JP6837863B2 - Red coloring composition - Google Patents

Description

The present invention relates to a red coloring composition.

Color filters are used in display devices such as liquid crystal display panels, electroluminescence panels, and plasma display panels.
Patent Document 1 describes a coloring composition capable of producing a high-contrast color filter. According to Patent Document 2, by adjusting the chromaticity of red, it is possible to adjust white to a target color temperature (K) and color difference (Δuv) without changing the chromaticity of blue, green, and red. A red coloring composition for a color filter is described.

Japanese Unexamined Patent Publication No. 2013-014750 Japanese Unexamined Patent Publication No. 2005-181384

An object of the present invention is to provide a red coloring composition capable of improving the contrast of a red color filter in particular. Another object of the present invention is to provide a red coloring composition, a color filter, and a display device including the color filter.

The present invention provides the red coloring composition, the color filter and the display device shown below.
[1] Red colorant and C.I. I. A red coloring composition comprising Pigment Blue 16.
[2] With respect to 100 parts by mass of the red colorant, C.I. I. The red coloring composition according to [1], wherein the content of Pigment Blue 16 is 0.005 part by mass or more and 1.5 part by mass or less.
[3] The red coloring composition according to [1] or [2], wherein the red coloring agent contains a compound having a diketopyrrolopyrrole skeleton.
[4] The red coloring composition according to any one of [1] to [3], further comprising a resin (B), a polymerizable compound (C) and a polymerization initiator (D).
[5] A color filter formed from the red coloring composition according to [4].
[6] A display device including the color filter according to [5].

By using the red coloring composition of the present invention, it is possible to provide a red color filter having improved contrast and a display device including the color filter.

<Red coloring composition>
The red coloring composition of the present invention comprises a red coloring agent and C.I. I. Includes Pigment Blue 16. The red coloring composition includes a red coloring agent and C.I. I. It may contain other coloring components other than Pigment Blue 16.
C.I. I. Pigment Blue 16 may be used as a contrast improver for improving the contrast of the red color filter.
Further, the red coloring composition may contain a resin (B), a polymerizable compound (C), and a polymerization initiator (D). In the following, the red colorant and C.I. I. A red coloring composition containing Pigment Blue 16, a resin (B), a polymerizable compound (C), and a polymerization initiator (D) may be particularly referred to as a "red coloring curable resin composition".
Unless otherwise specified, the compounds exemplified as each component in the present specification may be used alone or in combination of two or more.

Hereinafter, each component contained in the red coloring composition of the present invention will be described.
(Red colorant)
Examples of the red colorant include red pigments, red dyes, orange pigments, orange dyes and the like. The red colorant may consist of one type or may contain two or more types.

Examples of the red pigment include compounds having a diketopyrrolopyrrole skeleton and compounds classified as pigments in the Color Index (published by The Society of Dyers and Colorists).
The structure of the diketopyrrolopyrrole skeleton is represented by the following formula.

Examples of the compound having a diketopyrrolopyrrole skeleton include a compound represented by the following formula (P).

[In the formula (P), Ra ¹ , Ra ² , Ra ³ and Ra ⁴ independently represent a hydrogen atom, a halogen atom or a monovalent substituent, and at least one represents a halogen atom. ]

Examples of the halogen atom in R ^a1 , Ra ² , Ra ³ and Ra ⁴ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom and a bromine atom are preferable.

The ^{monovalent substituents in R a1} , R ^a2 , R ^a3 and R ^a4 include cyano groups, -CF ₃ , -R ^a5 , -OR ^a5 , -SR ^a5 , -SOR ^a5 , -S (O) ₂ R. ^Examples thereof include a5, -NR ^a6 COR ^a5 , -CONR ^a5 R ^a6 , and -CONH _2.
R ^a5 represents an alkyl group having 1 to 5 carbon atoms, a phenyl group or a naphthyl group, and -CH _2- ^{contained in the alkyl group is -NR a7-} , -O-, -S-, -SO- or It may be replaced by −S (O) _2−.
R ^a6 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and -CH _2- ^{contained in the alkyl group is -NR a7-} , -O-, -S-, -SO- or -S ( O) It may be replaced by _2-.
R ^a5 and R ^a6 may be combined to form an alkanediyl group having 2 to 8 carbon atoms, and −CH ₂ − contained in the alkanediyl group is −NR ^a7 −, −O−, −. It may be replaced by S-, -SO- or -S (O) _2-.
R ^a7 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an isopropyl group, an isobutyl group, a sec-butyl group and an isopentyl group.
The alkanediyl group having 2 to 8 carbon atoms includes an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, and a butane-1,3-diyl group. , Pentan-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group and the like.
Examples of −OR ^a5 include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group and the like.
Examples of -SR ^a5 include a methyl sulfanyl group, an ethyl sulfanyl group, a propyl sulfanyl group, a butyl sulfanyl group, a pentyl sulfanyl group and the like.
Examples of -SOR ^a5 include methylsulfinyl group, ethylsulfinyl group, propylsulfinyl group, butylsulfinyl group, pentylsulfinyl group and the like.
Examples of −S (O) ₂ R ^a5 include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, a pentylsulfonyl group and the like.
Examples of the -NR ^a6 COR ^a5 include an N-acetylamino group, an N-propionylamino group, an N-benzoylamino group, an N-methyl-N-acetylamino group and the like.
Among the -NR ^a6 COR ^a5 , examples of the group in which R ^a5 and R ^a6 form a ring include a group represented by the following formula.

The −CONR ^a5 R ^a6 includes an N-methylaminocarbonyl group, an N-ethylaminocarbonyl group, an N, N-dimethylaminocarbonyl group, an N, N-diethylaminocarbonyl group, an N, N-ethylmethylaminocarbonyl group and the like. Can be mentioned.
Among the −CONR ^a5 R ^a6 , examples of the group in which R ^a5 and R ^a6 form a ring include a group represented by the following formula.

In the compounds of represented by Formula ^(P), among ^{R a1,} R a2, R ^a3 and ^{R a4,} of ^{R a1} and ^{R a2,} it is preferable that at least one is a chlorine atom or a bromine ^{atom, R a1} is It is more preferable that the atom is a chlorine atom or a bromine atom and ^{Ra2 is a chlorine atom or a bromine atom.}
It is preferable that both R ^a3 and R ^{a4 are hydrogen atoms.}
Specifically, as the compound represented by the formula (P), R ^a1 and R ^a2 are both chlorine atoms, and R ^a3 and R ^a4 are both hydrogen atoms. I. Pigment Red 254 can be mentioned.

Further, examples of the compound represented by the formula (P) include a compound represented by the following formula.

Compounds classified as pigments in the above color index include the above-mentioned C.I. I. In addition to Pigment Red 254, for example, C.I. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 255, 264, 265 and the like.

Examples of the red dye include compounds classified as dyes in the above color index and known dyes described in dyeing notes (color dyeing company).
Specifically, C.I. I. As an acid dye, for example, C.I. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426 and the like can be mentioned.
C. I. As a direct dye, for example, C.I. I. 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 and the like can be mentioned.
C. I. As a modern dye, for example, C.I. I. Modant Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41 , 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95 and the like.

Examples of the orange pigment include compounds classified as pigments in the above color index.
Specifically, C.I. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and the like.

Examples of the orange dye include compounds classified as dyes in the above color index and known dyes described in the above dyeing notes.
Specifically, C.I. I. As an acid dye, for example, C.I. I. Acid oranges 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173 and the like can be mentioned.
C. I. As a direct dye, C.I. I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107 and the like can be mentioned.
C. I. As a modern dye, for example, C.I. I. Modant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48, etc. Can be done.

As the red dye and the orange dye, in addition to the above-mentioned ones, a xanthene dye having a red or orange color and containing a compound having a xanthene skeleton in the molecule, or a red or orange dye, which may be complex chloride with a metal atom in the molecule. A dye molecule containing a group, a metal complex salt dye obtained by complexing a metal atom, an azo dye exhibiting a red or orange color, or the like may be used.
The xanthene dyes having a red or orange color partially overlap with the above-mentioned dyes, but for example, C.I. I. Acid Red 51, 52, 87, 92, 94, 289, 388, C.I. I. Basic Red 1 (Rhodamine 6G), 8, C.I. I. Basic Red 10 (Rhodamine B), C.I. I. Solvent Red 218, C.I. I. Modant Red 27, C.I. I. Examples thereof include reactive red 36 (rose bengal B), sulforhodamine G, xanthene dyes described in JP-A-2010-32999, and xanthene dyes described in Japanese Patent No. 4492760.
The metal complex salt dye exhibiting a red or orange color partially overlaps with the above-mentioned dyes, but for example, C.I. I. Solvent Orange 5, 11, 20, 40: 1, 41, 45, 54, 56, 58, 62, 70, 81, 99, C.I. I. Solvent Red 8, 35, 83: 1, 84: 1, 90, 90: 1, 91, 92, 118, 119, 122, 124, 125, 127, 130, 132, 160, 208, 212, 214, 225, 233, 234, 243, C.I. I. Acid Orange 74, 162, C.I. I. Examples thereof include acid red 211, metal complex salt dyes described in JP-A-2010-170117 and JP-A-2011-59673.
Examples of the azo dye exhibiting a red or orange color include the azo dye described in JP2013-14750A.

As the red colorant, a red pigment and / or a red dye is preferably used, and more preferably a red pigment is used, from the viewpoint of improving the contrast obtained by the red coloring composition. Examples of the red pigment include C.I. I. When Pigment Blue 16 is used, it is preferable to use a compound having a diketopyrrolopyrrole skeleton because the contrast improvement of the red color filter is easy to see.
When the red colorant contains a compound having a diketopyrrolopyrrole skeleton, the content of the compound having a diketopyrrolopyrrole skeleton is preferably 1 to 100 parts by mass, more preferably 1 part by mass, based on 100 parts by mass of the total amount of the red colorant. Is 20 to 100 parts by mass, more preferably 40 to 100 parts by mass.

(CI Pigment Blue 16)
The red coloring composition of the present invention is a blue pigment, C.I. I. Includes Pigment Blue 16. C. I. Pigment Blue 16 can be used as a contrast improver for improving the contrast of the color filter. The red colorant composition of the present invention and the red colorant together with C.I. I. By using Pigment Blue 16, the contrast of the red color filter can be improved.

C. in the red coloring composition. I. The content of Pigment Blue 16 is not particularly limited as long as the red coloring composition exhibits the desired red color, but is 0.005 parts by mass with respect to 100 parts by mass of the red coloring agent in these red coloring compositions. The above is preferable, 0.4 parts by mass or more is more preferable, 1.5 parts by mass or less is preferable, and 0.8 parts by mass or less is more preferable. C. I. When the content of Pigment Blue 16 is less than 0.005 parts by mass, the effect of improving the contrast tends to be too small, and C.I. I. When the content of Pigment Blue 16 exceeds 1.5 parts by mass, it tends to be difficult to obtain the desired red hue.

(Other coloring components)
The red coloring composition of the present invention comprises a red coloring agent and C.I. I. It may contain other coloring components other than Pigment Blue 16. As the other coloring components, only one kind may be used, or two or more kinds may be used in combination. Other coloring components include C.I. I. Examples thereof include a blue colorant other than Pigment Blue 16, a yellow colorant, a green colorant, a violet colorant, a brown colorant, a black colorant, and the like, which may be a pigment or a dye. .. The content of the other coloring components is not particularly limited as long as the red coloring composition exhibits the desired red color, but the red coloring agent and C.I. I. It is preferably 0.005 to 10 parts by mass with respect to 100 parts by mass of the total amount of Pigment Blue 16.

(Resin (B))
The red coloring composition of the present invention may be a red coloring curable resin composition containing the resin (B), the polymerizable compound (C), and the polymerization initiator (D). The red colored curable resin composition may contain one kind or two or more kinds of resins (B). The resin (B) is preferably an alkali-soluble resin. Alkali-soluble refers to the property of being soluble in a developing solution, which is an aqueous solution of an alkaline compound. Examples of the resin (B) include the following resins [K1] to [K6].

Resin [K1]: At least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (a) [hereinafter, may be referred to as "(a)". ], And a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond [hereinafter, may be referred to as “(b)”. ) And a copolymer.
Resin [K2]: (a) and (b) and monomer (c) copolymerizable with (a) (however, different from (a) and (b)) [hereinafter "(c)" There is that. ] And copolymer.
Resin [K3]: A copolymer of (a) and (c).
Resin [K4]: A resin obtained by reacting (b) with a copolymer of (a) and (c).
Resin [K5]: A resin obtained by reacting (a) with a copolymer of (b) and (c).
Resin [K6]: A resin obtained by reacting (a) with a copolymer of (b) and (c) and further reacting with a carboxylic acid anhydride.

Specifically, as (a),
Unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid, 1,4-cyclohexendicarboxylic acid;
Methyl-5-norbornene-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] A bicyclounsaturated compound containing a carboxy group such as hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride);
Unsaturated mono [(meth) acryloyloxyalkyl] esters of divalent or higher valent carboxylic acids such as mono [2- (meth) acryloyloxyethyl] succinate and mono [2- (meth) acryloyloxyethyl] phthalates. ;
Examples thereof include unsaturated (meth) acrylic acid containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) (meth) acrylic acid.
Above all, from the viewpoint of copolymerization reactivity and solubility in an alkaline aqueous solution, (a) is preferably (meth) acrylic acid, maleic anhydride or the like.

In addition, in this specification, "(meth) acrylic" represents at least one kind selected from the group consisting of acrylic and methacrylic. The same applies to the notations such as "(meth) acryloyl" and "(meth) acrylate".

(B) is a polymerization having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxylan ring, an oxetane ring and a tetrahydrofuran ring (oxolane ring)) and an ethylenically unsaturated bond. Refers to a sex compound. Reference numeral (b) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group.
As (b), there is a monomer (b1) having an oxylanyl group and an ethylenically unsaturated bond [hereinafter, referred to as “(b1)”. ], Monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond [hereinafter, may be referred to as “(b2)”. ], Monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond [hereinafter, may be referred to as “(b3)”. ] Etc. can be mentioned.

As (b1), there is a monomer (b1-1) having a structure in which an unsaturated aliphatic hydrocarbon is epoxidized [hereinafter, referred to as “(b1-1)”. ], Monomer (b1-2) having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized [hereinafter, may be referred to as “(b1-2)”. ] Can be mentioned.

Examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p. -Vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene , 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene , 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (Glysidyloxymethyl) styrene and the like can be mentioned.

Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy4-vinylcyclohexane (for example, celloxide 2000; manufactured by Daicel Chemical Industries, Ltd.), and 3,4-epoxycyclohexylmethylacrylate (for example, cyclomer). A400; manufactured by Daicel Chemical Industry Co., Ltd., 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industry Co., Ltd.), a compound represented by the formula (I), formula (II). Examples thereof include compounds represented by.

[In formulas (I) and (II), ^Ra and R ^b independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group. It may be replaced with. X ¹ and X ² are each independently a single ^{bond, * - R c -, *} - R c -O -, * - R c -S-, or * represents a -R ^c -NH-. R ^c represents an alkanediyl group having 1 to 6 carbon atoms. * Represents a bond with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and the like.
Alkyl groups in which the hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group and 1-hydroxy. Examples thereof include -1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 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 and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.
The ^{alkanediyl group constituting R c} includes a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5-. Examples thereof include a diyl group and a hexane-1,6-diyl group.

X ¹ and X ² are preferably a single bond, a methylene group, an ethylene group, a * -CH _2- O- (* represents a bond with O) group, and a * -CH ₂ CH _2- O- group. , More preferably a single bond, * -CH ₂ CH _2- O- group.
Specific examples of the compound represented by the formula (I) include compounds represented by the formulas (I-1) to (I-15), preferably formulas (I-1) and (I-3). ), Formula (I-5), Formula (I-7), Formula (I-9), Formulas (I-11) to Formulas (I-15), and more preferably the formula (I-15). Examples thereof include compounds represented by I-1), formula (I-7), formula (I-9), and formula (I-15).

Specific examples of the compound represented by the formula (II) include compounds represented by the formulas (II-1) to (II-15), preferably formulas (II-1) and (II-). Examples thereof include compounds represented by 3), formula (II-5), formula (II-7), formula (II-9), formulas (II-11) to formulas (II-15), and more preferably the formulas. Examples thereof include compounds represented by (II-1), formula (II-7), formula (II-9), and 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. When two or more kinds are used in combination, the mixing ratio is the formula (I): formula (II) [molar ratio], preferably 5:95 to 95: 5, more preferably 20:80 to 80:20, and further. It is preferably 50:50 to 80:20.
The monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond is preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group.
Preferred examples of (b2) include 3-methyl-3- (meth) acryloyloxymethyloxetane, 3-ethyl-3- (meth) acryloyloxymethyloxetane, 3-methyl-3- (meth) acryloyloxyethyloxetane, and the like. 3-Ethyl-3- (meth) acryloyloxyethyl oxetane can be mentioned.
The monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond is preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group. Preferred examples of (b3) include tetrahydrofurfuryl acrylate (for example, Viscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate and the like.

As a specific example of (c),
Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, Lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8- Il (meth) acrylate [In the art, it is commonly referred to as "dicyclopentanyl (meth) acrylate". It may also be called "tricyclodecyl (meth) acrylate". ], Tricyclo [5.2.1.0 ^2,6 ] Decene-8-yl (meth) acrylate [In the art, it is commonly referred to as "dicyclopentenyl (meth) acrylate". ], Dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (Meta) acrylic acid esters such as (meth) acrylate;
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconic acid;
Bicyclo [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] 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] Bicyclounsaturated compounds such as hept-2-ene;
Dicarbonylimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, (meth) acrylonitrile, vinyl chloride, vinylidene chloride, (meth) acrylamide, vinyl acetate, 1,3-butadiene, Examples thereof include isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Among them, from the viewpoint of copolymerization reactivity and heat resistance, (c) includes benzyl (meth) acrylate, tricyclodecyl (meth) acrylate, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide. Bicyclo [2.2.1] hepto-2-ene and the like are preferable. Further, benzyl (meth) acrylate and tricyclodecyl (meth) acrylate are more preferable as (c) because they are excellent in developability at the time of pattern formation.

In the resin [K1], the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the resin [K1].
Structural units derived from (a), particularly structural units derived from (b1); 50-98 mol% (more preferably 55-90 mol%),
Structural unit derived from (b); 2-50 mol% (more preferably 10-45 mol%).
When the ratio of the structural units of the resin [K1] is within the above range, the storage stability, developability, and solvent resistance of the obtained pattern tend to be excellent.
The resin [K1] is described in the method described in the document "Experimental method for polymer synthesis" (written by Takayuki Otsu, published by Kagaku-Dojin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972) and the document. It can be manufactured with reference to the cited references.
Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent and the like are placed in a reaction vessel, and for example, oxygen is replaced with nitrogen to create a deoxidized atmosphere, and the mixture is stirred. Examples include heating and heat retention. The polymerization initiator, solvent, and the like used here are not particularly limited, and any of those usually used in the art can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.). Be done. The solvent may be any one that dissolves each monomer, and the solvent (E) described later can be used as the solvent for the red colored curable resin composition.
As the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation or the like. You may use it. In particular, by using the solvent (E) described later as the solvent in this polymerization, the solution after the reaction can be used as it is, and the production process can be simplified.

In the resin [K2], the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the resin [K2].
Structural unit derived from (a); 4 to 45 mol% (more preferably 10 to 30 mol%),
Structural units derived from (b), particularly structural units derived from (b1); 2-95 mol% (more preferably 5-80 mol%),
Structural unit derived from (c); 1-65 mol% (more preferably 5-60 mol%).
When the ratio of the structural units of the resin [K2] is within the above range, the storage stability, developability, solvent resistance of the obtained pattern, heat resistance and mechanical strength tend to be excellent.
The resin [K2] can be produced in the same manner as described as the method for producing the resin [K1]. Specifically, predetermined amounts of (a), (b) (particularly (b1)) and (c), a polymerization initiator and a solvent are charged in the reaction vessel, and stirred, heated and kept warm in a deoxidized atmosphere. There is a way to do it. As the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation or the like. You may use it.

In the resin [K3], the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the resin [K3].
Structural unit derived from (a); 2-55 mol% (more preferably 10-50 mol%),
Structural unit derived from (c); 45-98 mol% (more preferably 50-90 mol%).
The resin [K3] can be produced in the same manner as described as the method for producing the resin [K1].

The resin [K4] obtained a copolymer of (a) and (c), and (a) has a cyclic ether structure having 2 to 4 carbon atoms of (b), particularly an oxylane ring of (b1). It can be produced by adding it to a carboxylic acid and / or a carboxylic acid anhydride having it. Specifically, first, the copolymer of (a) and (c) is produced in the same manner as the method described as the method for producing the resin [K1]. In this case, the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the copolymer of (a) and (c).
Structural unit derived from (a); 5-50 mol% (more preferably 10-45 mol%),
Structural unit derived from (c); 50-95 mol% (more preferably 55-90 mol%).

Next, a part of the carboxylic acid and / or carboxylic acid anhydride derived from (a) in the above-mentioned copolymer has a cyclic ether structure having 2 to 4 carbon atoms, particularly (b1). React the oxylane ring. Specifically, following the production of the copolymer of (a) and (c), the atmosphere in the flask was replaced with air from nitrogen to obtain (b) (particularly (b1)), a carboxylic acid or a carboxylic acid anhydride. A reaction catalyst (for example, tris (dimethylaminomethyl) phenol, etc.) and a polymerization inhibitor (for example, hydroquinone, etc.) with the cyclic ether structure are placed in a flask and reacted at 60 to 130 ° C. for 1 to 10 hours. , Resin [K4] can be obtained.
The amount of (b) used, particularly the amount of (b1) used, is preferably 5 to 80 mol, more preferably 10 to 75 mol, with respect to 100 mol of (a). Within this range, the balance between storage stability, developability, solvent resistance, heat resistance, mechanical strength and sensitivity tends to be good. Since the cyclic ether structure is highly reactive and the unreacted (b) is unlikely to remain, (b1) is preferable as the (b) used for the resin [K4], and (b1-1) is more preferable.
The amount of the reaction catalyst used is preferably 0.001 to 5% by mass with respect to the total amount of (a), (b) (particularly (b1)) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5% by mass with respect to the total amount of (a), (b) and (c).
The reaction conditions such as the charging method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the calorific value due to polymerization and the like. As with the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

As the first step, the resin [K5] obtains a copolymer of (b) (particularly (b1)) and (c) in the same manner as in the method for producing the resin [K1] described above. In the same manner as above, the obtained copolymer may be a solution after the reaction as it is, a concentrated or diluted solution may be used, or a solid (powder) may be used by a method such as reprecipitation. You may use the one taken out as.
The ratio of the structural units derived from (b) (particularly (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-mentioned copolymer.
Structural units derived from (b), particularly structural units derived from (b1); 5 to 95 mol% (more preferably 10 to 90 mol%),
Structural unit derived from (c); 5 to 95 mol% (more preferably 10 to 90 mol%).

Further, under the same conditions as the method for producing the resin [K4], (a) is added to the cyclic ether structure derived from (b) of the copolymer of (b) (particularly (b1)) and (c). The resin [K5] can be obtained by reacting the carboxylic acid or the carboxylic acid anhydride having the resin. The amount of (a) to be reacted with the above copolymer is preferably 5 to 80 mol with respect to 100 mol of (b) (particularly (b1)). Since the cyclic ether structure is highly reactive and the unreacted (b) is unlikely to remain, (b1) is preferable as the (b) used for the resin [K5], and (b1-1) is more preferable.

The resin [K6] is a resin obtained by further reacting the resin [K5] with a carboxylic acid anhydride. The carboxylic acid anhydride is reacted with the hydroxy group generated by the reaction of the cyclic ether structure with the carboxylic acid or the carboxylic acid anhydride.
Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic acid 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 anhydride (hymic acid anhydride) and the like. Be done.

Among the resins [K1] to [K6], the preferred resin as the resin (B) is [K1] or [K2]. The resin (B) may be made of one kind of resin or may contain two or more kinds of resins.

The polystyrene-equivalent weight average molecular weight (Mw) 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, It is 000. When the weight average molecular weight (Mw) is in the above range, the unexposed portion tends to have high solubility in a developing solution, 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 1.1 to 6, and more preferably 1.2 to 4.
The solution acid value of the resin (B) is preferably 5 to 180 mg-KOH / g, more preferably 10 to 100 mg-KOH / g, and even more preferably 12 to 50 mg-KOH / g. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be determined by titration using, for example, an aqueous potassium hydroxide solution.
The content of the resin (B) is preferably 5 to 50% by mass, more preferably 15 to 45% by mass, and further preferably 25 to 25% by mass, based on 100% by mass of the solid content of the red colored curable resin composition. It is 40% by mass. When the content of the resin (B) is in the above range, the unexposed portion tends to have high solubility in the developing solution.

(Polymerizable compound (C))
The polymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by an active radical or the like generated from the polymerization initiator (D) by light irradiation or the like, and is a compound having a polymerizable ethylenically unsaturated bond or the like. Can be mentioned. The weight average molecular weight of the polymerizable compound (C) is preferably 3,000 or less.
Among them, the polymerizable compound (C) is preferably a photopolymerizable compound having three or more ethylenically unsaturated bonds, and is preferably trimethylpropantri (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol. Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate , Tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (meth) acrylate, propylene glycol-modified Examples thereof include pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate. Of these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like are preferable.
The red coloring composition (red coloring curable resin composition) of the present invention can contain one kind or two or more kinds of polymerizable compounds (C). The content of the polymerizable compound (C) is preferably 20 to 150 parts by mass, and more preferably 40 to 70 parts by mass with respect to 100 parts by mass of the resin (B) in the red colored curable resin composition. is there.

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

Examples of the polymerization initiator (D) include oxime compounds such as O-acyloxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds.
Two or more types of the polymerization initiator (D) may be used in combination in consideration of sensitivity, formability of a precise pattern shape, and the like. The polymerization initiator (D) preferably contains an oxime compound such as an O-acyloxime compound because it is advantageous in precisely forming a pattern shape having sensitivity and a desired line width.

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

Examples of such O-acyloxym compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane. -1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetyloxy-1- [9-ethyl-6 -(2-Methylbenzoyl) -9H-carbazole-3-yl] ethane-1-imine, N-acetyloxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-) 2,4-Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazole-3-yl] ethane-1-imine, N-acetyloxy-1- [9-ethyl-6- (2-methylbenzoyl)- 9H-carbazole-3-yl] -3-cyclopentylpropan-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -3- Cyclopentylpropan-1-one-2-imine, N-acetyloxy-1- [9- (2-ethylhexyl) -6- (2,4,6-trimethylbenzoyl) -9H-benzo [i] carbazole-3-3 Il] -3- [1- (2,2,3,3-tetrafluoropropyloxy) phenyl] methaneimine and the like. Commercially available products such as Irgacure OXE01, OXE02, OXE03 (all manufactured by BASF Corporation) and N-1919 (manufactured by ADEKA Corporation) may be used. With these O-acyloxime compounds, there is a tendency to obtain a color filter having excellent photolithography performance.

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

Examples of the compound having a structure represented by the formula (d4) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl). ) -2-Benzylbutane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1-one, etc. Be done. Commercially available products such as Irgacure 369, 907, 379 (all manufactured by BASF Limited) may be used.
Examples of the compound having a 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] Propane-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one oligomer, α, α-diethoxyacetophenone, benzyl Dimethylketal and the like can be mentioned.
In terms of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by the formula (d4).

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl) -4,4. ', 5,5'-Tetraphenylbiimidazole (see, for example, JP-A-6-75372, JP-A-6-75373, etc.), 2,2'-bis (2-chlorophenyl) -4,4' , 5,5'-Tetraphenyl biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2-) Chlorophenyl) -4,4', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (trialkoxyphenyl) Biimidazole (see, for example, Japanese Patent Publication No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.), imidazole in which the phenyl group at the 4,4', 5,5'-position is replaced with a carboalkoxy group. Examples thereof include compounds (see, for example, Japanese Patent Application Laid-Open No. 7-10913). Of these, compounds represented by the following formulas or mixtures thereof are preferable.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl). -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl)- 1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis ( Trichloromethyl) -6- [2- (fran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methyl) Phenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like can be mentioned. ..

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Further, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl- Benzoin compounds such as 4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrene quinone, Kinone compounds such as 2-ethylanthraquinone and camphorquinone; examples thereof include 10-butyl-2-chloroacrydone, benzyl, methyl phenylglycoxylate, titanosen compounds and the like. These are preferably used in combination with the polymerization initiation aid (D1) (particularly amine) described later.

The content of the polymerization initiator (D) is preferably 0.03 to 0.25 parts by mass, more preferably 0, with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is .05 to 0.15 parts by mass, more preferably 0.07 to 0.10 parts by mass. When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be increased and the exposure time tends to be shortened, so that the productivity of the color filter tends to be improved.

(Polymerization initiator (D1))
The polymerization initiator (D1) is a compound or a sensitizer used to promote the polymerization of a polymerizable compound whose polymerization has been initiated by the polymerization initiator. When the polymerization initiator (D1) is contained, it is used in combination with the polymerization initiator (D).
Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds and carboxylic acid compounds. Of these, thioxanthone compounds are preferred. Two or more kinds of polymerization initiation aids (D1) may be used in combination.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4-. 2-Ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4,4'-bis ( Ethylmethylamino) benzophenone and the like can be mentioned, and among them, 4,4'-bis (diethylamino) benzophenone is preferable. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-dibutoxy. Anthracene, 2-ethyl-9,10-dibutoxyanthracene and the like can be mentioned.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like can be mentioned.

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

(Solvent (E))
The red colored curable resin composition preferably contains one kind or two or more kinds of solvents (E). Examples of the solvent (E) include an ester solvent (solvent containing -COO-), an ether solvent other than the ester solvent (solvent containing -O-), an ether ester solvent (solvent containing -COO- and -O-), and the like. Examples thereof include a ketone solvent (solvent containing −CO−) other than the ester solvent, an alcohol solvent, an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide and the like.

Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate. , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone and the like.
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, and propylene glycol monoethyl ether. , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl Examples thereof include ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyletol and methyl anisol.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy. Ethyl propionate, 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 monomethyl Examples thereof include ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate.

Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone. And so on.

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

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

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

(Leveling agent (F-1))
The red-colored curable resin composition of the present invention may contain one or more leveling agents (F-1). Examples of the leveling agent (F-1) include a silicone-based surfactant (without a fluorine atom), a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

Examples of the silicone-based surfactant include surfactants having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Japan LLC), etc. Can be mentioned.

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

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

The content of the leveling agent (F-1) is usually 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more and 0.1% by mass in the red colored curable resin composition. Hereinafter, it is more preferably 0.004% by mass or more and 0.05% by mass or less. The content of the pigment dispersant is not included in this content.

(Other ingredients)
The red-colored curable resin composition of the present invention contains, if necessary, additives such as a filler, a polymer compound other than the resin (B), an antioxidant, an adhesion accelerator, an ultraviolet absorber, and an anti-aggregation agent. Can be contained in one kind or two or more kinds.

Red Coloring Agents in the curable resin composition and C.I. I. The total content of Pigment Blue 16 is preferably 10 to 50 parts by mass, more preferably 20 to 45 parts by mass, and even more preferably 20 parts by mass, based on 100 parts by mass of the solid content of the red colored curable resin composition. It is 30 to 40 parts by mass. When a resist pattern is formed using the red coloring curable resin composition as described later, the red coloring agent and C.I. I. The total content of Pigment Blue 16 is preferably 45 parts by mass or less with respect to 100 parts by mass of the solid content of the red colored curable resin composition.
In addition, in this specification, "solid content of a red color curable resin composition" refers to all components other than a solvent (E) among the components contained in a red color curable resin composition.

When the coloring component used for preparing the red coloring curable resin composition contains a pigment, the pigment is preferably in the state of a dispersion liquid uniformly dispersed in a solvent. Further, the pigment preferably has a uniform particle size. The dispersion can be obtained by mixing a pigment and a solvent. If necessary, a pigment dispersant may be mixed. By mixing the pigment dispersant and performing the dispersion treatment, it is possible to obtain a pigment dispersion liquid in which the pigment is uniformly dispersed in the solvent.
As the pigment dispersant, a commercially available surfactant can be used, and silicone-based, fluorine-based, ester-based (including polyester-based), cationic-based, anionic-based, nonionic-based, amphoteric, polyester-based, polyamine-based, and Examples include acrylic-based surfactants. Specific examples of surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimines and the like. In addition, the product names are KP (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by BASF Japan Co., Ltd.), Azispar (registered trademark) ) (Manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (manufactured by Big Chemie Co., Ltd.) and the like. As the pigment dispersant, only one kind may be used, or two or more kinds may be used in combination.

When a pigment dispersant is used, the amount used is preferably 100 parts by mass or less, and more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the pigment. When the amount of the pigment dispersant used is within the above range, it tends to be easy to obtain a pigment dispersion liquid in a uniformly dispersed state.

The solvent constituting the pigment dispersion is not particularly limited, and examples thereof include the same solvent as the solvent (E) described later, which can be contained in the red coloring curable resin composition. Among them, the solvents are 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-dimethylformamide and the like are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxy and the like are preferable. Butyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate and the like are preferable.

The amount of the solvent used is not particularly limited, but is an amount such that the concentration of the solid content in the pigment dispersion is preferably 3 to 25% by mass, more preferably 5 to 18% by mass.

The various pigments used in the preparation of the red-colored curable resin composition are, if necessary, rosin-treated, surface-treated with a pigment derivative having an acidic group or a basic group introduced, a pigment dispersant, or the like, and a polymer. Pigment surface treatment with compounds, atomization treatment with sulfuric acid atomization method, cleaning treatment with organic solvent or water to remove impurities, removal treatment with ion exchange method for ionic impurities, etc. It may have been done.

(Manufacturing method of red colored curable resin composition)
The red colored curable resin composition of the present invention comprises a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and if necessary, a solvent (E) and a thiol compound. It can be prepared by mixing (T), a leveling agent (F-1), a polymerization initiator (D1), an antioxidant (G), and other components.

<Color filter and its manufacturing method>
The red-colored curable resin composition of the present invention is useful as a material for obtaining a red color filter. The red color filter is a filter that transmits colored light having a main wavelength component in the wavelength range of 580 to 780 nm.
The color filter may be formed of a molded product of a red-colored curable resin composition, or may be formed as a cured product (coating film) of a red-colored curable resin composition applied on a substrate. It may be a cured product (pattern) of a red colored curable resin composition formed in a pattern on a substrate.
Examples of the method for producing a cured product of the red colored curable resin composition in a pattern include a photolithography method, an inkjet method, a printing method and the like, and a photolithography method is preferable. The photolithography method is a method in which a red colored curable resin composition is applied to a substrate and dried to form a composition layer, and the composition layer is exposed and developed through a photomask. In the photolithography method, the cured product of the composition layer can be formed as a coating film by not using a photomask at the time of exposure and / or not developing it.

The substrate includes a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass whose surface is silica-coated, a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, silicon, or the above substrate. Acrylic, silver, silver / copper / palladium alloy thin films, etc. are formed on the glass. Another color filter layer, resin layer, transistor, circuit, etc. may be formed on these substrates.

The coating film or pattern can be formed by the photolithography method under known or conventional equipment and conditions, and can be produced, for example, as follows. First, a red colored curable resin composition is applied onto a substrate and dried by heating and drying (prebaking) and / or under reduced pressure to remove volatile components such as a solvent to obtain a smooth composition layer. Examples of the coating method include a spin coating method, a slit coating method, a slit and spin coating method, and the like.
The temperature for heat drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. The heating time is preferably 10 seconds to 5 minutes, more preferably 30 seconds to 3 minutes. When drying under reduced pressure, it is preferable to carry out drying under a pressure of 50 to 150 Pa in a temperature range of 20 to 25 ° C. The film thickness of the composition layer is not particularly limited, and may be appropriately selected depending on the film thickness of the target color filter.
The composition layer is then exposed through a photomask when forming the desired pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used. It is not necessary to use a photomask when forming the coating film. As the light source used for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, light less than 350 nm is cut by using a filter that cuts this wavelength range, and light near 436 nm, 408 nm, and 365 nm is selectively extracted by using a bandpass filter that extracts these wavelength ranges. You may do it. Specific examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp and the like.
For exposure, it is possible to uniformly irradiate the entire exposed surface with parallel light rays and accurately align the photomask with the substrate on which the composition layer is formed. Therefore, an exposure device such as a mask aligner or a stepper can be used. It is preferable to use.
A pattern is formed on the substrate by bringing the exposed composition layer into contact with a developing solution for development. By development, the unexposed portion of the composition layer is dissolved in a developing solution and removed.
The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.
The developing method may be any of a paddle method, a dipping method, a spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development. After development, it is preferable to wash with water.
Further, it is preferable to post-bake the obtained red pattern. The post-bake temperature is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. The post-baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.
The film thickness of the coating film and the pattern after post-baking is generally preferably 3 μm or less, and more preferably 2.8 μm or less. The lower limit of the film thickness of the coating film and the pattern is not particularly limited, but is usually 1 μm or more, and may be 1.5 μm or more.
By using the red coloring curable resin composition of the present invention, it is possible to form a red color filter having improved contrast.

<Display device>
The color filter according to the present invention is useful as a red color filter used in display devices (liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image sensors.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these examples. In the examples,% and parts representing the content or the amount used are based on weight unless otherwise specified.

<Synthesis Example 1: Preparation of Resin (B)>
An appropriate amount of nitrogen was poured into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace it with a nitrogen atmosphere, 371 parts by weight of 1-methoxy-2-propyl acetate was added, and the mixture was heated to 85 ° C. with stirring. .. Then, 54 parts by weight of acrylic acid, 225 parts by weight of a mixture of 3,4-epoxytricyclo [5.2.1.02,6] decane-8 and / and 9-ylacrylate, vinyltoluene (isomer mixture) 81. A mixed solution of 80 parts by weight of 1-methoxy-2-propyl acetate was added dropwise over 4 hours. On the other hand, a solution prepared by dissolving 30 parts by weight of the polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 160 parts by weight of 1-methoxy-2-propyl acetate was added dropwise over 5 hours. After completion of dropping the initiator solution, the mixture was kept at the same temperature for 4 hours and then cooled to room temperature to have a B-type viscosity (23 ° C.) of 246 mPas, a solid content of 37.5% by weight, and a solution acid value of 43 mg-KOH / g. A copolymer was obtained. The weight average molecular weight Mw of the produced copolymer was 10600 and the dispersity was 2.01.
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained resin (B) were measured by using the GPC method under the following conditions. The ratio (Mw / Mn) of the polystyrene-equivalent weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained under the following conditions was defined as the molecular weight distribution.

Equipment; HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature; 40 ° C
Solvent; THF
Flow velocity; 1.0 mL / min
Test solution solid content concentration; 0.001 to 0.01% by mass
Injection volume; 50 μL
Detector; RI
Calibration standard material; TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500
(Made by Tosoh Corporation)

<Synthesis Example 2: Preparation of Red Pigment Dispersion Solution (A1)>
C. I. Pigment Red 254 10.8 parts Acrylic pigment dispersant 3.8 parts Propylene glycol monomethyl ether acetate 85.4 parts are mixed and the pigment is sufficiently dispersed using a bead mill. I. A red pigment dispersion (A1) containing Pigment Red 254 was obtained.

<Synthesis Example 3: Preparation of Red Pigment Dispersion Solution (A2)>
In formula (P), ^{a compound in which Ra 1} and Ra ² are bromine atoms and Ra ³ and Ra ⁴ are hydrogen atoms (hereinafter referred to as compound A) 12.0 parts Acrylic pigment dispersant 4.2 parts propylene 83.8 parts of glycol monomethyl ether acetate was mixed and the pigment was sufficiently dispersed using a bead mill to obtain a red pigment dispersion liquid (A2) containing the above compound A.

<Synthesis Example 4: Preparation of Red Pigment Dispersion Solution (A3)>
C. I. Pigment Red 242 12.0 parts Acrylic pigment dispersant 4.0 parts Propylene glycol monomethyl ether acetate 84.0 parts were mixed and the pigment was sufficiently dispersed using a bead mill. I. A red pigment dispersion (A3) containing Pigment Red 242 was obtained.

<Synthesis Example 5: Preparation of Blue Pigment Dispersion Solution (A4)>
C. I. Pigment Blue 16 11.8 parts Acrylic pigment dispersant 4.7 parts Propylene glycol monomethyl ether acetate 83.5 parts were mixed and the pigment was sufficiently dispersed using a bead mill. I. A blue pigment dispersion (A4) containing Pigment Blue 16 was obtained.

<Synthesis Example 6: Preparation of Blue Pigment Dispersion Solution (A5)>
C. I. Pigment Blue 15: 3 12.0 parts Acrylic pigment dispersant 3.6 parts Propylene glycol monomethyl ether acetate 84.4 parts were mixed and the pigment was sufficiently dispersed using a bead mill. I. A blue pigment dispersion (A5) containing Pigment Blue 15: 3 was obtained.

<Synthesis Example 7: Preparation of Blue Pigment Dispersion Solution (A6)>
C. I. Pigment Blue 15: 6 12.0 parts Acrylic pigment dispersant 2.0 parts Propylene glycol monomethyl ether acetate 86.0 parts are mixed and the pigment is sufficiently dispersed using a bead mill. I. A blue pigment dispersion (A6) containing Pigment Blue 15: 6 was obtained.

<Examples 1 to 3 and Comparative Examples 1 to 5>
(1) Preparation of Red Colored Curable Resin Composition The resin (B) obtained in Synthesis Example 1, the red pigment dispersions (A1) to (A3) obtained in Synthesis Examples 2 to 4, and Synthesis Examples 5 to 5 above. Table 1 shows the red pigment dispersions (A4) to (A6), the polymerizable compound (C-1), the polymerization initiator (D-1), and the leveling agent (F-1) obtained in 7. A red-colored curable resin composition was obtained by mixing so as to have a blending amount. In each Example and Comparative Example, propylene glycol monomethyl ether acetate was mixed so as to have a solid content (NV) in Table 8. The unit of the blending amount of each component in Table 1 is "part by mass", the blending amount is in terms of solid content, and the solid content (NV) is%. The polymerizable compound (C-1), the polymerization initiator (D-1), and the leveling agent (F-1) are as follows.
Polymerizable compound (C-1): dipentaerythritol hexaacrylate / dipentaerythritol pentaacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name "A-9550")
Polymerization initiator (D-1): A compound represented by the following formula (manufactured by BASF Corporation, trade name "Irgacure OXE03")

Leveling agent (F-1): Fluorine-containing group / lipophilic group-containing oligomer (manufactured by DIC Corporation, trade name "Megafuck F-554")

(2) Preparation of Coating Film A red colored curable resin composition was applied on a 2-inch square glass substrate (“Eagle XG” manufactured by Corning Inc.) by a spin coating method, and then prebaked at 100 ° C. for 3 minutes. After cooling, an exposure machine (“TME-150RSK” manufactured by Topcon Corporation) was used on a substrate coated with this red colored curable resin composition, and an exposure amount of ^{80 mJ / cm 2 (365 nm standard) was used in an atmospheric atmosphere.} ) Was irradiated with light. Then, it was post-baked in an oven at 230 ° C. for 30 minutes to obtain a coating film.

(3) Film thickness measurement With respect to the obtained 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 2.

(4) Measurement of chromaticity The obtained coating film was spectrophotometrically measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the CIE XYZ table was used using the characteristic function of the C light source. The xy chromaticity coordinates (x, y) and the lightness Y in the color system were measured. The results are shown in Table 2.

(5) Evaluation of contrast (CR) Contrast meter (CT-1; manufactured by Tsubosaka Electric Co., Ltd., color difference meter BM-5AS; manufactured by Topcon Co., Ltd., light source; F-10, polarizing film; pot; Using a product manufactured by Saka Electric Co., Ltd., the contrast was measured with a blank value of 10000. If the contrast in the coating film is high, it can be said that the pattern also has high contrast. The results are shown in Table 2.

From the comparison between Example 3 and Comparative Example 5, C.I. I. It can be seen that the contrast can be improved by using Pigment Blue 16.
From the comparison between Example 1 and Comparative Examples 1 and 2, the comparison between Example 2 and Comparative Example 3, and the comparison between Example 3 and Comparative Example 4, C.I. I. It can be seen that by using Pigment Blue 16, the contrast can be improved as compared with the case of using other blue pigments (CI Pigment Blue 15: 3, CI Pigment Blue 15: 6).
From these results, C.I. I. Pigment Blue 16 has been found to be useful as a contrast improver in red color filters.
Further, from the comparison between Examples 1 to 3 and Example 4, together with the red colorant containing a compound having a diketopyrrolopyrrole skeleton, C.I. I. It can be seen that the contrast can be further improved by using Pigment Blue 16.

Claims (5)

Red colorants and C.I. I. Pigment Blue 16 seen including,
A red coloring composition, wherein the red coloring agent contains a compound having a diketopyrrolopyrrole skeleton. With respect to 100 parts by mass of the red colorant, C.I. I. The red coloring composition according to claim 1, wherein the content of Pigment Blue 16 is 0.005 part by mass or more and 1.5 part by mass or less. The red coloring composition according to claim 1 or 2, further comprising a resin (B), a polymerizable compound (C) and a polymerization initiator (D). A color filter formed from the red coloring composition according to claim 3. A display device including the color filter according to claim 4.