Corning Co., Ltd.).

(2) Production of colored coating film

The colored curable resin composition was applied by spin coating on a 2-inch-by-2-inch glass substrate (“Eagle After cooling, the substrate to which this colored curable resin composition was applied was irradiated with light at an exposure dose of 80 mJ/cm2 (based on 365 nm) in an air atmosphere using an exposure machine (“TME-150RSK” manufactured by Topcon Co., Ltd.). did. After that, post-baking was performed at 230°C for 30 minutes in an oven to obtain a colored coating film.

(3) Measuring film thickness

For the obtained colored coating film, the film thickness was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 9.

(4) Chromaticity evaluation

For the obtained colored coating film, spectroscopy was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the xy chromaticity coordinates (x, y) was calculated. The results are shown in Table 9.

In Example 1 and Comparative Example 1, Example 2 and Comparative Example 2, and Example 3 and Comparative Example 3, respectively, the chromaticity coordinates (x, y) are (0.138, 0.058), which are examples of the target blue chromaticity coordinates. Unified to 0.144, 0.044), (0.148, 0.037). In order to achieve this unification, the blending amount of each colorant was adjusted as shown in Table 8. In Examples 1 to 3, the target chromaticity coordinates could be realized with thinner colored coating films compared to Comparative Examples 1 to 3, respectively. Additionally, the chromaticity coordinates (x, y) of blue in Rec.ITU-R BT.2020 are (0.131, 0.046).

(5) Developability

The colored curable resin composition was spin-coated on a 2-inch by 2-inch glass substrate (Eagle 2000; manufactured by Corning), and then prebaked at 100°C for 3 minutes in a clean oven to form a colored composition layer.

Next, the substrate on which the colored composition layer was formed was developed by immersing it in a developer (a water-based developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide) with a liquid temperature of 24°C. The time from the start of development until the end of dissolution of a portion 10 mm from the center of the substrate was measured as the dissolution time. If the dissolution time was 40 seconds or less, the developability was rated as good (○), and if it was longer than that, it was rated as poor (×). The results are shown in Table 10.

<Synthesis Example 5: Preparation of pigment dispersion (A3)>

Violet 23 12.0 parts

2.0 parts of acrylic pigment dispersant, and

Propylene glycol monomethyl ether acetate 86.0 parts

was mixed and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion liquid (A3) containing Violet 23.

<Examples 4 to 11 and Comparative Examples 4 to 11>

(1) Preparation of colored curable resin composition

Pigment dispersion (A3) obtained in Synthesis Example 5, any of the colorants (A-5) and (A-6) below, a resin solution containing the resin (B) obtained in Synthesis Example 2, and the pigment dispersion ( A1) or the pigment dispersion (A2), and the polymerizable compound (C-1), the polymerization initiator (D-1), the polymerization initiator (D-2), the polymerization initiator (D-3), and the leveling agent. The agent (E-1) was mixed so that the mixing amount shown in Tables 11 to 13 was obtained, and a colored curable resin composition was obtained.

In addition, in preparing the colored curable resin composition, propylene glycol monomethyl ether acetate was mixed so that the solid content of the colored curable resin composition was 20% by weight. The unit of the compounding amount of each component in Tables 11 to 13 is “part by weight,” and the compounding amount is converted to solid content. The details of each ingredient are as follows.

[1] Colorant (A-4): Pigment dispersion (A3) obtained in Synthesis Example 5

[2] Colorant (A-5): Acid Red 52

[3] Colorant (A-6): Basic Red 1

(2) Production of colored coating film

The colored curable resin composition was applied by spin coating on a 2-inch-by-2-inch glass substrate (“Eagle After cooling, the substrate to which this colored curable resin composition was applied was irradiated with light at an exposure dose of 80 mJ/cm2 (based on 365 nm) in an air atmosphere using an exposure machine (“TME-150RSK” manufactured by Topcon Co., Ltd.). did. After that, post-baking was performed at 230°C for 30 minutes in an oven to obtain a colored coating film.

(3) Measuring film thickness

For the obtained colored coating film, the film thickness was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Tables 14 to 16.

(4) Chromaticity evaluation

For the obtained colored coating film, spectroscopy was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the xy chromaticity coordinates (x, y) was calculated. The results are shown in Tables 14 to 16.

In Comparative Example 4, the same chromaticity coordinates (0.130, 0.107) as Example 4 could not be achieved. In Example 5 and Comparative Example 5, Example 6 and Comparative Example 6, the chromaticity coordinates (x, y) were unified to (0.135, 0.083) and (0.139, 0.066), which are examples of the target blue chromaticity coordinates, respectively. In Examples 4 and 5, the target chromaticity coordinates could be realized with thinner colored coating films compared to Comparative Examples 4 and 5, respectively.

In Comparative Example 7, the same chromaticity coordinates (0.135, 0.072) as Example 7 could not be achieved. In Example 8 and Comparative Example 8, Example 9 and Comparative Example 9, the chromaticity coordinates (x, y) were unified to (0.140, 0.054) and (0.144, 0.044), which are examples of the target blue chromaticity coordinates, respectively. In Examples 8 and 9, the target chromaticity coordinates could be realized with thinner colored coating films compared to Comparative Examples 8 and 9, respectively.

In Example 10 and Comparative Example 10, Example 11 and Comparative Example 11, the chromaticity coordinates (x, y) were unified to (0.135, 0.081) and (0.141, 0.059), which are examples of the target blue chromaticity coordinates, respectively. In Examples 10 and 11, the target chromaticity coordinates could be realized with thinner colored coating films compared to Comparative Examples 10 and 11, respectively.

Claims (6)

Containing a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D),
The colorant (A) includes CI Pigment Blue 16, a red colorant and/or a purple colorant,
The total content of CI Pigment Blue 16, red colorant and/or purple colorant is 70 to 100% by weight based on 100% by weight of colorant (A),
A colored curable resin composition in which the total content ratio of CI Pigment Blue 16, a red colorant, and/or a purple colorant is in the range of 1.1 to 10 based on weight. According to claim 1,
A colored curable resin composition in which the red colorant and/or the purple colorant is a dye. delete According to claim 1,
The colorant (A) is a colored curable resin composition containing CI Pigment Blue 16 and a red colorant. A color filter formed from the colored curable resin composition according to claim 1 or 2. A display device comprising the color filter according to claim 5.