TW201740192A - Colored curable resin composition, color filter and display device including same - Google Patents

Abstract

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

Description

Colored curable resin composition, color filter, and display device containing the same

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

In recent years, in the video format of the color reproduction area specified by Rec. ITU-R BT.2020, the demand for a liquid crystal display device having a wide color reproduction area can be improved, so that the liquid crystal display device is being used for The development of the color reproduction area that can be displayed. As one of the rings, it is more demanding.

As a method of coloring the color filter, a method of increasing the concentration of the coloring agent in the color filter can be cited. However, when the concentration of the colorant is increased, the deterioration of the shape of the pattern or the like deteriorates as the performance of the colored curable resin composition. On the other hand, by using a coloring agent having a high coloring power, patterning of a color filter having a rich color can be performed. However, when a coloring agent having a high coloring power is used, there is a case where the brightness is lowered. Further, a method of obtaining a color filter having a rich color by forming a color filter into a thick film may be mentioned. However, when thick film is formed, if it is applied to a liquid crystal display device, it is adjacent to the adjacent image. A mixture of light will occur between the elements.

Japanese Laid-Open Patent Publication No. 2012-088423 discloses a blue photosensitive resin composition as a photosensitive resin composition capable of improving a phase difference in a diagonal direction of a blue colored layer, the blue photosensitive resin composition containing: CI Pigment Blue 15:6, at least one of CI Pigment Blue 16, CI Pigment Blue 60, and CI Pigment Blue 80.

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

[1] A colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), wherein the colorant (A) contains CI Pigment Blue 16 with red colorant and / or purple colorant.

[2] The colored curable resin composition according to [1], wherein the red colorant and/or the violet colorant dye are used.

[3] The colored curable resin composition according to [1], wherein the red coloring agent and/or the purple coloring agent are compounds 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 comprising the color-curable resin composition according to any one of the above [1] to [4].

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

<Coloring 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) contains CI Pigment Blue 16 and a red colorant. And / or purple colorants.

By using a color-curable resin composition containing a specific combination of C.I. Pigment Blue 16 and a red colorant and/or a purple colorant, a color filter of a rich color can be obtained even with a film and a moderate colorant concentration.

In the present specification, the compounds exemplified as the respective components may be used singly or in combination of plural kinds unless otherwise specified.

[1] Colorant (A)

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

Since the colored curable resin composition of the present invention contains the coloring agent (A) described above, it is possible to obtain a colored coating film which is a film of a color with a moderate coloring agent concentration and a good color development property. Therefore, the colored curable resin composition can be used as a material of the coloring pattern.

Red colorants and purple colorants can be pigments or dye. The coloring agent (A) may contain one or more red coloring agents and/or purple coloring agents in addition to C.I. Pigment Blue 16, and may be used in combination with a pigment and a dye.

As the pigment of the red coloring agent and the purple coloring agent, a compound classified as a red pigment in the Color Index (published by The Society of Dyers and Colourists), for example, CI 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 are classified as purple pigments A compound such as a violet pigment such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38, or the like. It is also possible to use two or more kinds of pigments in combination.

For the dyes of the red coloring agent and the purple coloring agent, one or two or more kinds of conventionally known dyes can be used. Among them, from the viewpoint of obtaining a color filter of a rich color, the dye preferably contains a compound having a xanthene skeleton (hereinafter also referred to as "oxaxanthene dye"), and more preferably consists of the compound.

Further, from the viewpoint of obtaining a color filter of a rich color, the red colorant and/or the purple colorant are preferably composed of one or two or more kinds of dyes, and more preferably a compound represented by the formula (1). (Hereinafter, also known as "oxonium dye (1)"):

The xanthene dye (1) may be used alone or in combination of two or more.

In the 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 respectively. A ring containing a nitrogen atom is formed. The hydrogen atom contained in the aromatic hydrocarbon group may be via 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 are} substituted. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

R ⁵ represents -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 ₂ NR ⁹ R ¹⁰ .

The m system represents an integer of 0 to 5. When m is an integer of 2 or more, a plurality of R ^{5 's} may be the same or different from each other.

R ⁶ and R ⁷ each independently represent a hydrogen atom or a C 1 to 6 alkyl group. The M ⁺ system represents ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ . X is a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. a indicates 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 the -CH ₂ - contained in the saturated hydrocarbon group may be -S-, -O-, -CO- or -NR ¹¹ - replaced. 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 are a plurality of R ¹¹ , these may be all or part of 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 by -OH or a halogen atom, and the saturated aliphatic hydrocarbon group is contained -CH ₂ - may be substituted by -S-, -O-, -CO-, -NH- or -NR ⁸ -, and R ⁹ and R ¹⁰ may be bonded to each other to form a heterocyclic ring of 3 to 10 members containing a nitrogen atom. ring. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

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

Among R ¹ to R ⁴ in the formula (1), the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms preferably has a group selected from -SO ₃ -, -SO ₃ H, -SO ₃ ^- M ⁺ and -SO ₂ at least one of the groups of NR ⁹ R ¹⁰ is a substituent, and more preferably has at least one selected from the group consisting of -SO ₃ ^- M ⁺ and -SO ₂ NR ⁹ R ¹⁰ as a substituent. In the case of -SO ₃ ^- M ⁺ at this time, -SO ₃ ^-+ N(R ¹¹ ) _{4 is} preferred. When R ¹ to R ^{4 are} these groups, it is advantageous to form a color filter excellent in heat resistance.

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

In the case of R ⁸ to R ¹¹ in the formula (1), the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or an isobutyl group. Alkyl 1 to 20, such as pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, decyl, decyl, dodecyl, hexadecanyl, and decyl a cycloalkyl group having a carbon number of 3 to 20, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group or a tricyclodecyl group.

With respect to the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ⁸ , the aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted by a hydrogen atom may, for example, be a phenyl group, a tolyl group, a xylyl group or a mesitylene group. Base, propylphenyl and butylphenyl groups. The group substituted with -CH ₂ -R-S-, -O-, -CO- or -NR ¹¹ - contained in R ⁸ may, for example, be the following group.

The alkyl group having 1 to 6 carbon atoms in R ⁶ and R ⁷ in the formula (1) includes the above-exemplified alkyl groups and having 1 to 6 carbon atoms.

The group represented by -SO ₂ NR ⁹ R ¹⁰ may, for example, be a group represented by the following formula.

In the above formula, X ¹ represents a halogen atom. The halogen atom in X ¹ may, for example, be a fluorine atom, a chlorine atom or a bromine atom.

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

M ⁺ is ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ¹¹ ) ₄ . ⁺ N(R ¹¹ ) _{4 is} preferably at least 2 of 4 R ¹¹ is a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. Further, the total carbon number of the four R ¹¹ is preferably from 20 to 80, more preferably from 20 to 60.

The xanthene dye (1) is more preferably a compound represented by the formula (2):

In the 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 may pass through -SO ₃ - , -SO ₃ ^- M ^a+ , -SO ₃ H, -SO ₃ R ²⁶ or -SO ₂ NHR ^{26 is} substituted. X is a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

A1 indicates 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 ²⁷ groups independently represent a monovalent saturated hydrocarbon group or a benzyl group having 1 to 20 carbon atoms.

The monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ²¹ to R ²⁴ in the formula (2) may be the same as those exemplified as the aromatic hydrocarbon group in R ¹ to R ⁴ . Wherein R ²¹ and R ²³ are a hydrogen atom and R ²² and R ²⁴ are a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and when a hydrogen atom contained in the aromatic hydrocarbon group is substituted, the substituted group is preferably -SO ₃ -, -SO ₃ ^- M ⁺ , -SO ₃ H, -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ . Further, it is more preferred that R ²¹ and R ²³ are a hydrogen atom and R ²² and R ²⁴ are a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may pass through -SO ₃ ^- M ⁺ Or -SO ₂ NHR ²⁶ replacement. When R ²¹ to R ^{24 are} these groups, it is advantageous to form a color filter excellent in heat resistance.

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ²⁶ and R ²⁷ in the formula (2) may be the same as those exemplified as the saturated hydrocarbon group in R ⁸ to R ¹¹ . In the ²⁴ -R R (2) in the formula ²¹ to R ²⁶ each independently is preferably based hydrogen atom, methyl or ethyl.

Of formula (2) -SO ₃ R ²⁶ and -SO ₂ NHR ²⁶ R ²⁶ in terms of, preferably branched chain alkyl group having a carbon number of lines 3-20, the better system of 6 to 12 carbon atoms Branched chain alkyl, more preferably 2-ethylhexyl.

M ^a+ is ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ²⁷ ) ₄ . ⁺ N(R ²⁷ ) _{4 is} preferably at least 2 of 4 R ²⁷ being a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. Further, the total carbon number of the four R ²⁷ is preferably from 20 to 80, more preferably from 20 to 60.

The oxonium dye (1) is preferably a compound represented by the formula (1-1) to the formula (1-16). Further, in each formula, the Ra system represents 2-ethylhexyl.

Among these compounds, a sulfonium amidate of C.I. Acid Red 289 or a 4-grade ammonium salt of C.I. Acid Red 289 is more preferred. Examples of such a compound include each compound represented by the formula (1-1) to the formula (1-8), the formula (1-11), and the formula (1-12).

The compound of the formula (1-1) to the formula (1-16) can be produced by the method described in the method from the upper right column to the lower left column of page 3 of JP-A No. 3-78702. Similarly, it is produced by a method of reacting with an amine after chlorination.

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

The compound represented by the formula (1-17) to the formula (1-31) can be produced according to the method described in the upper right column to the lower left column of page 3 of JP-A-3-78702.

The method of reacting the compound represented by the formula (1a), the compound represented by the formula (1b) and the compound represented by the formula (1c) can be mentioned. In the formulae (1b) and (1c), R ¹ to R ⁴ each have the same meanings as described above.

As the xanthene dye (1), a commercially available xanthene dye (for example, "Chugai Aminol Fast Pink R-H/C" manufactured by Sino-foreign Chemical Co., Ltd., and "Rhodamin 6G" manufactured by Tajika Chemical Industry Co., Ltd.) can be used. A commercially available xanthene dye can also be used as a starting material, and it can be synthesized by referring to JP-A-2010-32999.

Specific examples of the xanthene dye (1) include CI acid red 51 (hereinafter, the description of CI acid red is omitted, only the number is described. The others are also the same), 52, 87, 92, 94, 289 388, etc. CI acid red dye; CI acid violet 9, 30, 102, etc. CI acid violet dye; CI alkaline red 1 (rose red 6G), 2, 3, 4, 8, 10 (Rose red B), 11 etc. CI basic red dye; CI alkaline purple 10, 11, 25 and other CI alkaline violet dye; CI solvent red 218 and other CI solvent red dye; CI mordant red 27 and other CI mordant red dye; CI active red 36 (Bangladesh rose red B), etc., a CI-reactive red dye; a sulphur rose red G (sulforhodamine G); a xanthene dye described in JP-A-2010-32999; and a xanthene dye described in Japanese Patent No. 4492760.

The content ratio of the total amount of the CI pigment blue 16 to the red colorant and the purple colorant in the colorant (A) (the total of the CI pigment blue 16/red colorant and the purple colorant) is usually 0.8 on a weight basis. Up to 20, from the viewpoint of obtaining a color filter of a rich color, it is preferably from 1 to 15, more preferably from 1.1 to 10, still more preferably from 1.2 to 8.

The colorant (A) may contain other colorants other than C.I. Pigment Blue 16, a red colorant, and a violet colorant. Other colorants may be pigments, dyes, or both. The other coloring agents may be used alone or in combination of two or more. Examples of the other pigments include organic pigments and inorganic pigments, and examples thereof include compounds classified as pigments in the color index (published by The Society of Dyers and Colourists).

As the other dye, a known dye can be used, and examples thereof include a solvent dye, an acid dye, a direct dye, a mordant dye, and the like. As the dye, a known dye described in a color index (published by The Society of Dyers and Colourists), which is classified into a pigment and has a hue, and a dyeing note (color dyeing company) can be cited. Further, depending on the chemical structure, an azo dye, a cyanine dye, a triphenylmethane dye, an anthraquinone dye, an anthraquinone dye, a naphthoquinone dye, a quinone imine dye, a methine dye, or an even Nitromethine dye, squarylium dye, acridine dye, styryl dye, coumarin dye, quinoline dye, nitro dye, and the like. Among these, an organic solvent-soluble dye is preferred.

The colorant (A) may contain other blue colorants (blue pigment and/or blue dye) other than C.I. Pigment Blue 16. As for other blue pigments, for example, C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60, and the like can be exemplified.

As the blue dye, CI solvent blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79 can be cited. , 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, CI solvent blue dyes such as 136, 139; CI 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, 236, 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340, etc. CI acid blue dye; CI 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, 16 0, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, CI1 direct blue dyes such as 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; CI disperse blue 1, 14, 56, 60, etc. Material; CI 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 and other CI alkaline blue dye; CI mord 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, etc. CI mordant blue dye or the like.

However, from the viewpoint of the enlargement of the color reproduction region which can be displayed, the higher the total content of C.I. Pigment Blue 16 and the red colorant and the purple colorant in the colorant (A), the better. Specifically, in 100% by weight of the colorant (A), the total content of the CI Pigment Blue 16 and the red colorant and the purple colorant in the colorant (A) is preferably from 50 to 100% by weight, more preferably 70. Up to 100% by weight, more preferably 80 to 100% by weight, particularly preferably 90 to 100% by weight.

In 100% by weight of the colorant (A), the content of the CI Pigment Blue 16 in the colorant (A) is usually 20 to 95% by weight, and from the viewpoint of obtaining a color filter of a rich color, the preferred system 40 Up to 90% by weight, more preferably 50 to 85% by weight.

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

The solid content of the colored curable resin composition is 100 weights In the %, the total content of the coloring agent (A) in the coloring curable resin composition is usually 10 to 50% by weight, but from the viewpoint of obtaining a color filter of a rich color, it is preferably 30% by weight or more. More preferably, it is 15 to 40% by weight, more preferably 20 to 35% by weight. The total content of the solid content of the colored curable resin composition is preferably 45% by weight or less, from the viewpoint of easiness of formation of the resist pattern.

According to the present invention, a color filter conforming to the color gamut of Rec. ITU-R BT.2020 can be formed. In the present specification, the "solid content of the colored curable resin composition" means all the components other than the solvent (E) in the component contained in the colored curable resin composition.

The various pigments used for the preparation of the colored curable resin composition are preferably in a state of dispersion in which a solvent is uniformly dispersed. Further, the pigment preferably has a uniform particle size. The above dispersion can be obtained by mixing a pigment with a solvent. A pigment dispersant may also be mixed as needed. A pigment dispersion liquid in a state in which the pigment is uniformly dispersed in a solvent can be obtained by containing a pigment dispersant and performing a dispersion treatment.

As the pigment dispersant, commercially available surfactants can be used, and examples thereof include polyfluorene-based, fluorine-based, ester-based (including polyester), cationic, anionic, nonionic, amphoteric, and polyester. A surfactant such as a polyamine system or an acrylic resin. Specific examples of the surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyethylene glycol diester, sorbitan fatty acid ester, fatty acid modified polyester, and tertiary amine. In addition to the modified polyurethane, polyethyleneimine, etc., the product name: KP (Shin-Etsu Chemical Co., Ltd.), Flowlen (Kyoei Chemical Co., Ltd.), Solsperse (manufactured by ZENECA Co., Ltd.), EFKA (manufactured by BASF Japan Co., Ltd.), Ajisper (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (manufactured by BYK-Chemie Co., Ltd.), and the like. The pigment dispersing agent may be used alone or in combination of two or more.

When the pigment dispersant is used, the pigment dispersant is preferably used in an amount of 100 parts by weight or less, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the pigment. When the amount of the pigment dispersant used is in the above range, there is a tendency that a pigment dispersion liquid in a uniformly dispersed state is easily obtained.

The solvent constituting the pigment dispersion liquid is not particularly limited, and examples thereof include the solvent similar to the solvent (E) described later, and the colored curable resin composition. Among them, the solvent is preferably propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, 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-di Methylformamide, etc., preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3- Methoxy-1-butanol, ethyl 3-ethoxypropionate, and the like.

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

Various pigments used for preparation of the coloring curable resin composition may be subjected to rosin treatment, surface treatment using a pigment derivative or a pigment dispersant having an acidic group or a basic group, or a polymer compound, etc., if necessary. Grafting treatment of pigment surface, by sulfuric acid micronization, etc. The micronization treatment, the cleaning treatment by an organic solvent and water for removing impurities, the removal treatment of an ionic impurity by an ion exchange method, or the like.

[2] Resin (B)

The colored curable resin composition of the present invention contains one or more resins (B). The resin (B) is preferably an alkali-soluble resin. The alkali solubility means a property of a developing solution dissolved in an aqueous solution belonging to an alkali compound. The resin (B) may, for example, be the following resins [K1] to [K6].

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

Resin [K2]: (a) and (b), and monomer (c) copolymerizable with (a) (except that is different from (a) and (b)) [hereinafter, sometimes referred to as "( Copolymer of c)"].

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

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

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

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

Specific examples of (a) include (meth)acrylic acid, crotonic acid, o-, m-, p-ethylene Unsaturated monocarboxylic acid such as benzoic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl decanoic acid, 3, 4, 5, Unsaturated dicarboxylic acid such as 6-tetrahydrofurfuric acid, 1,2,3,6-tetrahydrofurfuric acid, dimethyltetrahydrofurfuric acid or 1,4-cyclohexene dicarboxylic acid; methyl-5- Decalene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5 -Methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]g a carboxylic acid-containing bicyclic unsaturated compound such as 2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl anthracene Anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] Unsaturated dicarboxylic anhydride such as hept-2-ene anhydrate (Himic anhydride); succinic acid mono [2-(methyl) propylene decyloxyethyl] ester, citric acid Unsaturated mono[(meth)propene of 2 or more polycarboxylic acids such as mono[2-(methyl)propenyloxyethyl]ester A mercaptooxyalkyl] ester; such as an unsaturated (meth)acrylic acid having a hydroxyl group and a carboxyl group in the same molecule of α-(hydroxymethyl)(meth)acrylic acid.

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

In the present specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. "(A The same applies to the labels such as "acryloyl" and "(meth)acrylate".

(b) means a cyclic ether structure having a carbon number of 2 to 4 [e.g., selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring (oxolane ring)) a polymerizable compound with an ethylenically unsaturated bond. (b) is preferably a monomer having a cyclic ether structure of 2 to 4 carbon atoms and a (meth) propylene fluorenyloxy group.

(b), for example, a monomer (b1) having an oxirane group and an ethylenically unsaturated bond [hereinafter, sometimes referred to as "(b1)"], having an oxetane group Monomer (b2) having an ethylenically unsaturated bond [hereinafter, sometimes referred to as "(b2)"], a monomer having a tetrahydrofuranyl group and an ethylenically unsaturated bond (b3) [hereinafter, sometimes referred to as "( B3)"] and so on.

(b1), a monomer (b1-1) having a structure in which an unsaturated aliphatic hydrocarbon is epoxidized (hereinafter, sometimes referred to as "(b1-1)"), and having an unsaturated fat A monomer (b1-2) having a structure in which a cyclic hydrocarbon is epoxidized [hereinafter, sometimes referred to as "(b1-2)").

Examples of (b1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, and β-ethylglycidyl (meth)acrylate. Epoxypropyl vinyl ether, o-vinylbenzyloxypropyl ether, m-vinylbenzyloxypropyl ether, p-vinylbenzyloxypropyl ether, α-甲Base-o-vinylbenzyloxypropyl ether, α-methyl-m-vinylbenzyloxypropyl ether, α-methyl-p-vinylbenzyloxypropyl ether , 2,3-bis(glycidoxymethyl)styrene, 2,4-bis(glycidoxymethyl)styrene, 2,5-bis(epoxypropyloxymethyl) Styrene, 2,6-bis(glycidoxyoxymethyl)styrene, 2,3,4-paranium (epoxypropyl) Oxymethyl)styrene, 2,3,5-glycol(epoxypropyloxymethyl)styrene, 2,3,6-glycol(epoxypropyloxymethyl)styrene, 3, 4,5-glycol (epoxypropyloxymethyl)styrene, 2,4,6-glycol (epoxypropyloxymethyl)styrene, and the like.

(b1-2), vinylcyclohexene monooxide, 1,2-epoxy 4-vinylcyclohexane (for example, CELLOXIDE 2000; manufactured by Daicel Chemical Industry Co., Ltd.), ( 3,4-Epoxycyclohexylmethyl (meth)acrylate (for example, CYCLOMER A400; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, CYCLOMER) M100; manufactured by Daicel Chemical Industry Co., Ltd.), a compound represented by the following formula (I), a compound represented by the following formula (II), and the like.

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

The alkyl group having 1 to 4 carbon atoms may, for example, be methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl or t-butyl.

Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxyl group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, and a 2- Hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl group and the like.

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, more preferably a hydrogen atom or a methyl group.

Examples of the alkanediyl group constituting R ^c include a methylene group, an ethylidene group, a propane-1,2-diyl group, a propane-1,3-diyl group, and a butane-1,4-diyl group. Pentane-1,5-diyl, hexane-1,6-diyl and the like.

X ¹ and X ^{2 are} preferably a single bond, a methylene group, an ethylidene group, a *-CH ₂ -O- (* is a bond to the bond with O), and a *-CH ₂ CH ₂ -O- group. More preferably, it is a single bond, *-CH ₂ CH ₂ -O- group.

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

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

The compound represented by the formula (I) and the compound represented by the formula (II) can be used alone. These can be mixed in any ratio. When mixing, the mixing ratio is calculated by the formula (I): formula (II) [mole ratio], preferably 5:95 to 95:5, more preferably 10:90 to 90:10, and even more preferably 20 : 80 to 80:20.

The monomer (b2) having an oxetane group and an ethylenically unsaturated bond is preferably a monomer having an oxetanyl group and a (meth) acrylenyloxy group. Preferred examples of (b2) include 3-methyl-3-(methyl)propenylmethoxymethyloxetane and 3-ethyl-3-(methyl)propenyloxyl Methyl oxetane, 3-methyl-3-(methyl) propylene decyloxyethyl oxetane, 3-ethyl-3-(methyl) propylene decyloxyethyl Oxetane.

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

Specific examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, and (meth)acrylic acid. Third butyl ester, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopenta(meth)acrylate Ester, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl ester [in this technology] In the field, the customary name is called "dicyclopentanyl (meth)acrylate". Further, there is also a case called "tricyclodecyl (meth) acrylate], tricyclo [5.1.02 ^2,6 ]nonene-8-yl ester [in the technical field, conventionally used The name is called "dicyclopentenyl (meth)acrylate], dicyclopentyloxyethyl (meth)acrylate, isodecyl (meth)acrylate, adamantyl (meth)acrylate, (meth) acrylate such as allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate or benzyl (meth) acrylate; a hydroxyl group-containing (meth) acrylate such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate; diethyl maleate, diethyl fumarate, and itaconic acid Dicarboxylic acid diester such as ethyl ester; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2 - alkene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1 Hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2 .1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2 .2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]heptane- 2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5- Ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-t-butoxycarbonylbicyclo[2.2.1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis (p. a tricyclic unsaturated compound such as tributoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-benzene Kamalyimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimido-3-maleimide benzoate, N- Amber succinimide-4-maleimide butyrate, N-succinimide-6-maleimide caproate, N-succinimide-3-malaya Dicarbonyl ruthenium imide such as amine propionate or N-(9-acridinyl)maleimide; styrene, α-methylstyrene, m-methylstyrene, p-methylbenzene Ethylene, vinyl toluene, p-Methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene , 2,3-dimethyl-1,3-butadiene, and the like.

Among them, (c) is preferably benzyl (meth) acrylate, tricyclodecyl (meth) acrylate, styrene, N-phenyl maleate from the viewpoints of copolymerization reactivity and heat resistance. Imine, N-cyclohexylmaleimide, N-benzylmaleimine, bicyclo[2.2.1]hept-2-ene, and the like. Further, (c) is preferably benzyl (meth) acrylate or tricyclodecyl (meth) acrylate because it is excellent in developability at the time of pattern formation.

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

Structural unit derived from (a): 2 to 50 mol% (better 10 to 45 mol%), the structural unit derived from (b), especially the structural unit derived from (b1): 50 to 98 mol% (more preferably 55 to 90 mol%).

When the ratio of the structural unit of the resin [K1] is in the above range, it has a tendency to preserve stability and developability, and the solvent resistance of the obtained pattern is excellent.

Resin [K1] can be found in the literature "Experimental Methods for Polymer Synthesis" (Dazu Takashi, Institute of Chemicals, the first edition of the first brush, issued on March 1, 1972) and the literature Manufactured from the cited references.

Specifically, a method of feeding a predetermined amount of (a) and (b) (especially (b1)), a polymerization initiator, a solvent, and the like into a reaction vessel, and stirring, heating, and heat-retaining in a deoxidizing environment . In addition, the polymerization initiator, the solvent, and the like used herein are not particularly limited, and any of the usual users in the field can be used. Examples of the polymerization initiator include an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.), and organic Oxide (benzaldehyde peroxide, etc.). The solvent is not particularly limited as long as it dissolves each monomer, and a solvent (E) or the like described later can be used as a solvent for the colored curable resin composition.

Further, the copolymer obtained may be a solution directly after the reaction, a solution which is concentrated or diluted, or a solid (powder) which is taken out by a method such as reprecipitation. In particular, in the polymerization, by using the solvent (E) described below as a solvent, the solution after the reaction can be used as it is, and the production steps can be simplified.

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

The structural unit derived from (a): 4 to 45 mol% (more preferably 10 to 30 mol%), the structural unit derived from (b), especially the structural unit derived from (b1): 2 to 95 Mole% (more preferably 5 to 80 mol%), structural unit derived from (c): 1 to 65 mol% (more preferably 5 to 60 mol%).

When the ratio of the structural unit of the resin [K2] is in the above range, there is a tendency to preserve stability, developability, solvent resistance, heat resistance and mechanical strength of the obtained pattern.

The resin [K2] can be produced in the same manner as the method described in the production method of the resin [K1]. Specifically, a predetermined amount of (a), (b) (especially (b1)) and (c), a polymerization initiator and a solvent are fed into the reaction vessel, and stirred, heated, and kept in a deoxidizing environment. The method. The obtained copolymer may be directly used as a solution after the reaction, or a solution which is concentrated or diluted, or may be used as a solid (powder) by reprecipitation or the like.

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

Structural unit derived from (a): 2 to 55 mol% (more preferably 10 to 50 mol%), structural unit derived from (c): 45 to 98 mol% (more preferably 50 to 90 mol) ear%).

The resin [K3] can be produced in the same manner as the method described in the production method of the resin [K1].

The resin [K4] can be obtained by: obtaining a copolymer of (a) and (c) such that (b) has a cyclic ether structure having a carbon number of 2 to 4, particularly (e.g.) The cycloaddition is produced by the carboxylic acid and/or carboxylic anhydride contained in (a). Specifically, first, the copolymers of (a) and (c) are produced in the same manner as the method described in the method for producing the resin [K1]. In this case, the ratio of the structural unit derived from each of them is preferably in the following range among all the structural units constituting the copolymer of (a) and (c).

Structural unit derived from (a): 5 to 50 mol% (more preferably 10 to 45 mol%), structural unit derived from (c): 50 to 95 mol% (more preferably 55 to 90 mol) ear%).

Then, the cyclic ether structure of the carboxylic acid and/or carboxylic anhydride derived from (a) and (b) having a carbon number of 2 to 4 in the above copolymer, especially the ring of (b1) The oxyethylene ring is reacted. Specifically, after the manufacture of the copolymer of (a) and (c), the environment inside the flask is then replaced with nitrogen from air, and (b) (especially (b1)), a carboxylic acid or a carboxylic anhydride and a ring The reaction catalyst of the ether structure (for example, ginseng (dimethylaminomethyl) phenol, etc.] and a polymerization inhibitor (for example, hydroquinone or the like) are placed in a flask, and reacted at 60 to 130 ° C for 1 to 10 hours. This gave the resin [K4].

The amount of use (b), particularly (b1), is preferably from 5 to 80 moles, more preferably from 10 to 75 moles, relative to (a) 100 moles. By setting it as this range, it has storage stability, imaging property, solvent resistance, heat resistance, The balance between mechanical strength and sensitivity tends to be good. Since the reactivity of the cyclic ether structure is high, unreacted (b) is not easily left, and (b) used in the resin [K4] is preferably (b1), more preferably (b1-1).

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

The reaction conditions such as the feeding method, the reaction temperature, and the time can be appropriately adjusted in consideration of the manufacturing equipment, the calorific value due to the polymerization, and the like. In addition, the feeding method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the calorific value due to the polymerization, and the like in the same manner as the polymerization conditions.

Resin [K5], as the first stage, a copolymer of (b) (especially (b1)) and (c) is obtained in the same manner as in the above-mentioned method for producing the resin [K1]. Similarly to the above, the obtained copolymer may be directly used as a solution after the reaction, or a solution which is concentrated or diluted, or may be used as a solid (powder) by reprecipitation or the like.

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

The structural unit derived from (b), especially the structural unit derived from (b1): 5 to 95 mol% (more preferably 10 to 90 mol%), structural unit derived from (c): 5 to 95 Molar% (more preferably 10 to 90 mol%).

Furthermore, it can be the same as the manufacturing method of the resin [K4] a condition in which (b) (especially the (b1)) and (c) copolymers have a cyclic ether structure derived from (b) and (a) a carboxylic acid or a carboxylic acid anhydride, thereby obtaining Resin [K5]. The amount of (a) to be reacted with the above copolymer is preferably from 5 to 80 moles relative to (b) (particularly (b1)) 100 moles. Since the cyclic ether structure has high reactivity and does not easily remain unreacted (b), the (b) used in the resin [K5] is preferably (b1), more preferably (b1-1).

The resin [K6] is a resin obtained by further reacting the resin [K5] with a carboxylic acid anhydride. The hydroxyl group produced by the reaction of a cyclic ether structure with a carboxylic acid or a carboxylic acid anhydride is reacted with a carboxylic acid anhydride.

The carboxylic anhydride may, for example, be maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1, 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydrate (seamic anhydride) and the like.

Among the resins [K1] to [K6], the preferred resin system [K1] or [K2] of the resin (B). The resin (B) may be one type of resin or two or more types of resins.

The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, still more preferably from 5,000 to 30,000. When the molecular weight is in the above range, the solubility of the unexposed portion in the developing solution is high, and the residual film ratio and hardness of the obtained pattern tend to be high. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably from 1.1 to 6, more preferably from 1.2 to 4.

The acid value of the solution of the resin (B) is preferably from 5 to 180 mg-KOH/g, more preferably from 10 to 100 mg-KOH/g, and even more preferably 12 Up 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 from 5 to 50% by weight, more preferably from 10 to 40% by weight, still more preferably from 15 to 30% by weight, based on 100% by weight of the solid content of the colored curable resin composition. When the content of the resin (B) is in the above range, the solubility of the unexposed portion in the developing solution tends to be high.

[3] Polymeric compound (C)

The polymerizable compound (C) is a compound which can be polymerized by an active radical generated from a polymerization initiator (D) by light irradiation or the like, and is not particularly limited, and examples thereof include a polymerizable ethylenically unsaturated bond. Compounds and the like. The weight average molecular weight of the polymerizable compound (C) is preferably 3,000 or less.

In particular, the polymerizable compound (C) is preferably a photopolymerizable compound having three or more ethylenically unsaturated bonds, and examples thereof include trimethylolpropane tri(meth)acrylate and pentaerythritol. Tris (meth) acrylate, neopentyl alcohol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricotine Alcohol octa (meth) acrylate, trinekapentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol 九 (meth) acrylate, ginseng 2-(Methyl)propenyloxyethyl)trimeric isocyanate, ethylene glycol modified neopentyl alcohol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(methyl) Acrylate, propylene glycol modified neopentyl alcohol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol IV (Meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, and the like. Among them, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like are preferable.

The colored curable resin composition of the present invention may contain one or more polymerizable compounds (C). The content of the polymerizable compound (C) is preferably from 20 to 150 parts by weight, more preferably from 80 to 120 parts by weight, per 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 capable of generating a living radical, an acid or the like by the action of light or heat, and is not particularly limited, and a known polymerization initiator can be used.

Examples of the polymerization initiator (D) include an anthraquinone compound such as an O-mercaptopurine compound, an alkylphenone compound, a biimidazole compound, and the like. a compound, a mercaptophosphine oxide compound or the like. The polymerization initiator (D) may be used in combination of two or more kinds in consideration of sensitivity, formation of a fine pattern shape, and the like. The polymerization initiator (D) preferably contains an oxime compound such as an O-indenyl ruthenium compound because it is advantageous in sensitivity and precision in the pattern shape having a desired line width.

The O-indenyl compound is a compound having a structure represented by the formula (d). Hereinafter, * indicates a keying key.

The O-mercaptopurine compound is preferably selected, for example, from a compound represented by the formula (d1) (hereinafter sometimes referred to as "compound (d1)") or a compound represented by the formula (d2) (hereinafter, sometimes referred to as At least one of the group of the compound (d2) and the compound represented by the formula (d3) (hereinafter sometimes referred to as "the compound (d3)").

In the formulae (d1) to (d3), R ^d1 represents 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, and a carbon which may have a substituent An alkyl group of 1 to 15 or a group which may have a substituent in combination with an aromatic hydrocarbon group and an alkanediyl group derived from the alkyl group, and the methylene group (-CH ₂ -) contained in the above alkyl group may be - O-, -CO-, -S-, -SO ₂ - or -NR ^d5 - substituted, R ^d2 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, a heterocyclic group having 3 to 36 carbon atoms or a carbon number of 1 to An alkyl group of 10, 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, and R ^d4 represents a carbon number which may have a substituent An aromatic hydrocarbon group of 6 to 18 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 above aliphatic hydrocarbon group may be -O-, -CO- or - The S-substituted, methine group (-CH<) contained in the above aliphatic hydrocarbon group may be substituted by -PO ₃ <, the hydrogen atom contained in the above aliphatic hydrocarbon group may be substituted by an OH group, and R ^d5 represents a carbon number of 1 to The alkyl group of 10, the methylene group (-CH ₂ -) contained in the alkyl group may be substituted by -O- or -CO-.

The number of carbon atoms of the aromatic hydrocarbon group represented by R ^d1 is preferably from 6 to 15, more preferably from 6 to 12, still more preferably from 6 to 10. The aromatic hydrocarbon group may, for example, be a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a biphenyl group or a terphenyl group. More preferably, it is a phenyl group or a naphthyl group, and more preferably a phenyl group.

The aromatic hydrocarbon group represented by R ^d1 may have 1 or more substituents.

The substituent is preferably substituted at the α-position or the γ-position of the aromatic hydrocarbon group, and more preferably at the γ-position. The substituent may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an eleven group, a dodecyl group or a thirteen group. An alkyl group having 1 to 15 carbon atoms such as a tetradecyl group or a fifteen group; a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom or a bromine atom; and the like.

The carbon number of the alkyl group as the above substituent is preferably from 1 to 10, more preferably from 1 to 7. The alkyl group as the substituent may be any of a linear chain, a branched chain, and a cyclic group, or may be a group in which a chain group and a cyclic group are combined. The methylene group (-CH ₂ -) contained in the alkyl group as the substituent may be substituted by -O- or -S-. Further, the hydrogen atom contained in the alkyl group may be substituted by a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom or a bromine atom, and is preferably substituted by a fluorine atom.

In the aromatic hydrocarbon group represented by R ^d1 , the alkyl group as a substituent may, for example, be a group represented by the following formula. Where * is a bond key.

In the case of R ^d1 , the aromatic hydrocarbon group which may have a substituent may, for example, be a group represented by the following formula. Where * is a bond key.

In the case of R ^d1 , the aromatic hydrocarbon group which may have a substituent is preferably a group represented by the following formula.

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

The alkyl group represented by R ^{d6 is the same} as the alkyl group exemplified as the substituent of the aromatic hydrocarbon group represented by R ^d1 . The carbon number of R ^d6 is preferably from 2 to 7, more preferably from 2 to 5. Further, the alkyl group represented by R ^d6 may be any of a linear chain, a branched chain and a ring, and is preferably a chain.

Examples of the halogen atom which can replace the hydrogen atom contained in R ^d6 include a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom, and particularly preferably fluorine. Further, it is preferred that two or more and ten or less hydrogen atoms contained in R ^d6 are substituted by a halogen atom, and preferably three or more and six or less hydrogen atoms are substituted with a halogen atom. The substitution position of the R ^d6 O-group is preferably an ortho position, a para position, and a particularly good alignment. Further, m2 is preferably 1 to 2, and particularly preferably 1.

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

The heterocyclic group represented by R ^d1 may have 1 or more substituents. The substituent is the same as the group exemplified as the substituent which the aromatic hydrocarbon group represented by R ^d1 may have.

The number of carbon atoms of the alkyl group represented by R ^d1 is preferably from 1 to 12. Examples of the alkyl group represented by R ^d1 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an eleven group, and a dodecyl group. , thirteen bases, fourteen bases and fifteen bases. The alkyl group may be any of a linear chain, a branched chain, and a cyclic group, or may be a group in which a chain group and a cyclic group are combined. Further, 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 pass through OH. Substituted or SH group substituted.

R ^d5 represents an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group may be a chain (linear or branched chain), may be cyclic, or may be linear, branched, and cyclic, or may be a combination of a chain and The base of the cyclic base. Further, in the alkyl group of R ^d5 , the methylene group (-CH ₂ -) may be substituted by -O- or -CO-.

In the case of R ^d1 , the alkyl group which may have a substituent is specifically a group represented by the following formula. * indicates the bond key.

Further, in R ^d1 , the carbon number of the group in which the aromatic hydrocarbon group and the alkanediyl group are combined is preferably from 7 to 33, more preferably from 7 to 18, still more preferably from 7 to 12. The group to be combined may have one or two or more substituents, and examples of the substituent include the same groups as those exemplified as the aromatic hydrocarbon group or the substituent which the alkyl group may have. The group in which the aromatic hydrocarbon group and the alkanediyl group are represented by R ^{d1 is} aralkyl group, and specific examples thereof include a group represented by the following formula. Where * is a bond key.

Among them, in the case of R ^d1 , an aromatic hydrocarbon group which may have a substituent or an alkyl group which may have a substituent, and more preferably an aromatic hydrocarbon group which may have a substituent.

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

The number of carbon atoms of the heterocyclic group represented by R ^d2 is preferably from 3 to 20, more preferably from 3 to 10, still more preferably from 3 to 5. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, a decyl group, a benzofuranyl group, and an oxazolyl group.

The number of carbon atoms of the alkyl group represented by R ^d2 is preferably from 1 to 7, more preferably from 1 to 5, still more preferably from 1 to 3. The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group or a fluorenyl group. The alkyl group may be any of a linear chain, a branched chain, and a cyclic group, or may be a group in which a chain group and a cyclic group are combined.

With respect to R ^d2 , a linear alkyl group is preferred, a chain alkyl group having 1 to 5 carbon atoms is more preferred, and a chain alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group is particularly preferred.

The carbon number of the aromatic hydrocarbon group represented by R ^d3 is preferably from 6 to 15, more preferably from 6 to 12, still more preferably from 6 to 10. The aromatic hydrocarbon group may, for example, be a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a biphenyl group or a terphenyl group, and more preferably a phenyl group or a naphthyl group.

The aromatic hydrocarbon group represented by R ^d3 may have 1 or more substituents. The substituent is preferably substituted at the alpha position or the gamma position of the aromatic hydrocarbon group. The substituent is preferably an aliphatic hydrocarbon group having 1 to 15 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and a fluorene group. Alkyl groups having 1 to 15 carbon atoms such as a fluorenyl group; a vinyl group having 1 to 15 carbon atoms such as a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, a nonenyl group and a decyl group; Base;

In R ^d3 , the aliphatic hydrocarbon group which the aromatic hydrocarbon group may have has a carbon number of 1 to 7, and the aliphatic hydrocarbon group may be any of a linear chain, a branched chain and a ring, or may be a combination chain. A group formed by a group and a cyclic group. Further, the methylene group (-CH ₂ -) contained in the aliphatic hydrocarbon group may be substituted by -O-, -CO- or -S-, and the methine group (-CH<) may be substituted by -N<.

In the case of R ^d3 , the aliphatic hydrocarbon group which the aromatic hydrocarbon group may have may be a group represented by the following formula. Where * is a bond key.

In the R ^d , the aromatic hydrocarbon group which may have a substituent may, for example, be a group represented by the following formula. Where * is a bond key.

The number of carbon atoms of the heterocyclic group represented by R ^d3 is preferably from 3 to 20, more preferably from 3 to 10, still more preferably from 3 to 5. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, a decyl group, a benzofuranyl group, and an oxazolyl group. The heterocyclic group represented by R ^d3 may have one or two or more substituents, and the substituent may be the same as those exemplified as the substituent which the aromatic hydrocarbon group represented by R ^d1 may have.

Wherein R ^{d3 is} preferably an aromatic hydrocarbon group having a substituent, and in the case of the substituent, a chain alkyl group having 1 to 7 carbon atoms (more preferably 1 to 3 carbon atoms) is preferred. The number is preferably two or more and five or less.

The number of carbon atoms of the aromatic hydrocarbon group represented by R ^d4 is preferably from 6 to 15, more preferably from 6 to 12, still more preferably from 6 to 10. The aromatic hydrocarbon group may, for example, be a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a biphenyl group or a terphenyl group. More preferably, it is a phenyl group and a naphthyl group, and still more preferably a phenyl group. The aromatic hydrocarbon group represented by R ^d4 may have 1 or more substituents. The substituent may be the same as the substituent which the aromatic hydrocarbon group of R ^d1 may have.

The aliphatic hydrocarbon group represented by R ^d4 preferably has a carbon number of from 1 to 13, more preferably from 2 to 10, still more preferably from 4 to 9. Examples of the aliphatic hydrocarbon group represented by R ^d4 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an eleven group, and a twelfth group. Alkyl groups such as decyl, thirteen, tetradecyl and pentadecanyl; vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl Alkenyl groups such as undecenyl, dodecenyl, tridecenyl, tetradecenyl and pentadecenyl; and the like. These aliphatic hydrocarbon groups may be in the form of a chain (linear or branched chain), may be cyclic, or may be a group in which a chain group and a cyclic group are combined. Further, in the aliphatic hydrocarbon group of R ^d4 , the methylene group (-CH ₂ -) may be substituted by -O-, -CO- or -S-, and the methine group (-CH<) may be substituted by -PO ₃ <. The hydrogen atom contained in the above aliphatic hydrocarbon group may be substituted with an OH group.

The aliphatic hydrocarbon group which may have a substituent represented by R ^d4 may, for example, be a group represented by the following formula. Where * is a bond key.

R ^{d4 is} preferably a chain aliphatic hydrocarbon group which may have a substituent, more preferably a chain alkyl group which has no substituent, and more preferably a branched chain alkyl group which has no substituent.

Specific examples of the compound represented by the compound (d1) and (d1) include a compound having each substituent described in (d1-1) to a compound having each substituent described in (d1-67). In Tables 1 to 7, * is a bonding key.

In particular, a compound having a substituent described in (d1-3), a compound having each substituent described in (d1-6), and a compound having each substituent described in (d1-18) are preferred. a compound having each substituent described in (d1-52), a compound having each substituent described in (d1-55), a compound having each substituent described in (d1-56), and having (d1- 60) The compound of each of the substituents described above, and the compound having each substituent described in (d1-61), more preferably a compound having each substituent described in (d1-3) to have (d1-6) a compound of each substituent described, having (d1-18) The compound of each of the substituents described above is a compound having each substituent described in (d1-41), more preferably a compound having each substituent described in (d1-24), and having (d1-36) The compound of each of the substituents described above is a compound having each substituent described in (d1 to 40), and particularly preferably a compound having each substituent described in (d1-24).

The compound (d1) can be produced, for example, by the production method described in JP-A-2014-500852.

The compound (d2) is preferably: 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, and R ^d3 is a carbon number 6 to 18 which may have a substituent. The aromatic hydrocarbon group, R ^d4 is a compound having an aliphatic hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, more preferably R ^d1 represents a methyl group, an ethyl group or a propyl group, and 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 wherein R ^d4 is a methyl group, an ethyl group or a propyl group, and more preferably, R ^d1 and R ^d2 are a methyl group, and R ^d3 is an o-tolyl group. R ^d4 is an ethyl compound.

The compound (d3) is preferably a compound wherein R ^d1 is an alkyl group having 1 to 15 carbon atoms which may have a substituent, and R ^d2 is an aromatic hydrocarbon group having 6 to 18 carbon atoms, more preferably R ^d1 is a hexyl group and R ^D2 is a compound of phenyl.

As such an O-indenyl ruthenium compound, N-benzylideneoxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzene Mercaptooxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylthiophenyl) --3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole -3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4 -dioxolylmethyloxy)benzhydryl}-9H-indazol-3-yl]ethane-1-imine, N-ethyloxy-1-[9-ethyl -6-(2-methylbenzimidyl)-9H-oxazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzylideneoxy-1-[9- Ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure OXE01, OXE02, OXE03 (above, BASF) and N-1919 (made by ADEKA) can also be used. In the case of these O-fluorenyl ruthenium compounds, there is a tendency to obtain a color filter excellent in etching performance.

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

As the compound having a structure represented by the formula (d4), 2-methyl-2-morpholinyl-1-(4-methylthiophenyl)propan-1-one, 2-di Methylamino-1-(4-morpholinylphenyl)-2-benzylidenebutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl) Methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one and the like. Commercial products such as Irgacure 369, 907, and 379 (above, manufactured by BASF Corporation) can also be used.

Examples of the compound having the structure represented by the formula (d5) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1-[4] -(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1 a ketone oligomer, α,α-diethoxyacetophenone, benzyldimethylketal, and the like.

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

As the biimidazole compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3) can be cited. -Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (refer to JP-A-6-75372, JP-A-6-75373, etc.), 2,2'-double (2-Chlorophenyl)-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'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'- Bis(2-chlorobenzene -4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (refer to Japanese Patent Publication No. Sho 48-38403, JP-A-62-174204, etc.), 4, 4 The imidazole compound in which the phenyl group at the 5, 5'-position is substituted with an alkoxycarbonyl group (see Japanese Patent Laid-Open Publication No. Hei 7-10913, etc.). Among them, a compound represented by the following formula or a mixture of the above is preferred.

Just three The compound is exemplified by 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-three. , 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-three 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-three Wait.

Examples of the mercaptophosphine oxide compound include 2,4,6-trimethylbenzimidyldiphenylphosphine oxide.

Further, examples of the polymerization initiator (D) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like. Benzoin compound; benzophenone, o-benzhydryl Methyl benzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra (t-butylperoxy) a benzophenone compound such as carbonyl)benzophenone or 2,4,6-trimethylbenzophenone; an anthracene compound such as 9,10-phenanthrenequinone, 2-ethylhydrazine, camphorquinone; Alkyl-2-chloroacridone, benzhydrin, methyl phenylglyoxylate, a titanocene compound, and the like. These are preferably used in combination with a polymerization initiation aid (D1) (particularly an amine) described later.

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

[5] Polymerization start aid (D1)

The polymerization initiation aid (D1) is a compound or a sensitizer for promoting polymerization of a polymerizable compound which starts polymerization by a polymerization initiator. When the polymerization initiation aid (D1) is contained, it can be used in combination with the polymerization initiator (D).

The polymerization starting aid (D1) may, for example, be an amine compound, an alkoxy fluorene compound, a thioxanthone compound or a carboxylic acid compound. Among them, a thioxanthone compound is preferred. Two or more kinds of polymerization starting aids (D1) may also be used in combination.

As the amine compound, there may be mentioned, for example, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-di Isoamyl methylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate Ester, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michlerone), 4,4'-bis(diethylamino) Benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, etc., among which 4,4'-bis(diethylamino)benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

As the alkoxy oxime compound, there may be mentioned: 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-B. A group of 9,9-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene or the like.

As the thioxanthone compound, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthiaxanone, 2,4-dichloro Xanthone, 1-chloro-4-propoxythiaxanone, and the like.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, and dimethylphenylthioacetic acid. , methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthyl Sulfuric acid, N-naphthylglycine, naphthoxyacetic acid, and the like.

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

[6] thiol compound (T)

The colored curable resin composition of the present invention may contain one or more kinds of thiol compounds (T). The thiol compound (T) is particularly preferably used when the polymerization initiator (D) is an anthraquinone compound such as an O-fluorenyl hydrazine compound and/or a biimidazole compound. The thiol compound (T) is a compound having at least one thio group (-SH) in the molecule. The thiol compound (T) is preferably a compound having one thio group in the molecule.

For a compound having one thio group in the molecule, a 2-thio group is exemplified. Oxazole, 2-thiothiazole, 2-thiobenzimidazole, 2-thiobenzothiazole, 2-thiobenzophenone Azole, 2-thionicotinic acid, 2-thiopyridine, 2-thiopyridin-3-ol, 2-thiopyridine-N-oxide, 4-amino-6-hydroxy-2-thio Pyrimidine, 4-amino-6-hydroxy-2-thiopyrimidine, 4-amino-2-thiopyrimidine, 6-amino-5-nitroso-2-thiouracil, 4,5-di Amino-6-hydroxy-2-thiopyrimidine, 4,6-diamino-2-thiopyrimidine, 2,4-diamino-6-thiopyrimidine, 4,6-dihydroxy-2- Thiopyrimidine, 4,6-dimethyl-2-thiopyrimidine, 4-hydroxy-2-thio-6-methylpyrimidine, 4-hydroxy-2-thio-6-propylpyrimidine, 2- Thio-4-methylpyrimidine, 2-thiopyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazolium-2-sulfate Alcohol, 2-thioimidazole, 2-thio-1-methylimidazole, 4-amino-3-indolyl-5-thio-1,2,4-triazole, 3-amino-5- Thio-1,2,4-triazole, 2-methyl-4H-1,2,4-triazole-3-thiol, 4-methyl-4H-1,2,4-triazole-3 -thiol, 3-thiol 1H-1,2,4-triazole-3-thiol, 2-amino-5-thio-1,3,4-thiadiazole, 5-amino-1 , 3,4-thiadiazole-2-thiol, 2,5-dithio-1,3,4-thiadiazole, (furan-2-yl)methanethiol, 2-thio-5- Thiazolone, 2-thiothiazoline, 2-thio-4(3H )-quinazolinone, 1-phenyl-1H-tetrazol-5-thiol, 2-quinoline thiol, 2-thio-5-methylbenzimidazole, 2-thio-5-nitrate Benzimidazole, 6-amino-2-thiobenzothiazole, 5-chloro-2-thiobenzothiazole, 6-ethoxy-2-thiobenzothiazole, 6-nitro-2 -thiobenzothiazole, 2-thionaphthoimidazole, 2-thionaphthyl Oxazole, 3-thio-1,2,4-triazole, 4-amino-6-thiopyrazolo[2,4-d]pyridine, 2-amino-6-anthracenethiol, 6- Thioquinone and 4-thio-1H pyrazolo[2,4-d]pyrimidine and the like.

Examples of the compound having two or more sulfur groups in the molecule include hexane dithiol, decane dithiol, 1,4-bis(methylthio)benzene, butanediol bis (3- Thiopropionate), butanediol bis(3-thioacetate), ethylene glycol bis(3-thioacetate), trimethylolpropane ginseng (3-thioacetate) ), butanediol bis(3-thiopropionate), trimethylolpropane ginseng (3-thiopropionate), trimethylolpropane ginseng (3-thioacetate), new Pentaerythritol strontium (3-thiopropionate), neopentyl quinone oxime (3-thioacetate), hydroxyethyl ginseng (3-thiopropionate), neopentyl pentoxide ( 3-thiobutyrate) and 1,4-bis(3-thiobutyloxy)butane.

The content of the thiol compound (T) is preferably from 0.5 to 50 parts by weight, more preferably from 5 to 45 parts by weight, still more preferably from 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, the sensitivity tends to be high and the developability tends to be good.

[7] Solvent (E)

The colored curable resin composition of the present invention preferably contains one or more solvents (E). Examples of the solvent (E) include an ester solvent (a solvent containing -COO-), an ether solvent other than an ester solvent (a solvent containing -O-), and an ether ester solvent (containing -COO- and -O- Solvent), ketone solvent other than ester solvent (containing -CO- Solvent), alcohol solvent, aromatic hydrocarbon solvent, guanamine solvent, and dimethyl hydrazine.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and acetic acid. Amyl ester, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate , cyclohexanol acetate and γ-butyrolactone.

Examples of the ether solvent 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-two Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, benzo Ether, phenethyl ether and methyl anisole.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxyl. Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxy Ethyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl acetate -3-methoxybutyl ester, 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.

As the ketone solvent, there may be mentioned, for example, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl- 2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

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

The solvent (E) preferably contains an organic solvent having a boiling point of from 120 ° C to 180 ° C at 1 atm from the viewpoint of coatability and drying property. Wherein the solvent (E) preferably contains a solvent selected from the group consisting of propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, and Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone And at least one group of N,N-dimethylformamide, more preferably selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, At least one selected from the group consisting of ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, and ethyl 3-ethoxypropionate.

The content of the solvent (E) in the colored curable resin composition is preferably from 70 to 95% by weight, more preferably from 75 to 92% by weight. In other words, The solid content of the colored curable resin composition is preferably from 5 to 30% by weight, more preferably from 8 to 25% by weight. When the content of the solvent (E) is in the above range, the flatness at the time of coating is improved, and the color density is not insufficient when the color filter is formed, and the display property tends to be good.

[8] Leveling agent (F)

The colored curable resin composition of the present invention may contain one or more kinds of leveling agents (F). Examples of the leveling agent (F) include a polyfluorene-based surfactant (having no fluorine atom), a fluorine-based surfactant, and a polyfluorene-based surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

The polyoxo-based surfactant (not having a fluorine atom) may, for example, be a surfactant having a decane bond in the molecule. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name: Dow Corning Toray) ; KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemical Co., Ltd.); TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (Momentive Performance Materials Japan Contract Company) System) and so on.

The fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon chain in the molecule. Specifically, Fluorad (registered trademark) FC430, Fluorad FC431 (Sumitomo 3M (share) system); Megaafac (Note) Registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac RS-718-K (made by DIC); Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (Mitsubishi Materials Electronics Co., Ltd.); Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (made by Asahi Glass Co., Ltd.); and E5844 (Daikin Fine Chemical Research Institute) System) and so on.

Examples of the polyfluorene-based surfactant having a fluorine atom include a surfactant having a decane bond and a fluorocarbon chain in the molecule. Specific examples include Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac F443 (manufactured by DIC).

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 or less. the following. Further, the content does not include the content of the above pigment dispersant.

[9] Antioxidants (G)

The colored curable resin composition preferably contains an antioxidant from the viewpoint of improving the heat resistance and light resistance of the colorant (A). The antioxidant is not particularly limited as long as it is generally used industrially, and a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, or the like can be used. Two or more types of antioxidants can be used.

Examples of the phenolic antioxidant include Irganox 1010 (neopentitol oxime [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Co., Ltd. ), Irganox 1076 (octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoate, manufactured by BASF), Irganox 1330 (3,3', 3'',5,5',5''-hexa-t-butyl-a,a',a''-(mesitylene-2,4,6-triyl)tri-p-cresol, BASF , Irganox 3114 (1,3,5-gin (3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-three -2,4,6(1H,3H,5H)-trione, BASF (manufactured by BASF), Irganox 3790 (1,3,5-para ((4-tert-butyl-3-hydroxy-2,6) -xylyl)methyl)-1,3,5-three -2,4,6(1H,3H,5H)-trione, manufactured by BASF Co., Ltd., Irganox 1035 (thiodiethylidene bis[3-(3,5-di-t-butyl-4) -hydroxyphenyl)propionate], manufactured by BASF Co., Ltd., Irganox 1135 (phenylpropionic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxyl, C7-C9 side chain Alkyl ester, manufactured by BASF Co., Ltd., Irganox 1520L (4,6-bis(octylthiomethyl)-o-cresol, manufactured by BASF Co., Ltd.), Irganox 3125 (manufactured by BASF Co., Ltd.), Irganox 565 (2,4-bis(n-octylthio)-6-(4-hydroxy 3',5'-di-t-butylanilino)-1,3,5-three , BASF (share) system, ADKSTAB AO-80 (3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanyloxy)- 1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, manufactured by ADEKA Co., Ltd., Sumilizer BHT (manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GS (manufactured by Sumitomo Chemical Co., Ltd.), Cyanox 1790 (manufactured by Cytec Co., Ltd.), and Vitamin E (manufactured by Eisai Co., Ltd.).

Examples of the phosphorus-based antioxidant include Irgafos 168 (parameter (2,4-di-t-butylphenyl) phosphite, manufactured by BASF), and Irgafos 12 (see [2-[[2 ,4,8,10-tetra-t-butyldibenzo[d,f][1,3,2] Oxaphosphino-6-yl]oxy]ethyl]amine, manufactured by BASF Co., Ltd., Irgafos 38 (bis(2,4-bis(1,1-dimethylethyl)-6-methyl phosphite) Phenyl phenyl) ethyl ester, manufactured by BASF Co., Ltd., ADKSTAB 329K (made by Adeka), ADKSTAB PEP36 (made by Adeka), ADKSTAB PEP-8 (made by Adeka), Sandstab P- EPQ (manufactured by Clariant), Weston 618 (manufactured by GE), Weston 619G (manufactured by GE), Ultranox 626 (manufactured by GE), and Sumilizer GP (6-[3-(3-tert-butyl-4-hydroxyl) -5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenzo[d,f][1.3.2]dioxaphosphanee) Sumitomo Chemical Co., Ltd.).

Examples of the sulfur-based antioxidant include a dialkyl thiodipropionate compound such as dilauryl thiodipropionate, dimyristyl ester or distearyl ester, and hydrazine [methylene group (3-tine group). Sulfur) propionate] a β-alkylmercaptopropionate compound of a polyhydric alcohol such as methane.

[10] Other ingredients

The colored curable resin composition of the present invention may contain one or two or more kinds of additives as needed, and the additives are a filler, a polymer compound other than the resin (B), an adhesion promoter, an ultraviolet absorber, and an anti-aggregation. Agents, organic acids, organic amine compounds, hardeners, and the like.

Examples of the filler include glass, cerium oxide, aluminum oxide, and the like. Examples of the polymer compound other than the resin (B) include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate.

As for the adhesion promoter, it can be cited as: vinyl trimethyl Oxy decane, vinyl triethoxy decane, vinyl ginseng (2-methoxyethoxy) decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy Decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methacryloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, and the like.

The ultraviolet absorber may, for example, be a benzotriazole compound such as 2-(2-hydroxy-3-t-butyl-5-methylphenyl)-5-chlorobenzotriazole; 2-hydroxyl a benzophenone compound such as 4-octyloxybenzophenone; 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate Benzoate-based compound; 2-(4,6-diphenyl-1,3,5-three -2-yl)-5-hexyloxyphenol, etc. A compound or the like. Examples of the anti-agglomerating agent include sodium polyacrylate and the like.

The organic acid can be used for the adjustment of imaging properties, and the like, and specifically, fats such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, caproic acid, diethyl acetic acid, heptanoic acid, and octanoic acid are mentioned. Group of monocarboxylic acids; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, tridecanedioic acid, methyl propylene Acid, ethylmalonic acid, dimethylmalonic acid, methyl succinic acid, tetramethyl succinic acid, cyclohexane dicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, medium An aliphatic dicarboxylic acid such as a benic acid; Aliphatic tricarboxylic acid such as tricarballylic acid, aconitic acid, camphoronic acid, benzoic acid, methylbenzoic acid, p-cumenebenzoic acid, 3,4- An aromatic monocarboxylic acid such as hemellitic acid or mesitylenic acid; an aromatic dicarboxylic acid such as citric acid, isophthalic acid or p-citric acid; 1,2,4-benzene Trimellitic acid, trimesic acid, 1,2,3,5-benzenetetracarboxylic acid (mellophanic acid), 1,2,4,5-benzenetetracarboxylic acid (pyromellitic) An aromatic polycarboxylic acid such as acid).

As the organic amine compound, there may be mentioned n-propylamine, isopropylamine, n-butylamine, isobutylamine, second butylamine, tert-butylamine, n-pentylamine, n-hexylamine. a monoalkylamine such as n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, n-dodecylamine; cyclohexylamine, 2-methylcyclohexylamine, Monocyclic alkylamine such as 3-methylcyclohexylamine or 4-methylcyclohexylamine; methylethylamine, diethylamine, methyl-n-propylamine, ethyl-n-propylamine, di-n-propyl Dioxanes such as monoamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-secondbutylamine, di-t-butylamine, di-n-pentylamine, di-n-hexylamine a monoalkyl monocycloalkylamine such as methylcyclohexylamine or ethylcyclohexylamine; a dicycloalkylamine such as dicyclohexylamine; dimethylethylamine, methyldiethylamine, and tris Ethylamine, Dimethyl n-propylamine, diethyl n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, a trialkylamine such as triisobutylamine, tri-t-butylamine, tri-t-butylamine, tri-n-pentylamine or tri-n-hexylamine; dimethylcyclohexylamine, diethylcyclohexyl a dialkyl monocycloalkylamine such as an amine; a monoalkylbicycloalkylamine such as methyl dicyclohexylamine, ethyl dicyclohexylamine or tricyclohexylamine; 2-aminoethanol, 3-amino group- a monoalkanolamine such as 1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol or 6-amino-1-hexanol; Monocycloalkanolamines such as 4-amino-1-cyclohexanol; diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n-pentanolamine, a dialkanolamine such as di-n-hexanolamine; a dicycloalkanolamine such as bis(4-cyclohexanol)amine; triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, and triisobutylene a trialkanolamine such as an alkanolamine, tri-n-pentanolamine or tri-n-hexanolamine; a tricycloalkanolamine such as tris(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-propanediol, 3 -Amino group such as diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1,3-propanediol An alkanediol; an amine cycloalkylene glycol such as 4-amino-1,2-cyclohexanediol or 4-amino-1,3-cyclohexanediol; 1-aminocyclopentanone methanol, 4-aminocyclopentanone methanol or the like containing an amino group of a cycloalkanone methanol; 1-aminocyclohexanone methanol, 4-aminocyclohexanone methanol, 4-dimethylaminocyclopentane methanol, 4- Aminoalkylcyclopentane methanol, 4-dimethylaminocyclohexane methanol, 4-diethylaminocyclohexane methanol, etc., amine-containing cycloalkane methanol; β-alanine, 2-amine Butyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminopentanoic acid, 5-aminopentanoic acid, 6- Aminocarboxylic acid such as aminocaproic acid, 1-aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid; aniline, o-methylaniline, m-A Aniline, p-methylaniline, p-ethylaniline, p-propylaniline, p-isopropylaniline, p-n-butylaniline, p-t-butylaniline, 1-naphthylamine, 2- Aromatic amines such as naphthylamine, N,N-dimethylaniline, N,N-diethylaniline, p-methyl-N,N-dimethylaniline; o-aminobenzyl alcohol, m-amine Benzomethanol, p-amino group Aminobenzyl alcohol such as benzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol; o-aminophenol, m-aminophenol, p-aminophenol, p-dimethyl Aminophenols such as aminoaminophenol and p-diethylaminophenol; m-aminobenzoic acid, p-aminobenzoic acid, p-dimethyl Aminobenzoic acid, amino-benzoic acid such as p-diethylaminobenzoic acid, and the like.

Examples of the curing agent include a compound which can react with a carboxyl group in the resin (B) by heating to crosslink the resin (B), a compound which can be polymerized by itself and a colored pattern, and the like. a compound, an oxetane compound, or the like.

Examples of the epoxy compound include a bisphenol A epoxy resin, a hydrogenated bisphenol A epoxy resin, a bisphenol F epoxy resin, a hydrogenated bisphenol F epoxy resin, and a novolak type. Epoxy resin, epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, epoxypropyl ester resin, epoxypropylamine resin, epoxidized oil, etc. An epoxide of an aliphatic, alicyclic or aromatic epoxy compound other than a brominated derivative of the epoxy resin, an epoxy resin or a brominated derivative thereof, or a (co)polymer of butadiene An epoxide of a (co)polymer of isoprene, a (co)polymer of glycidyl (meth)acrylate, a triepoxypropyl triisocyanurate or the like. For the commercially available epoxy resin, an o-cresol novolac type epoxy resin, "SUMIEPOXY (registered trademark) ESCN-195XL-80" (manufactured by Sumitomo Chemical Co., Ltd.), and the like are mentioned.

The oxetane compound may, for example, be a carbonate dioxetane, a benzene dimethyl oxetane, an adipate dioxetane or a phthalic acid ester. Oxetane, cyclohexanedicarboxylic acid dioxetane, and the like.

When the colored curable resin composition of the present invention contains an epoxy compound, an oxetane compound or the like as a curing agent, it may contain an epoxy group or an oxetane compound of an epoxy compound. alkyl A compound in which a skeleton is ring-opened and polymerized. Examples of the compound include a polyvalent carboxylic acid, a polyvalent carboxylic anhydride, an acid generator, and the like.

As the polyvalent carboxylic acid, there may be mentioned: 3,4-dimethylnonanoic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,4,5,8- An aromatic polycarboxylic acid such as naphthalenetetracarboxylic acid or 3,3',4,4'-benzophenonetetracarboxylic acid; an aliphatic polycarboxylic acid such as 1,2,3,4-butanetetracarboxylic acid; Hydrogen decanoic acid, 3,4-dimethyltetrahydrofurfuric acid, hexahydroisodecanoic acid, hexahydropyridinic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohexane An alicyclic polycarboxylic acid such as a tricarboxylic acid, a cyclopentanetetracarboxylic acid or a 1,2,4,5-cyclohexanetetracarboxylic acid.

Examples of the polycarboxylic acid anhydride include phthalic anhydride, 1,2,4,5-benzenetetracarboxylic anhydride, 1,2,4-benzenetricarboxylic anhydride, and 3,3',4,4'-benzophenone. An aromatic polycarboxylic acid anhydride such as tetracarboxylic dianhydride; itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, 1,2,3-propane tricarboxylic anhydride, maleic anhydride, 1, 2, 3, An aliphatic polycarboxylic acid anhydride such as 4-butane tetracarboxylic dianhydride; hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentane tricarboxylic anhydride, 1,2,4 - alicyclic polycarboxylic anhydride such as cyclohexanetricarboxylic anhydride, cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, seamic anhydride, nadic acid anhydride A carboxylic acid anhydride containing an ester group such as ethylene glycol bis1,2,4-benzenetricarboxylic anhydride or glycerin, and 1,2,4-benzenetricarboxylic anhydride.

As the carboxylic acid anhydride, it can be used in the form of an epoxy resin hardener in the market. The epoxy resin hardener is exemplified by the trade name "ADEKA HARDENER (registered trademark) EH-700" (manufactured by ADEKA) and the product name "RIKACID (registered trademark) HH" (New Japan Physical and Chemical Co., Ltd.) System), the product name "MH-700" (New Japan Physical and Chemical Co., Ltd.) and so on.

Examples of the acid generator include 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethyloxyphenylene. Methyl hydrazine p-toluene sulfonate, 4-ethyl methoxy phenyl / methyl / benzyl hydrazine hexafluoroantimonate, triphenyl sulfonium p-toluene sulfonate, triphenyl sulfonium hexafluoroantimonate An acid salt, a diphenylsulfonium p-toluenesulfonate, a phosphonium salt such as diphenylsulfonium hexafluoroantimonate; a nitrobenzyl methyl tosylate; a benzoin tosylate;

<Method for Producing Colored Curable Resin Composition>

The colored curable resin composition of the present invention can be obtained by using a coloring agent (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and optionally a solvent (E), a mercaptan. The compound (T), the leveling agent (F), the polymerization starting aid (D1), the antioxidant (G), and other components are mixed and prepared.

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

The color hardening resin composition of the present invention can be used as a material of a color filter. The color filter formed of the colored curable resin composition of the present invention is also within the scope of the present invention. Color filters can also be formed Color pattern.

Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithography method, an inkjet method, a printing method, and the like. Among them, photolithography is preferred. The photo-etching method is a method in which a colored curable resin composition is applied onto a substrate, dried to form a colored composition layer, and the colored composition layer is exposed and exposed through a photomask. In the photoetching method, a coloring coating film of a cured product belonging to the above-mentioned colored composition layer can be formed by using no mask and/or no image formation at the time of exposure. The colored pattern and colored coating film formed from the colored curable resin composition of the present invention are the color filters of the present invention.

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

As the substrate, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass coated with cerium oxide, or the like; polycarbonate, polymethyl methacrylate, poly A resin plate such as ethylene phthalate; ruthenium; an aluminum, silver, silver/copper/palladium alloy film or the like formed on the substrate. Additional color filter layers, resin layers, transistors, circuits, and the like may be formed on the substrates.

The formation of the pixels of the respective colors by the photolithography method can be carried out by known or conventional devices and conditions, and can be produced, for example, as follows. First, the colored curable resin composition is applied onto a substrate, and the volatile components such as a solvent are removed by heat drying (pre-baking) and/or drying under reduced pressure to dry, thereby obtaining a smooth colored composition layer. Examples of the coating method include a spin coating method, a slit coating method, and a slit-spin coating method.

The temperature at the time of heat drying is preferably from 30 to 120 ° C, more preferably from 50 to 110 ° C. Further, in terms of heating time, it is preferably from 10 seconds to 5 minutes, more preferably from 30 seconds to 3 minutes. When drying under reduced pressure, it is preferably carried out at a temperature of from 20 to 25 ° C under a pressure of from 50 to 150 Pa. The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected in accordance with the film thickness of the target color filter.

According to the present invention, a color filter which is rich in color even if it is a film can be formed.

Then, the colored composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern corresponding to the intended use can be used. As the light source for exposure, a light source which generates light of a wavelength of 250 to 450 nm is preferred. For example, a filter that blocks a wavelength region of less than 350 nm can be used to block light of less than 350 nm, and a band pass filter that takes out a wavelength region of around 436 nm, around 408 nm, and around 365 nm can be used to selectively take out the vicinity of 436 nm. Light near 408 nm and around 365 nm. Specifically, examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, and the like.

Since the entire surface of the exposure surface can be uniformly irradiated with parallel rays and the alignment of the mask and the correct position of the substrate on which the colored composition layer is formed can be performed, an exposure apparatus such as a mask aligner and a stepper is preferably used for the exposure.

A colored pattern is formed on the substrate by bringing the exposed coloring composition layer into contact with the developing liquid and developing the image. By developing, the unexposed portions of the colored composition layer are dissolved in the developing solution and removed.

The developing solution is preferably an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide. The concentration of the basic compound in the aqueous solution is preferably from 0.01 to 10% by weight, more preferably from 0.03 to 5% by weight. Further, the developing solution may also contain a surfactant.

The development method may be any one of a puddle method, a dipping method, and a spray method. Furthermore, the substrate can be tilted at any angle during development. It is preferred to carry out water washing after development.

Preferably, the resulting colored pattern is post-baked. The post-baking temperature is preferably from 150 to 250 ° C, more preferably from 160 to 235 ° C. The post-baking time is preferably from 1 to 120 minutes, more preferably from 10 to 60 minutes.

Since the film thickness of the resulting colored coating film affects adjacent pixels, it is preferably as thin as possible. In particular, when a thick film is formed, when a liquid crystal panel is produced, light of a light source leaks through two or more pixels, and when the panel is viewed obliquely, color sharpness is lost. The film thickness of the colored coating film after post-baking is preferably 3 μm or less, more preferably 2.8 μm or less. The lower limit of the film thickness of the colored coating film is not particularly limited, and is usually 1 μm or more, and may be 1.5 μm or more.

As described above, according to the present invention, a color filter which is rich in color even in the form of a film can be formed. Further, since the colored coating film exhibits excellent developability, it is excellent as a material of a color filter.

The brightness of the colored coating film is preferably as high as possible, and is preferably 38.5 or more, more preferably 39 or more, and the upper limit is not particularly limited, and is usually 70 or less.

The color filter of the present invention can be used as a display device (liquid crystal display device, organic EL device, electronic paper, etc.) and a solid image sense Color filter for measuring components.

(Example)

Hereinafter, the present invention will be more specifically described by showing examples and comparative examples, but the present invention is not limited to the examples. In the examples, the content and the % and the amount of the use amount are indicated on the basis of the weight unless otherwise specified.

<Synthesis Example 1: Modulation of xanthene dye>

Under the light-shielding condition, 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, and the resulting solution was Stir at 110 ° C for 6 hours.

After the obtained reaction liquid was cooled to room temperature, it was added to a mixed liquid of 800 parts of water and 50 parts by weight of hydrochloric acid, and the mixture was stirred at room temperature for 1 hour to precipitate crystals. The precipitated crystal is obtained as a residue which is filtered and then dried to obtain a compound represented by the above formula (1-24). Hereinafter, this compound is referred to as "oxaxanthene dye (A-3)".

<Synthesis Example 2: Modulation of Resin (B)>

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

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

Device: HLC-8120GPC (manufactured by TOSOH), column: TSK-GELG2000HXL, column temperature: 40 ° C, solvent: THF, flow rate: 1.0 mL / min, solid concentration of test solution: 0.001 to 0.01 wt% Injecting amount: 50 μL, detector: RI, standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by TOSOH).

<Synthesis Example 3: Preparation of Pigment Dispersion (A1)>

The following were mixed: CI Pigment Blue 16 12.1 parts of an acrylic pigment dispersant 5.4 parts, and propylene glycol monomethyl ether acetate 82.5 parts, and the pigment was sufficiently dispersed using a bead mill, thereby obtaining CI Pigment Blue 16 Pigment dispersion (A1).

<Synthesis Example 4: Modulation of Pigment Dispersion (A2)>

The following were mixed: CI Pigment Blue 15:6 12.0 parts of an acrylic pigment dispersant 2.0 parts, and propylene glycol monomethyl ether acetate 86.0 parts, and the pigment was sufficiently dispersed using a bead mill, thereby obtaining a CI pigment blue 15:6 pigment dispersion (A2).

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

(1) Modulation of coloring curable resin composition

The xanthene dye (A-3) obtained in the above Synthesis Example 1, the resin solution containing the resin (B) obtained in the above Synthesis Example 2, the pigment dispersion liquid (A1) obtained in the above Synthesis Example 3, or the above Synthesis Example 4 were obtained. Pigment dispersion (A2) and polymerizable compound (C-1), polymerization initiator (D-1), polymerization initiator (D-2), polymerization initiator (D-3), leveling agent (E-1) The mixture was mixed so as to have a blending amount as shown in Table 8, and a colored curable resin composition was obtained.

Furthermore, modulation of the coloring curable resin composition At this time, 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 blending amount of each component in Table 8 is "parts by weight", and the blending amount is a solid fraction conversion. The details of each component are as follows.

[1] Colorant (A-1): CI Pigment Blue 16, [2] Colorant (A-2): CI Pigment Blue 15: 6, [3] Colorant (A-3): Formula (1-24) (a compound (B), a resin (B), and a polymerizable compound (C-) contained in the resin solution obtained in Synthesis Example 2; 1): pentaerythritol triacrylate (trade name "A-TMM-3LM-N" manufactured by Shin-Nakamura Chemical Co., Ltd.), [6] polymerization initiator (D-1): Compounds shown,

[7] Polymerization initiator (D-2): 2,2',4-gin(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl Base-1,1'-biimidazole (trade name "TCDM" manufactured by CHEMBRIDGE INTERNATIONAL CORPORATION), [8] polymerization initiator (D-3): 2-mercaptobenzothiazole (Sanshin Chemical Industry Co., Ltd.) Trade name "SANCELER M"), [9] Leveling agent (F): Polyether modified polyoxygenated oil (Dow Corning) Toray Silicone SH8400 is the product name of Toray.

(2) Production of colored coating film

The colored curable resin composition was applied by spin coating to a glass substrate ("EAGLE XG" manufactured by Corning Co., Ltd.) of 2 Å square, and then prebaked at 100 ° C for 3 minutes. After cooling, the substrate on which the colored curable resin composition was applied was subjected to an exposure machine ("TME-150RSK" manufactured by TOPCON Co., Ltd.), and exposed to an exposure amount of 80 mJ/cm ² (365 nm) in an atmosphere. Light irradiation is performed. Then, post-baking was carried out in an oven at 230 ° C for 30 minutes to obtain a colored coating film.

(3) Film thickness measurement

With respect to 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) Chroma evaluation

For the obtained colored coating film, the color separation was measured using a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the xy chromaticity coordinate in the XYZ color system of CIE was calculated using the characteristic function of the C light source (x). , y). The results are shown in Table 9.

Example 1 and Comparative Example 1, Example 2 and Comparative Example 2, Example 3 and Comparative Example 3, respectively, the chromaticity coordinates (x, y) are unified into the blue chromaticity coordinates of the target (0.138, 0.058). ), (0.144, 0.044), (0.148, 0.037).

In order to achieve this uniformity, the blending amount of each coloring agent was adjusted as shown in Table 8. In Examples 1 to 3, when compared with Comparative Examples 1 to 3, respectively, the target chromaticity coordinates can be achieved with a film-forming film of a more film. Furthermore, the blue chromaticity coordinates (x, y) of Rec. ITU-R BT.2020 are (0.131, 0.046).

(5) Imaging

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

Then, the substrate on which the colored composition layer was formed was immersed in a developing liquid (water-based developing liquid containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide) at a liquid temperature of 24 ° C to develop the substrate. The time from the start of development until the portion where the center of the substrate was dissolved by 10 mm was measured as the dissolution time. When the dissolution time is 40 seconds or less, the development property is good (○), and when it is longer than 40 seconds, it is defective (×). The results are shown in Table 10.

<Synthesis Example 5: Modulation of Pigment Dispersion (A3)>

Mix the following:

C.I. Pigment Violet 23 12.0 parts

Acrylic pigment dispersant 2.0 parts, and propylene glycol monomethyl ether acetate 86.0 parts

And using a bead mill to fully disperse the pigment, thereby obtaining a C.I. Pigment dispersion (A3) of Violet 23.

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

(1) Modulation of coloring curable resin composition

Any one of the pigment dispersion liquid (A3) obtained in Synthesis Example 5, the following colorant (A-5), and the following colorant (A-6), and the resin containing the resin (B) obtained in Synthesis Example 2 Solution, the above pigment dispersion liquid (A1) or the above pigment dispersion liquid (A2), and the above polymerizable compound (C-1), the above polymerization initiator (D-1), and the above polymerization initiator (D-2) The polymerization initiator (D-3) and the leveling agent (E-1) were mixed in such a manner as to be in the amounts shown in Tables 11 to 13, to obtain a colored curable resin composition.

In the preparation of 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 blending amount of each component in Tables 11 to 13 is "parts by weight", and the blending amount is a solid fraction conversion. The details of each component 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 to a glass substrate ("EAGLE XG" manufactured by Corning Co., Ltd.) of 2 Å square, and then prebaked at 100 ° C for 3 minutes. After cooling, the substrate on which the colored curable resin composition was applied was subjected to an exposure machine ("TME-150RSK" manufactured by TOPCON Co., Ltd.), and exposed to an exposure amount of 80 mJ/cm ² (365 nm) in an atmosphere. Light irradiation is performed. Then, it was post-baked in an oven at 230 ° C for 30 minutes to obtain a colored coating film.

(3) Film thickness measurement

With respect to 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) Chroma evaluation

For the obtained colored coating film, the color separation was measured using a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the xy chromaticity coordinate in the XYZ color system of CIE was calculated using the characteristic function of the C light source (x). , y). The results are shown in Tables 14 to 16.

In Comparative Example 4, the same chromaticity coordinates (0.130, 0.107) as in Example 4 could not be obtained. In the fifth embodiment, the comparative example 5, the sixth embodiment, and the comparative example 6, the chromaticity coordinates (x, y) are unified into the target blue chromaticity coordinates (0.135, 0.083) and (0.139, 0.066), respectively. Embodiments 4 and 5, respectively Compared to Examples 4 and 5, the target chromaticity coordinates can be achieved with a more pigmented coating film.

In Comparative Example 7, the same chromaticity coordinates (0.135, 0.072) as in Example 7 could not be obtained. In the eighth embodiment, the comparative example 8, the ninth embodiment, and the comparative example 9, the chromaticity coordinates (x, y) are unified into the target blue chromaticity coordinates (0.140, 0.054) and (0.144, 0.044), respectively. In Examples 8 and 9, when compared with Comparative Examples 8 and 9, respectively, it was possible to achieve the target chromaticity coordinates with a more pigmented color coating film.

In the tenth embodiment, the comparative example 10, the eleventh embodiment, and the comparative example 11, the chromaticity coordinates (x, y) are unified into the target blue chromaticity coordinates (0.135, 0.081) and (0.141, 0.059), respectively. In Examples 10 and 11, when compared with Comparative Examples 10 and 11, respectively, it is possible to achieve the target chromaticity coordinates with a more colored coating film.

Claims (6)

A colored curable resin composition containing a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D); and the colorant (A) contains CI Pigment Blue 16 and a red colorant And / or purple colorants. The colored curable resin composition according to claim 1, wherein the red coloring agent and/or the purple coloring agent are dyes. The colored curable resin composition according to the first or second aspect of the invention, wherein the red coloring agent and/or the purple coloring agent are compounds having a xanthene skeleton. The colored curable resin composition according to claim 1, wherein the colorant (A) contains C.I. Pigment Blue 16 and a red colorant. A color filter formed of the colored curable resin composition described in claim 1 or 2. A display device comprising the color filter of claim 5 of the patent application.