TW201807036A - The colored curable resin composition - Google Patents

Abstract

The present invention provides a colored curable resin composition which comprises a phthalocyanine type pigment, a yellow coloring agent, a resin (B), a polymerizable compound (C), a polymerization initiator (D) and a metal compound (M) (however, the metal compound (M) is different from the phthalocyanine type pigment and the yellow coloring agent).

Description

Colored curable resin composition

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

The colored curable resin composition is used in the manufacture of color filters used in display devices such as liquid crystal display devices, electroluminescent display devices, and plasma displays. The colored curable resin composition may include two or more coloring agents having different colors in order to obtain a desired color tone or the like.

For example, Japanese Patent Application Laid-Open No. 2013-242551 describes a color hardening resin composition containing C.I. pigment green 58 (C.I. pigment green 58) and C.I. pigment yellow 138 (C.I. pigment yellow 138).

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

[1] A colored hardening resin composition comprising a phthalocyanine pigment, a yellow colorant, a resin (B), a polymerizable compound (C), and a polymerization initiation Agent (D) and metal compound (M) (however, the metal compound (M) is different from a phthalocyanine pigment and a yellow colorant).

[2] The colored curable resin composition according to [1], wherein the phthalocyanine pigment is a halogenated phthalocyanine pigment.

[3] The colored curable resin composition according to [1] or [2], which is a green colored curable resin composition.

[4] A color filter formed of the colored hardening resin composition according to the above [1] to [3].

[5] A display device including the color filter according to the above [4].

According to the colored hardening resin composition of the present invention, a color filter having good light resistance and a display device including the color filter can be provided.

In this specification, unless otherwise stated, the compound system exemplified as each component may be used alone or in combination of plural kinds.

<Colored curable resin composition>

The colored curable resin composition of the present invention includes a phthalocyanine pigment, a yellow colorant, a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a metal compound (M).

The metal compound (M) is different from a phthalocyanine pigment and a yellow colorant.

According to the colored curable resin composition of the present invention, a cured film (such as a color filter) having good light resistance can be obtained.

The metal compound (M) may be a compound exhibiting an arbitrary color as long as it satisfies the following elements. In the present specification, pigments (dye, pigment) other than the metal compound (M) exhibiting an arbitrary color are collectively referred to as a colorant (A).

[1] Colorant (A)

The colored curable resin composition of the present invention contains a phthalocyanine pigment and a yellow colorant. As described later, the colored curable resin composition may further include a coloring agent other than a phthalocyanine pigment and a yellow coloring agent as the coloring agent (A).

The phthalocyanine pigment is preferably a halogenated phthalocyanine pigment.

The phthalocyanine pigment is not particularly limited, and a conventional pigment can be used, for example, a pigment classified as a pigment in a color index (published by The Society of Dyers and Colorists).

Specific examples of halogenated phthalocyanine pigments include copper halide phthalocyanine pigments such as copper fluoride phthalocyanine pigments, copper chloride phthalocyanine pigments, and copper bromide phthalocyanine pigments; zinc fluoride phthalocyanine pigments, and chloride Zinc phthalocyanine pigments such as zinc phthalocyanine pigments and zinc bromide phthalocyanine pigments.

Specific examples of the non-halogenated phthalocyanine pigment include copper phthalocyanine pigment, zinc phthalocyanine pigment, and the like.

Specific examples of the phthalocyanine pigment include green pigments such as C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Green 59, and the like; C.I. Pigment Blue 15, C.I. Pigment Blue 15: 1, C.I. Pigment Blue 15: 2, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Pigment Blue 16, and other blue pigments.

The phthalocyanine pigment of the present invention is more preferably the above-mentioned green pigment, and even more preferably C.I. Pigment Green 58 and C.I. Pigment Green 59.

The yellow colorant may be a pigment or a dye, and may include both a pigment and a dye.

The yellow pigment is not particularly limited, and conventional pigments can be used, such as pigments classified as pigments in the Color Index (published by The Society of Dyers and Colorists).

Specific examples of the yellow pigment include, for example, CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214, etc.

The yellow dye is not particularly limited, and conventional dyes such as solvent dyes, acid dyes, direct dyes, and mordant dyes can be used. Examples of the yellow dye include conventional dyes classified in the hue index (published by The Society of Dyers and Colorists) as those having a hue other than pigments, and as described in Dyeing Notes (Dyeing Company).

Specific examples of the yellow dye include CI solvent yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117, 162, 163, 167, 189, etc. CI solvent dyes; CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, CI acid dyes such as 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47 , 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141 and other CI direct dyes; CI Disperse Yellow 51, 54, 76 CI disperse dyes; CI reactive yellow 2, 76, 116 and other CI reactive dyes; CI mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65 and other mordant dyes.

The colored hardening resin composition of the present invention preferably contains at least one yellow pigment as a yellow colorant, and more preferably a yellow pigment classified as a quinophthalone pigment or an isoindoline. good. As the yellow colorant of the present invention, C.I. Pigment Yellow 138 and C.I. Pigment Yellow 185 are more preferred.

The total content of the colorant (A) is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, and still more preferably 10 to 50% by mass based on the total solid content of the colored curable resin composition. .

When the total content of the colorant (A) is within the aforementioned range, the colorant has sufficient color density when it is used as a color filter, and the required amount of the resin (B) and the polymerizable compound (C) can be contained in the composition. Forms mechanical strength charge Graphic.

Here, the "total amount of solid content" in the present specification refers to an amount in which the content of the solvent is removed from the total amount of the coloring curable resin composition. The total amount of the solid components and the content of each component relative to the total amount of the solid components can be measured, for example, by a conventional analysis means such as liquid chromatography or gas chromatography.

Of 100% by mass of the colorant (A), the total content ratio of the phthalocyanine pigment and the yellow colorant of the colorant (A) is usually 10 to 100% by mass. From the viewpoint of achieving good brightness, it is preferably 30 to 100% by mass, more preferably 40 to 100% by mass, still more preferably 45 to 100% by mass, and even more preferably 90 to 100% by mass.

From the viewpoint of achieving good brightness, the content of the phthalocyanine pigment and the yellow colorant is preferably 1 to 1,000 parts by mass, more preferably 10 to 800 parts by mass, and more relative to 100 parts by mass of the phthalocyanine pigment. It is preferably 50 to 600 parts by mass.

The coloring curable resin composition of the present invention is preferably a green coloring curable resin composition.

When the colored curable resin composition is green, the colored curable resin composition can be made into a coating film having a thickness of 2.5 μm, and the obtained coating film can be subjected to an ultraviolet-visible spectrophotometer (V-650DS; manufactured by JASCO Corporation). , Using a substrate holder), and measured the transmission spectrum to confirm. As long as the colored curable resin composition is green, the transmission spectrum satisfies the following factors.

Element: The maximum value of the transmittance from 400 to 460nm is 0 In the range of 40 to 40%, the maximum value of the transmittance of 460 to 620 nm is in the range of 50 to 100%, and the maximum value of the transmittance of 620 to 680 nm is in the range of 0 to 40%.

The colored curable resin composition of the present invention may contain a phthalocyanine pigment and a colorant other than a yellow colorant.

The other colorants may be pigments or dyes, and may include both pigments and dyes. Other colorants may be used alone or in combination of two or more.

Examples of other pigments include pigments other than phthalocyanine-based pigments and yellow pigments among pigments classified as pigments in the Colorants Index (published by The Society of Dyers and Colorists).

Specific examples of other pigments include: CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; CI Pigment Red 9 , 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and other red pigments; CI Pigment Blue 60 Blue pigments other than phthalocyanine blue pigments; CI pigments purple 1, 19, 23, 29, 32, 36, 38; purple pigments such as CI pigment brown 23, 25; CI pigments black 1, 7 And other black pigments.

As other dyes, conventional dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of dyes include: The Society of Dyers and Colorists published) are classified as compounds having a hue other than pigments; among the conventional dyes described in Dyeing Notes (Color Dyeing Corporation), dyes other than yellow dyes. More specifically, examples of other dyes include azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, anthraquinone dyes, naphthoquinone dyes, quinone imine dyes, and methine. Base dye, methine azo dye, squarine dye, acridine dye, styrene dye, coumarin dye, quinoline dye, nitro dye, phthalocyanine dye, etc. Among these, organic solvent-soluble dyes are preferred.

Specific examples of other dyes include CI solvent red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222 , 227, 230, 245, 247; CI solvent orange 2, 7, 11, 15, 26, 56, 77, 86; CI solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47 , 48, 51, 59, 60; CI Solvent Blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33 , 34, 35, CI Solvent Blue 38, 44, 67, 70 and other CI solvent dyes; CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37 , 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133 , 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426; CI Acid Orange 6, 7 , 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; CI Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102; CI Acid Blue 1, 3, 5, 7, 9, 9, 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, 2 03, 204, 205, 210, 213, 229, 234, 236, 242, 243, 249, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340; CI Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50: 1, 58, 63, 65, 80 , 104, 105, 106, 109 and other CI acid dyes; CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; CI Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57 , 61, 64, 65, 68, 70, 96, 97, 106, 107; CI Direct Purple 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; 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, 87, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117 , 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189 , 190, 192, 193, 194, 195, 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, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; CI Direct Green 25, 27, 31, 32, 34 Direct CI dyes such as 37, 63, 65, 66, 67, 68, 69, 72, 79, 82; CI disperse violet 26, 27; CI disperse blue 1, 14, 56, 60; CI disperse dyes; CI basic red 1, 10; 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; CI basic violet 2; CI basic red 9; CI basic green 1; etc. CI basic dyes; CI reactive orange 16; CI reactive red 36; etc. CI reactive dyes; CI mordant red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95; CI mordant oranges 3, 4, 5, 8, 12, 13, 14 , 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CI mordant purple 1, 1: 1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58; CI Mordant Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26 , 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84; CI mordant green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53, CI mordant dyes; CI reduced green (C I. Vat Green) 1 and other C.I. vat dyes and the like.

The pigment used for the preparation of the coloring curable resin composition may be subjected to a rosin treatment, a surface treatment using a pigment derivative introduced with an acidic group or a basic group, etc., as required, or a polymer compound or the like. Grafting treatment on the surface of the pigment, micronization treatment by the sulfuric acid microparticle method or the like, washing treatment by organic solvents and water, etc. to remove impurities, and removal treatment by the ion exchange method such as ionic impurities.

It is preferable that the pigment used for the preparation of the coloring curable resin composition has a uniform particle diameter. By containing a pigment dispersant and performing a dispersion treatment, a pigment dispersion liquid in a state where a pigment is uniformly dispersed in a solution can be obtained.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants can be used alone or in combination of two or more. Examples of the pigment dispersant include: KP (Shin-Etsu Chemical Industry Co., Ltd.), FLOREN (Kyoeisha Chemical Co., Ltd.), SOLSPERSE (Zeneca Co., Ltd.), EFKA (CIBA), AJISPER (Taste (Fine-Techno Corporation), Disperbyk (BYK-Chemie).

When a pigment dispersant is used, its use amount is preferably 1% by mass or more and 100% by mass or less, more preferably 5% by mass or more and 50% by mass or less with respect to the total amount of the pigment. When the amount of the pigment dispersant used is in the aforementioned range, there is a tendency that a pigment dispersion liquid in a uniformly dispersed state is obtained.

[2] Metal compound (M)

The colored curable resin composition of the present invention contains a metal compound (M). Thereby, the light resistance of a cured film (color filter, etc.) can be improved.

In this specification, the "metal compound (M)" means a compound different from a phthalocyanine pigment and a yellow colorant, and is a metal atom and A compound having a coordination bond between ligands.

In the metal compound (M), a metal atom usually exists as a metal ion.

The metal compound (M) may include an ionic bond in addition to a coordination bond.

As the metal compound (M), a gram extinction coefficient ε in a specific region (wavelength 460 to 620 nm) is preferably smaller.

Ε of the metal compound (M) is obtained by diluting 0.1 g of the metal compound (M) with dimethylformamide or ethyl lactate to 0.250 L to prepare a solution, and measuring the solution in the visible light region with an ultraviolet-visible spectrophotometer. The absorption spectrum was calculated by using Lambert-Beer law.

The maximum value of ε of the metal compound (M) is preferably 100 or less, more preferably 50 or less, still more preferably 30 or less, more preferably 20 or less, and particularly preferably 10 or less. When ε is within the above range, it is preferable because the brightness of the color filter tends to increase.

The metal constituting the metal compound (M) may be a typical metal or a transition metal.

Specific examples of typical metals include: Group 2 elements of the periodic table such as Be, Mg, Ca; Group 12 elements such as Zn, Cd; Group 13 elements such as Al, Ga, In; Ge, Sn, etc. Group 14 elements; etc.

Specific examples of the transition metal include: Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and other metal elements belonging to the fourth period of the periodic table; Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, etc. belong to Zhou Metal elements in the fifth period of the periodic table; lanthanides (La, Ce, etc.), Hf, Ta, W, Re, Os, Ir, Pt, Au and other metal elements belonging to the sixth period of the periodic table.

From the viewpoint of improving light resistance, examples of the metal constituting the metal compound (M) include Al, Zn, Cr, Fe, Ni, V, and Co, and more preferably, Fe, V, and Co. More preferred examples include Fe.

The content of the metal compound (M) is preferably 0.01 to 25% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.5 to 15% by mass with respect to the total amount of the solid content of the colored curable resin composition. Particularly preferred is 1 to 10% by mass. When the content of the metal compound (M) is within the aforementioned range, light resistance can be significantly improved.

When the total amount of the phthalocyanine pigment and the yellow colorant is 100 parts by mass, the content of the metal compound (M) is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 15 parts by mass, and even more preferably 0.5 to 13 Parts by mass.

From the viewpoint of improving the brightness of the obtained cured film, the structure of the metal compound (M) having a complex having any one of the formula (F1), the formula (F2), and the formula (F3) is preferable.

[In the formula (F1), X ₁ and X ₂ represent an independent oxygen atom or a sulfur atom, and Z ₁ represents a carbon atom or a sulfur atom. R ₁ represents a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom may be substituted with a halogen atom or an amine group which may have a monovalent substituent. M ₁ represents a typical metal ion or a transition metal ion, and a represents an integer of 1 to 4. When a is an integer of 2 or more, the plurality of R ₁ , X _1, and X ₂ may be the same as each other or different from each other.

In the formula (F2), R ₂ and R ₃ each independently represent a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms. M ₂ represents a typical metal ion or a transition metal ion, and b represents an integer of 1 to 4. When b is an integer of 2 or more, the plural R ₂ and R ₃ may be the same or different from each other. c represents an integer from 0 to 6.

In the formula (F3), X ₃ and X ₄ represent mutually independent oxygen atoms, nitrogen atoms, and carbonyl-containing groups, and R ₄ to R ₇ represent mutually independent monovalent aliphatic hydrocarbon groups having 1 to 8 carbon atoms. Further, two adjacent substituents of R ₄ to R ₇ may be bonded to each other (R ₄ and R ₅ ; R ₅ and R ₆ ; and R ₆ and R ₇ ) to form a ring. M ₃ represents a typical metal ion or transition metal ion, d represents an integer of 1 to 4, and when d is an integer of 2 or more, a plurality of R ₄ to R ₇ , X ₃ and X ₄ may be the same or different from each other . ]

The above-mentioned aliphatic hydrocarbon group of R ₁ is preferably an alkyl group having 1 to 20 carbon atoms. The alkyl group may be a straight chain or a branched chain. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl. Examples of the halogen atom of R ₁ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

R ₁ is preferably an alkyl group having 1 to 20 carbon atoms.

Examples of the amine group represented by R ₁ include a monoalkylamino group and a dialkylamino group. Examples of the alkyl group of the monoalkylamino group and the dialkylamino group include an alkyl group (methyl, ethyl, propyl, butyl, etc.) having 1 to 8 carbon atoms.

a is preferably an integer representing 1 to 2.

The above-mentioned aliphatic hydrocarbon group of R ₂ and R ₃ is preferably an alkyl group having 1 to 20 carbon atoms. The alkyl group may be a straight chain or a branched chain. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl.

The aromatic hydrocarbon group of R ₂ and R ₃ is preferably a phenyl group or a naphthyl group.

R ₂ and R ₃ are each independently an alkyl group having 1 to 20 carbon atoms.

Regarding M ₁ , M ₂ and M ₃ , examples of the metal atom forming the metal ion include Al, Zn, Cr, Fe, Ni, V, Co, etc., more preferably Fe, V, Co, etc., and even more preferably Fe.

b is preferably an integer of 2 to 4.

Examples of the groups represented by X ₃ and X ₄ include:-(CO) _m1- (O) _m2- (CH ₂ ) _m3- [m1 and m2 represent 0 or 1, and m3 represents an integer of 0 to 4. But m1 + m2 + m3 = 1 to 6,-(CO) _m1 -is bonded to a benzene ring],-(O) _m4- (CO) _m5- (CH ₂ ) _m6- [m4 and m5 represent 0 or 1, m6 represents an integer from 0 to 4. However, m4 + m5 + m6 = 1 to 6,-(O) _m4 -is bonded to a benzene ring] and an amine group.

X ₃ and X _{4 are} preferably each independently —CO—O— or —O—.

Examples of the ring formed by bonding two adjacent substituents of R ₄ to R ₇ to each other include a benzene ring, a naphthalene ring, and a cycloalkane ring.

Examples of the aliphatic hydrocarbon group represented by R ₄ to R ₇ include alkyl groups having 1 to 8 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, and hexyl. d is preferably an integer of 1 to 3.

From the viewpoint of improving the light resistance of the obtained cured film, it is preferable that the metal compound (M) has a monodentate ligand or a bidentate ligand.

Examples of the metal compound (M) include the following compounds.

Cobalt (II) chloride hexahydrate, octacarbonyl dicobalt, cobalt (III) hexaammonium chloride, bis (3,5-di-3rd-butylsalicylic acid) iron (III), bis (3,5 -Di- (3,5-di-salicylic acid) aluminum (III), bis (3,5-di-3rd-butylsalicylic acid) chromium (III), bis (3,5-di-3rd-butylwater) Salicylic acid) zinc (II), nickel (II) dibutyldithiocarbamate, iron (III) diethyldithiocarbamate, ginseng (2,2'-bipyridine) cobalt (II) bis ( Hexafluorophosphate), iron (II) sulfate ethylenediamine tetrahydrate, iron (II) gluconate hydrate, ethanoferrocene, ferrocene carboxylic acid, bis (cyclopentadienyl) cobalt ( III) Hexafluorophosphate, vanadium dichloride, iron (III) hexafluoroacetamidine, iron (III) tris (benzylidenemethane), hemin, hexacyanide Iron (II) acid iron (III), sodium ginseng (5,6-diamino-1,3-naphthalenedisulfonate) iron (III), bis (2,4-pentanedione acid) cobalt ( II), bis (2,4-pentanedionate) cobalt (II) dihydrate, titanium (2,4-pentanedionate) titanium (IV), ginseng (2,4-pentanedionate) cobalt (III), ginseng (2,4-pentanedionate) indium (III), bis (2,4-pentanedionate) manganese (II) dihydrate, ginseng (2,4-pentanedionate) Manganese (III), bis (2,4-pentanedionate) zinc (II), trifluoromethyl Copper (II) sulfonate, Zirconium (IV) (2,4-pentanedionate), Tin (IV) bis (2,4-pentanedionate) dichloride, bis (2,4-pentanedionate) Keto acid) vanadium (IV) oxide, bis (2,4-pentanedione acid) copper (II), bis (hexafluoroacetamidinepyruvate) cobalt (II) hydrate, Ginseng (2,4-pentanedionate) iron (III), ginseng (2-ethylhexylcarboxylic acid) iron (III), iron (III) stearate, cobalt (II) stearate, stearic acid Vanadium (IV) oxide, triisopropoxy vanadium (V) oxide, ginseng (2,4-pentanedionate) lanthanum (III) hydrate, ginseng (2,4-pentanedionate) aluminum ( III), ginseng (2,4-pentanedionate) hydrazone (III) dihydrate, silver (I) trifluoromethanesulfonate, silver (I) cobalt (II) tetraphenylporphyrin, bis Salicylamine cobalt (Salcomine).

[3] Resin (B)

The resin (B) is not particularly limited, and is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6] and the like.

Resin [K1]: at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (a) (hereinafter referred to as "(a)") and cyclic ethers having 2 to 4 carbon atoms Copolymer of monomer (b) (hereinafter referred to as "(b)") with structure and ethylenically unsaturated bond; resin [K2]: (a), (b) and copolymerizable with (a) Copolymer of monomer (c) (but different from (a) and (b)) (hereinafter referred to as "(c)"); resin [K3]: copolymer of (a) and (c) ; Resin [K4]: Resin for reacting (a) with (c) copolymer and (b); Resin [K5]: Resin for reacting (b) with (c) copolymer and (a); resin [K6]: A resin obtained by reacting the copolymer of (b) with (c) and (a), and then reacting with a carboxylic anhydride.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, butenoic acid, o-, m-, and p-vinyl benzoic acid; maleic acid, fumaric acid, and the like Diacid, citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclic [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] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] heptane 2-enes and other bicyclic unsaturated compounds containing carboxyl groups; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4 , 5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2. 1] Unsaturated dicarboxylic anhydrides such as hept-2-ene anhydride; mono [2- (meth) propenyloxyethyl] succinate, mono [2- (meth) propenyloxy] phthalate Unsaturated mono [(meth) acryloxyethyl] esters of polyvalent carboxylic acids such as ethyl] esters; such as α- (hydroxy Meth) acrylic acid of an unsaturated acrylate containing a hydroxyl group in the same molecule and a carboxyl group.

Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable from the point of copolymerization reactivity and the solubility of the obtained resin with respect to an alkaline aqueous solution.

(b) For example, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxetane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond Polymerizable compound. (b) A monomer having a cyclic ether having 2 to 4 carbon atoms and (meth) acryloxy good.

In addition, in this specification, "(meth) acrylic acid" means at least 1 sort (s) chosen from the group which consists of acrylic acid and methacrylic acid.

The expressions such as "(meth) acrylfluorenyl" and "(meth) acrylate" have the same meaning.

Examples of (b) include a monomer (b1) having an oxepropyl group and an ethylenically unsaturated bond (hereinafter referred to as "(b1)"), an oxetanyl group, and an ethylenic group. An unsaturated bond monomer (b2) (hereinafter referred to as "(b2)"), a monomer having a tetrahydrofuran group and an ethylenically unsaturated bond (b3) (hereinafter referred to as "(b3)" )Wait.

Examples of (b1) include a monomer (b1-1) (hereinafter referred to as "(b1-1)") having a structure in which an aliphatic unsaturated hydrocarbon having a linear or branched chain is epoxidized. Case), a monomer (b1-2) having an epoxidized structure of an alicyclic unsaturated hydrocarbon (hereinafter referred to as "(b1-2)"), and the like.

Examples of (b1-1) include glycidyl (meth) acrylate, beta-methylglycidyl (meth) acrylate, beta-ethylglycidyl (meth) acrylate, and epoxy Propyl vinyl ether, o-vinyl benzyl epoxy propyl ether, m-vinyl benzyl epoxy propyl ether, p-vinyl benzyl epoxy propyl ether, α-methyl- O-vinyl benzyl epoxy propyl ether, α-methyl-m-vinyl benzyl epoxy propyl ether, α-methyl-p-vinyl benzyl epoxy propyl ether, 2 , 3-bis (glycidoxymethyl) styrene, 2,4-bis (glycidoxymethyl) styrene, 2,5-bis (glycidoxymethyl) styrene, 2,6-bis (glycidoxymethyl) styrene, 2,3,4-gins (glycidoxymethyl) styrene, 2,3,5-gins (glycidoxymethyl) Based) styrene, 2,3,6-ginseng (propylene oxide Oxymethyl) styrene, 3,4,5-gins (glycidoxymethyl) styrene, 2,4,6-gins (glycidyloxymethyl) styrene, etc.

Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE2000; manufactured by DAICEL Corporation), (meth) acrylic acid 3, 4-epoxycyclohexyl methyl ester (e.g. CYCLOMER A400; manufactured by DAICEL Corporation), 3,4-epoxy cyclohexyl methyl (meth) acrylate (e.g. CYCLOMER M100; manufactured by DAICEL Corporation), formula (I ) And compounds represented by formula (II).

[In formulae (I) and (II), R ^a and R ^b 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 ^a and X ^b represents a single ^{bond, -R c -, * - R} c -O -, * - R c -S- or * -R ^c -NH-. R ^c represents an alkanediyl group having 1 to 6 carbon atoms. * Indicates a bond with O].

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

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

As R ^a and R ^b, preferred include a hydrogen atom, methyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, more preferably include a hydrogen atom, a methyl group.

Examples of the alkanediyl group include methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, and pentane-1,5- Diyl, hexane-1,6-diyl, etc.

As X ^a and X ^b , a single bond, methylene, ethylidene, * -CH ₂ -O- and * -CH ₂ CH ₂ -O- are preferable, and a single bond, * -CH is more preferable. ₂ CH ₂ -O- (* indicates a bond with O).

Examples of the compound represented by the formula (I) include compounds represented by any one of the formulae (I-1) to (I-15). Among them, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), or formula (I-11) to formula (I) are preferred. The compound represented by -15) is more preferably a compound represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15).

Examples of the compound represented by the formula (II) include compounds represented by any one of the formulae (II-1) to (II-15). Among them, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II) are preferred The compound represented by -15) is more preferably a compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15).

The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or in combination of two or more kinds. When the compound represented by the formula (I) and the compound represented by the formula (II) are used in combination, the content ratio of these [compound represented by the formula (I): compound represented by the formula (II)] is based on Mohr, and is preferably 5:95 to 95: 5, more preferably 20:80 to 80:20.

As (b2), a monomer having an oxetanyl group and a (meth) acryloxy group is more preferable. Examples of (b2) include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, 3- Ethyl-3-methacryloxymethyloxetane, 3-ethyl-3-propenemethyloxetane, 3-methyl-3-methacryloxy Ethylethyloxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methacryloxyethyloxetane, 3 -Ethyl-3-propenyloxyethyloxetane and the like.

(B3) More preferably, it is a monomer which has a tetrahydrofuranyl group and a (meth) acryloxy group. Specific examples of (b3) include tetrahydrofuran acrylate (e.g., VISCOAT V # 150, Osaka Organic Chemical Industry Co., Ltd.) Company), tetrahydrofuran methacrylate, etc.

As (b), (b1) is preferable from the point that the reliability of the obtained color filter, such as heat resistance and chemical resistance, can be further improved. Furthermore, it is more preferable (b1-2) from the point which the storage stability of a coloring curable resin composition is favorable.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, second butyl (meth) acrylate, and third (meth) acrylate Butyl ester, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-ester (commonly known in its technical field) "(Dicyclopentyl (meth) acrylate". In some cases, it is called "tricyclodecyl (meth) acrylate"), tricyclo (meth) acrylate [5.2.1.0 ^2,6 ] decane Ene-8-ester (commonly known in its technical field as "dicyclopentenyl (meth) acrylate"), dicyclopentyloxyethyl (meth) acrylate, isoamyl (meth) acrylate, ( Adamantane (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate Iso (meth) acrylate; 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid 2 -(Meth) acrylic acid esters containing hydroxyl groups such as hydroxypropyl esters; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl iconate; bicyclic [2.2. 1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybicyclo [2.2.1] heptane 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- Bis (2'-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] hept-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- 3rd butoxycarbonyl bicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonyl bicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] heptane -2-ene, 5,6-bis (thirdbutoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2. 1] Bicyclic unsaturated compounds such as hept-2-ene; N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimide Nyl-3-maleimide imino benzoate, N-succinimide imino-4-maleimide butyrate, N-succinimide imino-6-maleimide hexanoic acid Esters, N-succinylideneimido-3-maleimideimide propionate, N- (9-acridyl) maleimide imide and other dicarbonylamide derivatives; styrene, α-form Styrene, m-methylstyrene, p-methylstyrene, 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, styrene, vinyltoluene, N-benzylmaleimide, N-cyclohexylmaleimide, and N are preferred in terms of copolymerization reactivity and heat resistance. -Benzyl maleimide, bicyclic [2.2.1] Hept-2-ene, etc.

For the resin [K1], the proportion derived from each structural unit, among all the structural units constituting the resin [K1], preferably the structural unit from (a): 2 to 60 mole%

Construction unit from (b): 40 to 98 mol%, more preferably construction unit from (a): 10 to 50 mol%

Tectonic unit from (b): 50 to 90 mole%.

When the ratio of the structural unit of the resin [K1] is within the above range, the storage stability of the colored curable resin composition, the developability when a colored pattern is formed, and the solvent resistance of the obtained color filter tend to be good.

Resin [K1] can be referred to, for example, the method described in the document "Experimental Method of Polymer Synthesis" (Otsu Takayuki Publishing House, Chemical Dojin Co., Ltd., 1st Edition, 1st Issue, March 1, 1972) and the document It is manufactured by citations.

Specifically, for example, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are fed into a reaction vessel, for example, nitrogen is substituted for oxygen, thereby becoming a deoxygenated gas environment, and heated while stirring and Method of insulation. The polymerization initiator, solvent, and the like used herein are not particularly limited, and those generally used in the technical field can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.), organic solvents, and the like. An oxide (such as benzamyl peroxide) may be used as a solvent as long as it can dissolve each monomer. The solvent etc. which are the solvent (E) of the coloring curable resin composition of this invention.

The obtained copolymer may be used directly after the reaction, a solution obtained by concentrating or diluting the solution after the reaction, or may be used as a solid (powder) by a method such as reprecipitation. In particular, by using the solvent contained in the colored curable resin composition of the present invention as the solvent during the polymerization, the solution after the reaction can be directly used to prepare the colored curable resin composition of the present invention, so that the present invention can be simplified. Steps for producing a coloring curable resin composition.

For the resin [K2], the proportion derived from each structural unit, among all the structural units constituting the resin [K2], the structural unit derived from (a) is preferred: 2 to 45 mol%

Construction unit from (b): 2 to 95 mol% Construction unit from (c): 1 to 65 mol%, more preferably construction unit from (a): 5 to 40 mol%

Tectonic unit from (b): 5 to 80 mole%

Tectonic unit from (c): 5 to 60 mole%.

When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability of the colored curable resin composition, the developability when a colored pattern is formed, and the solvent resistance, heat resistance, and mechanical properties of the obtained color filter Tendency to good strength.

The resin [K2] can be produced, for example, by the same method as described in the production method of the resin [K1].

For resin [K3], the proportion from each structural unit, in the structure Among all the structural units of the resin [K3], the structural unit from (a) is preferred: 2 to 60 mole%

Tectonic unit from (c): 40 to 98 mole%, more preferably from (a): 10 to 50 mole%

Tectonic unit from (c): 50 to 90 mole%.

The resin [K3] can be produced, for example, by the same method as described in the production method of the resin [K1].

For the resin [K4], a copolymer of (a) and (c) can be obtained, and a cyclic ether having 2 to 4 carbon atoms in (b) can be added to the carboxylic acid and / or (a). Or carboxylic anhydride.

First, the copolymer of (a) and (c) was manufactured by the same method as described in the manufacturing method of the resin [K1]. In this case, the ratio from each structural unit is preferably the same ratio as that exemplified by the resin [K3].

Then, a part of the carboxylic acid and / or carboxylic acid anhydride derived from (a) in the copolymer is reacted with a cyclic ether having 2 to 4 carbon atoms in (b).

After the copolymer of (a) and (c) is produced, the gas environment in the flask is replaced by nitrogen to air, and the reaction catalyst of (b), carboxylic acid or carboxylic anhydride and cyclic ether (for example, reference (dimethylformate) Resin [K4] can be produced by feeding a reaction such as aminoaminomethyl) phenol, and a polymerization inhibitor (hydroquinone, etc.) into a flask, for example, by performing a reaction at 60 to 130 ° C for 1 to 10 hours.

The use amount of (b) is preferably 5 to 80 moles, more preferably 10 to 75 moles, with respect to (a) 100 moles. Due to this range, the storage stability of the colored curable resin composition and the developability during pattern formation are related. And the balance of solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern tends to be better. Since the cyclic ether has high reactivity and does not easily leave unreacted (b), (b) used as the resin [K4] is preferably (b1), more preferably (b1-1).

The use amount of the reaction catalyst is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b), and (c). The use amount of the polymerization inhibitor is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b), and (c).

The reaction conditions such as the feeding method, reaction temperature, and time can be appropriately adjusted in consideration of manufacturing equipment, heat generation due to polymerization, and the like. In addition, similarly to the polymerization conditions, it is possible to appropriately adjust the feeding method and reaction temperature in consideration of manufacturing equipment, heat generation due to polymerization, and the like.

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

The ratio of the structural units derived from (b) and (c) to the total molar number of all the structural units constituting the aforementioned copolymer is preferably the structural unit derived from (b): 5 to 95 moles %

Construction unit from (c): 5 to 95 mole%, more preferably construction unit from (b): 10 to 90 mole%

Tectonic unit from (c): 10 to 90 mole%.

Furthermore, under the same conditions as the method for producing the resin [K4], the cyclic ether derived from (b) and the carboxylic acid and (a) contained in the copolymer of (b) and (c) were used. The carboxylic anhydride is reacted to obtain a resin [K5].

The amount of (a) to be reacted with the copolymer is preferably 5 to 80 moles relative to (b) 100 moles. Since the cyclic ether has high reactivity and does not easily leave unreacted (b), (b) used in the resin [K5] is preferably (b1), more preferably (b1-1).

Resin [K6] is a resin that further reacts resin [K5] with carboxylic anhydride. The hydroxy group generated by the reaction of a cyclic ether with a carboxylic acid or a carboxylic acid anhydride reacts with a carboxylic acid anhydride.

Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydro Phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene Anhydride, etc. The amount of carboxylic anhydride used is preferably 0.5 to 1 mole relative to the amount of (a) used.

Specific examples of the resin (B) include 3,4-epoxycyclohexyl methyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxy tricycloacrylic acid [5.2 .1.0 ^2,6 ] decyl ester / (meth) acrylic copolymer resins [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, ( Glycidyl acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] decyl / (meth) acrylic acid / N-ring Hexyl maleimide copolymer, resins such as 3-methyl-3- (meth) acryloxymethyloxetane / (meth) acrylic acid / styrene copolymer [K2]; Base) resins such as benzyl acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer [K3]; addition to benzyl (meth) acrylic acid / (meth) acrylic acid copolymer Resin with glycidyl (meth) acrylate, resin with addition of (meth) acrylic acid to tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, and Tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic copolymer Resin [K4], such as a resin containing propylene oxide (meth) acrylate; a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / propylene oxide (meth) acrylate with (meth) acrylic acid Resin, resin such as tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate copolymer and (meth) acrylic acid, etc. [K5]; Resin such as cyclodecyl ester / glycidyl (meth) acrylate copolymer reacted with (meth) acrylic acid, and resin which reacts with tetrahydrophthalic anhydride [K6], etc. Among them, the resin (B) is preferably resin [K1] and resin [K2].

The weight average molecular weight (Mw) of the polystyrene of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000. When the weight average molecular weight (Mw) is within the aforementioned range, the hardness of the color filter is increased, the residual film ratio is high, the solubility of the unexposed portion to the developing solution is good, and the resolution of the colored pattern tends to be improved.

The dispersion [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

The acid value of the resin (B) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150 mg-KOH / g, and still more preferably 70 to 135 mg-KOH / g. Here, the acid value is a value for measuring the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and it can be obtained by, for example, titration with an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass based on the total amount of the solid content of the colored curable resin composition. . When the content of the resin (B) is within the aforementioned range, a colored pattern can be formed, and the resolution and the residual film rate of the colored pattern tend to be improved.

[4] Polymerizable compound (C)

The polymerizable compound (C) is a compound that can be polymerized by living radicals and / or acids generated from the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, and the like, A (meth) acrylate compound is preferable.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri (meth) acrylate, neopentaerythritol tri (meth) acrylate, neopentaerythritol tetra (meth) acrylate, and dineopentyl. Tetraol penta (meth) acrylate, dinepentaerythritol hexa (meth) acrylate, trinepentaerythritol octa (meth) acrylate, trinepentaerythritol hepta (meth) acrylate, tetra Neopentaerythritol deca (meth) acrylate, tetranepentaerythritol nona (meth) acrylate, ginseng (2- (meth) acryloxyethyl) trimer isocyanate, ethylene glycol modified new Pentaerythritol tetra (meth) acrylate, ethylene glycol modified dinepentaerythritol hexa (meth) acrylate, propylene glycol modified neopentaerythritol tetra (meth) acrylate, propylene glycol modified dinepentyl Tetraol hexa (meth) acrylate, caprolactone Modified neopentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, and the like.

Among them, dinepentaerythritol penta (meth) acrylate and dinepentaerythritol hexa (meth) acrylate are preferred.

The weight average molecular weight of the polymerizable compound (C) is preferably from 150 to 2,900, and more preferably from 250 to 1,500.

The content of the polymerizable compound (C) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, and even more preferably from 17 to 55% by mass based on the total solid content of the colored curable resin composition. . When the content ratio of the polymerizable compound (C) is within the above range, the residual film rate at the time of forming a colored pattern and the chemical resistance of the color filter tend to be improved.

[5] Polymerization initiator (D)

The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active radicals, acids, and the like by the action of light and heat and starts polymerization, and a conventional polymerization initiator can be used. Examples of the polymerization initiator that generates living radicals include alkyl phenone compounds, (triazine) compound, fluorenyl phosphine oxide compound, O-fluorenyl oxime compound, and biimidazole compound.

The O-fluorenyl oxime compound is a compound having a structure represented by formula (d1). In the following, * indicates a bond key.

Examples of the O-fluorenyl oxime compound include N-benzyloxy-1- (4-phenylthiophenyl) butane-1-one-2-imine, and N-benzidine Oxy-1- (4-phenylthiophenyl) octane-1-one-2-imine, N-benzyloxy-1- (4-phenylthiophenyl) -3- Cyclopentylpropane-1-one-2-imine, N-ethoxyl-1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl ] Ethane-1-imine, N-ethoxyl-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxa Cyclopentylmethyloxy) benzylidene} -9H-carbazol-3-yl] ethane-1-imine, N-acetamidooxy-1- [9-ethyl-6- (2 -Methylbenzyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzyloxy-1- [9-ethyl-6- ( 2-methylbenzylidene) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-one-2-imine and the like. Commercial products such as Irgacure OXE01, OXE02 (above, made by BASF Corporation), N-1919 (made by ADEKA Corporation) can also be used. Among these, the O-fluorenyl oxime compound is preferably selected from the group consisting of N-benzyloxy-1- (4-phenylthiophenyl) butane-1-one-2-imine, and N-benzyl Ethoxy-1- (4-phenylthiophenyl) octane-1-one-2-imine and N-benzyloxy-1- (4-phenylthiophenyl) -3 -At least one group of cyclopentylpropane-1-one-2-imines, more preferably N-benzyloxy-1- (4-phenylthiophenyl) octane-1- Keto-2-imine. If it is such an O-fluorenyl oxime compound, there is a tendency to obtain a color filter with high brightness.

The alkyl phenone compound is a compound having a structure represented by formula (d2) or a structure represented by formula (d3). In these structures, the benzene ring may have a substituent. * Indicates a bond key.

Examples of the compound having a structure represented by the formula (d2) include 2-methyl-2-morpholinyl-1- (4-methylhydrothiophenyl) propane-1-one, and 2- Dimethylamino-1- (4-morpholinylphenyl) -2-benzylbutane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl ) Methyl] -1- [4- (4-morpholinyl) phenyl] butane-1-one and the like. Commercial products such as Irgacure 369, 907, and 379 (the above are made by BASF Corporation) can also be used.

Examples of the compound having a structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropane-1-one and 2-hydroxy-2-methyl-1- [4- (2- Hydroxyethoxy) phenyl] propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1-one Polymers, α, α-diethoxyacetophenone, benzyldimethylketal, etc.

In terms of sensitivity, the alkyl phenone compound is preferably a compound having a structure represented by the formula (d2).

As the aforementioned three Compounds include: 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-tri , 2,4-bis (trichloromethyl) -6-piperyl-1,3,5-tri , 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5-tris Wait.

Examples of the fluorenylphosphine oxide compound include 2,4,6-trimethylbenzylfluorenyldiphenylphosphine oxide and the like. Commercial products such as Irgacure (registered trademark) 819 (manufactured by BASF Corporation) can also be used.

Examples of the biimidazole compound include 2,2'-bis (2- (Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenyl Glycidazole (refer to Japanese Patent Application Laid-Open No. 6-75372, Japanese Patent Application Laid-Open No. 6-75373), 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrabenzene Bisimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorobenzene) ) -4,4 ', 5,5'-tetrakis (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetrakis (Trialkoxyphenyl) biimidazole (for example, refer to Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62-174204, etc.), and 4,4 ', 5,5'-phenyl phenyl An oxycarbonyl-substituted imidazole compound (see Japanese Patent Application Laid-Open No. 7-10913, etc.) and the like.

Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone and o-benzene Methyl amidinobenzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetrakis Benzophenone compounds such as 3butylcarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone; 10-butyl-2-chloroacridone, benzil, methyl phenylglyoxylate, titanocene compound and the like. These are preferably used in combination with a polymerization initiator (D1) (especially amines) described later.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethoxyloxyphenyldimethylformate. Hydrazone p-toluenesulfonate, 4-ethoxyfluorenyl / methyl / benzylfluorene hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate Salts, onium salts such as diphenylphosphonium p-toluenesulfonate, diphenylphosphonium hexafluoroantimonate; nitrobenzyl tosylate, benzoin toluene Sulfonates and so on.

As the polymerization initiator (D), it is selected from the group consisting of Polymerization initiators of at least one group of compounds, fluorenylphosphine oxide compounds, O-fluorenyl oxime compounds, and biimidazole compounds are preferred, and polymerization initiators containing O-fluorenyl oxime compounds are more preferred .

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to increase and the exposure time tends to be shortened, so that the productivity of the color filter is improved.

[6] Polymerization starting aid (D1)

The colored curable resin composition of the present invention may contain a polymerization initiator (D1). The polymerization initiator (D1) is a compound or a sensitizer used to promote the polymerization of a polymerizable compound that is polymerized by a polymerization initiator. When a polymerization initiator (D1) is included, it is usually used in combination with a polymerization initiator (D). Examples of the polymerization initiation aid (D1) include an amine compound, an alkoxyanthracene compound, a thioxanthone compound, and a carboxylic acid compound.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylamine. Isoamyl isobenzoate, 2-dimethylamino ethyl benzoate, 2-ethylhexyl 4-dimethylamino benzoate, N, N-dimethyl-p-toluidine, 4, 4'-bis (dimethylamino) benzophenone (commonly known as Michelin), 4,4'-bis (diethylamino) benzophenone, Of these, 4,4'-bis (ethylmethylamino) benzophenone is preferred, and 4,4'-bis (diethylamino) benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl -9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

Examples of the thiaxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorosulfan Heteranthrone, 1-chloro-4-propoxythioanthrone and the like.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, Methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthio Acetic acid, N-naphthyl glycine, naphthyloxyacetic acid, and the like.

When using these polymerization initiation aids (D1), the content is preferably 0.1 to 30 parts by mass, and more preferably 100 parts by mass relative to the total amount of the resin (B) and the polymerizable compound (C). 1 to 20 parts by mass. When the content of the polymerization initiator (D1) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of a color filter tends to be improved.

[7] Solvent (E)

The colored curable resin composition of the present invention may further contain a solvent (E). The solvent (E) is not particularly limited and can be used in this field Used solvents. Examples include: ester solvents (solvents containing -COO- and -O-free in the molecule), ether solvents (solvents containing -O- and -COO-free in the molecule), ether ester solvents (in the molecule Solvents containing -COO- and -O-), ketone solvents (solvents containing -CO-, -COO-free), alcohol solvents (containing OH, -O-, -CO free) -And -COO- solvents), aromatic hydrocarbon solvents, amidine solvents, dimethylsulfinium, and the like.

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 isoamyl acetate. , Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl 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, and Ethylene 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, tetrahydropiran, 1,4-di Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyl ether and Methyl anisole and so on.

Examples of the ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropionic acid. Methyl ester, ethyl 3-methoxypropionate, Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, Methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol mono Methyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like.

Examples of the ketone solvent include 4-hydroxy-4-ethyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, and 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 glycerol.

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

Examples of the amidine solvent include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

Among the above solvents, an organic solvent having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm in terms of coatability and drying properties is preferred. As the solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethyl ether are preferred. Diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone and N, N-dimethylformamide, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and Ethyl 3-ethoxypropionate.

The content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass based on the total amount of the coloring curable resin composition of the present invention. In other words, the total amount of the solid content of the colored curable resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. When the content of the solvent (E) is within 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. Therefore, the display characteristics tend to be improved.

[8] Leveling agent (F)

The colored curable resin composition of the present invention may further contain a leveling agent (F). Examples of the leveling agent (F) include a polysiloxane surfactant (without a fluorine atom), a fluorine surfactant (different from the polysiloxane surfactant), and a polysiloxane interface with a fluorine atom. Active agent etc. These may have a polymerizable group in a side chain.

Examples of the polysiloxane-based surfactant (without a fluorine atom) include a surfactant having a siloxane bond in the molecule. Specifically, it can be listed: TORAY SILICONE DC3PA, SH7PA of the same series, DC11PA of the same series, SH21PA of the same series, SH28PA of the same series, SH29PA of the same series, SH30PA of the same series, SH8400 of the same series (brand name: TORAY ‧DOW CORNING Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Shinyue Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 Momentive Performance Materials Japan).

As the aforementioned fluorine-based surfactant (different from polysiloxane Surfactants) include surfactants having a fluorocarbon chain in the molecule. Specific examples include: FLUORAD (registered trademark) FC430, the same series of FC431 (made by Sumitomo 3M Corporation), Megafac (registered trademark) F142D, the same series of F171, the same series of F172, the same series of F173, the same series F177, F183 of the same series, F554 of the same series, R30 of the same series, RS-718-K of the same series (manufactured by DIS Corporation), EFTOP (registered trademark) EF301, EF303 of the same series, EF351 of the same series, The same series of EF352 (Mitsubishi Materials Electronics Co., Ltd.), SURFLON (registered trademark) S381, the same series S382, the same series SC101, the same series SC105 (made by Asahi Glass Co., Ltd.) and E5844 (Daikin Precision Chemical Research Joint stock company system) and so on.

Examples of the polysiloxane-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples include Megafac (registered trademark) R08, BL20 of the same series, F475 of the same series, F477 of the same series, and F443 of the same series (made by DIS Corporation).

The content of the leveling agent (F) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less with respect to the total amount of the coloring curable resin composition of the present invention. More preferably, it is 0.01 mass% or more and 0.05 mass% or less. Note that the pigment dispersant is not included in the content ratio. When the content ratio of the leveling agent (F) is within the aforementioned range, the flatness of the color filter can be made good.

[9] other ingredients

The colored curable resin composition of the present invention may further include a filler if necessary. Fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, and other additives known in this technical field.

<Manufacturing method of colored curable resin composition>

The colored curable resin composition of the present invention can be mixed with a phthalocyanine pigment, a yellow colorant, a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a metal compound (M), and It is prepared according to the solvent (E), leveling agent (F), polymerization initiator (D1), and other components to be used.

Pigments such as phthalocyanine-based pigments are preferably mixed with a part or all of the solvent (E) in advance, and dispersed with a ball mill or the like until the average particle diameter of the pigment is 0.2 μm or less. In this case, a part or all of the pigment dispersant and the resin (B) may be blended as necessary. Since the pigment dispersion liquid thus obtained is mixed with the remaining components so as to have a predetermined concentration, the intended colored curable resin composition can be prepared.

When a dye is contained as a yellow colorant or the like, the dye can be separately dissolved in a part or all of the solvent (E) to prepare a solution. The metal compound (M) is prepared by dissolving a part or all of the solvent (E) in advance to prepare a solution, and the metal compound (M) may be dispersed in the same manner as the pigment. This solution is preferably filtered using a filter having a pore size of about 0.01 to 1 μm.

The mixed colored curable resin composition is preferably filtered using a filter having a pore size of about 0.01 to 10 μm.

<Manufacturing Method of Color Filter>

The colored curable resin composition of the present invention is suitable as a material for a color filter. A color filter formed from the coloring curable resin composition of the present invention is also one aspect of the present invention.

The color filter of the present invention can be formed by a method including the steps of applying the coloring curable resin composition to a substrate and drying it to form a colored composition layer, and exposing the coloring composition layer by exposing or the like. A step of hardening the colored composition layer. The color filter of the present invention has a colored pattern or a colored coating film.

Specific methods for producing a colored pattern include a photoetching method, an inkjet method, and a printing method, and a photoetching method is preferred.

The photoetching method is a method in which a colored curable resin composition is applied to a substrate and dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the photoetching method, a colored coating film of the cured product of the coloring composition layer can be formed by not using a photomask and / or not developing during exposure.

The film thickness of the color filter of the present invention is not particularly limited, and may be appropriately adjusted depending on the purpose and application, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

As the substrate, glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, and soda-lime glass coated with silicon oxide, polycarbonate, polymethyl methacrylate, and polyethylene terephthalate can be used. Resin plates, such as diesters, and silicon, are formed on the substrate with aluminum, silver, silver / copper / palladium alloy films, or the like. On these substrates, other color filter layers, resin layers, transistors, circuits, etc. can also be formed.

The formation of the pixels of each color by the photo-etching method can be performed using a conventional or conventional apparatus and conditions. For example, it can be produced as follows.

First, a colored curable resin composition is applied to a substrate. The board is dried by heating (pre-baking) and / or drying under reduced pressure to remove a volatile component such as a solvent, and drying it to obtain a smooth colored composition layer.

Examples of the coating method include a spin coating method, a slit coating method, a slit and a spin coating method, and the like.

The temperature during heating and drying is preferably 30 to 120 ° C, and more preferably 50 to 110 ° C. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.

When performing drying under reduced pressure, it is preferably performed at a temperature in the range of 20 to 25 ° C. under a pressure of 50 to 150 Pa.

The film thickness of the colored curable resin composition is not particularly limited, and may be appropriately selected depending on the film thickness of the intended color filter.

Next, the colored composition layer is exposed through a photomask for forming a desired colored pattern. The pattern on the reticle is not particularly limited, and a pattern corresponding to the intended use can be used.

As the light source used for the exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferred. For example: a filter that blocks light in a wavelength region up to 350 nm can be used to block light in that wavelength region; a filter that picks up light in a wavelength region near 436 nm, 408 nm, and 365 nm can be used to selectively remove the light Light of constant wavelength. Specific examples include a mercury lamp, a light-emitting diode, a metal halide lamp, and a halogen lamp.

Since the entire exposure surface can be uniformly irradiated with parallel light rays, and the photomask can be accurately aligned with the substrate on which the colored composition layer is formed, it is preferable to use an exposure device such as a photomask aligner and a stepper.

The exposed coloring composition layer is brought into contact with a developing solution to develop Shadow, thereby forming a colored pattern on the substrate. By development, the unexposed part of the colored composition layer is dissolved in the developing solution and removed. As the developing solution, for example, an aqueous solution of a basic compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide is preferred. The concentration in the aqueous solution of these basic compounds is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. Furthermore, the developing solution may contain a surfactant.

The development method may be any of a puddle method, a dipping method, and a spray method. Furthermore, the substrate can be tilted at any angle during development. After development, it is preferable to wash.

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

According to the colored curable resin composition of the present invention, a color filter excellent in light resistance can be produced. This color filter is a color filter used as a display device (liquid crystal display device, organic EL device, electronic paper, etc.) and a solid-state imaging element.

[Example]

Hereinafter, the colored curable resin composition of the present invention will be described in more detail by way of examples. Unless otherwise stated, "%" and "part" in the examples are mass% and mass part.

<Synthesis Example 1: Preparation of Resin (B)>

Nitrogen was passed through the flask equipped with a reflux cooler, a dropping funnel, and a stirrer to replace the nitrogen atmosphere, and 280 parts of propylene glycol monomethyl ether acetate was fed, and heated to 80 ° C. while stirring. Then, 38 parts of acrylic acid, 289 parts of a mixture of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8 and / or 9-ester, and propylene glycol monomethyl ether acetic acid were added dropwise over 5 hours. A mixed solution of 125 parts of ester. On the other hand, it took 6 hours to drip into a mixed solution in which 33 parts of 2,2-azobis (2,4-dimethylvaleronitrile) was dissolved in 235 parts of propylene glycol monomethyl ether acetate. After the dropwise addition, the mixture was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer [resin (B)] having a B-type viscosity (23 ° C) of 125 mPas, a solid content of 37.0%, and a solution acid value of 27 mg-KOH / g . The weight average molecular weight (Mw) of the copolymer was 9,200, and the degree of dispersion was 2.08.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured using the GPC method under the following conditions.

Installation: K2479 (made by Shimadzu Corporation)

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 ℃

Solvent: Tetrahydrofuran [THF]

Flow rate: 1.0mL / min

Sensor: RI

Calibration reference materials: TSK standard polystyrene F-40, F-4, F-288, A-2500, A-500 (manufactured by TOSOH Corporation).

The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the converted polystyrene obtained above was defined as the degree of dispersion.

<Synthesis Example 2: Preparation of Pigment Dispersion Liquid (A1)>

The following components were mixed and the pigment was dispersed using a ball mill, thereby obtaining a pigment dispersion liquid (A1).

C.I.Pigment Green 58 14.0 parts

Acrylic pigment dispersant 1.9 parts

84.1 parts of propylene glycol monomethyl ether acetate.

<Synthesis Example 3: Preparation of Pigment Dispersion Liquid (A2)>

The following ingredients were mixed and the pigment was dispersed using a ball mill, thereby obtaining a pigment dispersion liquid (A2) C.I. Pigment Yellow 138 12.0 parts

Acrylic pigment dispersant 6.0 parts

82.0 parts of propylene glycol monomethyl ether acetate.

<Synthesis Example 4: Preparation of Pigment Dispersion Liquid (A3)>

The following ingredients were mixed and the pigment was dispersed using a ball mill, thereby obtaining a pigment dispersion liquid (A3) C.I. Pigment Yellow 150 12.0 parts

Acrylic pigment dispersant 6.0 parts

82.0 parts of propylene glycol monomethyl ether acetate.

<Synthesis Example 5: Preparation of Pigment Dispersion Liquid (A4)>

The following ingredients were mixed and the pigment was dispersed using a ball mill, thereby obtaining a pigment dispersion liquid (A4) C.I. Pigment Yellow 185 5.0 parts

3.5 parts of acrylic pigment dispersant

88.0 parts of propylene glycol monomethyl ether acetate.

<Synthesis Example 6: Preparation of Pigment Dispersion Liquid (A5)>

The following ingredients were mixed and the pigment was dispersed using a ball mill, thereby obtaining a pigment dispersion liquid (A5) C.I. Pigment Green 59 11.0 parts

Acrylic pigment dispersant 3.6 parts

81.0 parts of propylene glycol monomethyl ether acetate.

<Examples 1 to 53 and Comparative Examples 1 to 3>

(1) Preparation of colored curable resin composition

The components described in Table 1 were mixed to obtain a colored curable resin composition. When preparing the colored curable resin composition, propylene glycol monomethyl ether acetate was mixed so that the solid content of the colored curable resin composition was 20% by mass. The unit of the amount of each component in Tables 1 and 2 is "mass part".

Each component shown in Table 1 is as follows.

[1] Metal compound (M1): a compound represented by the following formula,

[2] Metal compound (M2): a compound represented by the following formula,

[3] Metal compound (M3): a compound represented by the following formula,

[4] Metal compound (M4): a compound represented by the following formula,

[5] Metal compound (M5): a compound represented by the following formula (nickel dibutyldithiocarbamate),

[6] Metal compound (M6): a compound represented by the following formula (ethynylferrocene),

[7] Metal compound (M7): a compound represented by the following formula (ferrocenecarboxylic acid),

[8] Metal compound (M8): a compound represented by the following formula (refer to (hexafluoroacetamidineacetone) iron (III)),

[9] Metal compound (M9): a compound represented by the following formula (cf. (dibenzofluorenylmethane) iron (III)),

[10] Metal compound (M10): a compound represented by the following formula (hemin),

[11] Metal compound (M11): a compound represented by the following formula,

[12] Metal compound (M12): a compound represented by the following formula (bis (2,4-pentanedionate) cobalt (II)),

[13] Metal compound (M13): a compound represented by the following formula (bis (2,4-pentanedionate) cobalt (II) dihydrate)

[14] Metal compound (M14): a compound represented by the following formula (titanium (2,4-pentanedionate) titanium (IV))

[15] Metal compound (M15): a compound represented by the following formula (cf. (2,4-pentanedionate) cobalt (III))

[16] Metal compound (M16): a compound represented by the following formula (cf. (2,4-pentanedionate) indium (III))

[17] Metal compound (M17): a compound represented by the following formula (bis (2,4-pentanedionate) manganese (II) dihydrate)

[18] Metal compound (M18): a compound represented by the following formula (bis (2,4-pentanedionate) zinc (II))

[19] Metal compound (M19): a compound represented by the following formula (copper (II) trifluoromethanesulfonate)

[20] Metal compound (M20): a compound represented by the following formula (Zirconium (IV) (2,4-pentanedionate))

[21] Metal compound (M21): a compound represented by the following formula (bis (2,4-pentanedionate) tin (IV) dichloride)

[22] Metal compound (M22): a compound represented by the following formula (bis (2,4-pentanedionate) vanadium (IV) oxide)

[23] Metal compound (M23): a compound represented by the following formula (bis (2,4-pentanedionate) copper (II))

[24] Metal compound (M24): a compound represented by the following formula (bis (hexafluoroacetamidinepyruvate) cobalt (II) hydrate),

[25] Metal compound (M25): a compound represented by the following formula (cf. (2,4-pentanedionate) iron (III))

[26] Metal compound (M26): a compound represented by the following formula (cf. (2-ethylhexylcarboxylic acid) iron (III))

[27] Metal compound (M27): Compound represented by the following formula (iron (III) stearate)

[28] Metal compound (M28): a compound represented by the following formula (cobalt (II) stearate)

[29] Resin (B): resin (B) contained in the resin solution obtained in Synthesis Example 1,

[30] Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.),

[31] Polymerization initiator (D): N-benzyloxy-1- (4-phenylthiophenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE01; (Made by BASF Japan),

[32] Leveling agent (F): polyether modified silicone oil (TORAY SILICONE S8400; TORAY‧DOW CORNING Co., Ltd.).

[Calculation of molar absorption coefficient]

In a measuring flask, 0.1 g of a metal compound was fed, and then diluted to 0.250 L with dimethylformamide (DMF) or ethyl lactate. For this solution, an ultraviolet-visible spectrophotometer (V-650DS; manufactured by JASCO Corporation) (quartz colorimeter tube, optical path length; 1 cm) was used to measure the absorption spectrum, and the visible light region (460 to 460) was calculated using Lambert-Beer law 620 nm), the maximum value [ε]. The results are shown in Table 3.

(2) Production of colored graphics

The colored curable resin composition was applied on a 5 cm square glass substrate (EAGLE2000; manufactured by CORNING) by a spin coating method, and then prebaked at 100 ° C for 3 minutes to form a colored composition layer. After leaving to cool, the distance between the substrate on which the colored composition layer was formed and a mask made of quartz glass was set to 100 μm, and an exposure machine (TME-150RSK; manufactured by TOPCON Corporation) was used at 150 mJ / cm ² in an atmospheric environment The exposure amount (based on 365 nm) was irradiated with light. As the mask, a mask having a 1: 1 line and space pattern of 100 μm formed was used. The coloring composition layer after light irradiation was immersed in an aqueous developing solution containing 0.12% of a non-ionic surfactant and 0.04% of potassium hydroxide at 24 ° C for 60 seconds and developed. After washing, it was 230 ° C in an oven. After 20 minutes of post-baking, a colored pattern was obtained. The film thickness of the obtained colored pattern was 2.5 μm in all Examples and Comparative Examples.

(3) Measurement of initial brightness

With respect to the obtained coloring pattern, a spectrometer (OSP-SP-200; manufactured by OLYMPUS Co., Ltd.) was used to measure the spectrometry, and a characteristic function of the C light source was used to measure the xy chromaticity coordinates (x, y) and Stimulus value Y. A larger value of Y indicates higher brightness. When the stimulus value Y of the coloring pattern made of the coloring curable resin composition of Comparative Examples 1 to 3 is set to 100%, the relative value (%) of the tristimulus value Y of the coloring pattern made of each example and comparative example It is shown in the "initial brightness" column of Tables 4 and 5.

(4) Evaluation of light resistance

A UV blocking filter (COLORED OPTICAL GLASS L38; manufactured by HOYA Corporation; Light at 380 nm or less) was irradiated with light from a xenon lamp for 48 hours using a light resistance tester (SUNTEXT CPS +: manufactured by Toyo Seiki Seisakusho Co., Ltd.). The relative value (%) of the stimulus value Y after the xenon lamp light irradiation when the stimulus value Y before the xenon lamp irradiation (the initial brightness obtained in (3) above) is set to 100% is shown in Tables 4 and 5 under "Brightness Rate of Change "field. The closer the brightness change rate is to 100%, the higher the light resistance.

[Industrial availability]

According to the colored curable resin composition of the present invention, a color filter having good light resistance and a display device including the same can be provided.

Claims (5)

A colored hardening resin composition comprising a phthalocyanine pigment, a yellow colorant, a resin (B), a polymerizable compound (C), a polymerization initiator (D) and a metal compound (M). The compound (M) is different from a phthalocyanine pigment and a yellow colorant. The colored curable resin composition according to item 1 of the patent application scope, wherein the phthalocyanine pigment is a halogenated phthalocyanine pigment. The colored curable resin composition according to item 1 or 2 of the patent application scope is a green colored curable resin composition. A color filter is formed of the color-hardening resin composition described in item 1 or 2 of the scope of patent application. A display device includes a color filter described in item 4 of the scope of patent application.