TW201835247A - Red colored composition - Google Patents

Abstract

The present invention provides a red colored composition, comprising red colorant and C.I. pigment Blue-16.

Description

   Red coloring composition   

The present invention relates to a red colored composition.

Display devices such as liquid crystal display panels, electroluminescent panels, and plasma display panels use color filters.

JP2013-014750 describes a coloring composition capable of producing a high-contrast color filter. In JP 2005-181384, it is described that by adjusting the brightness of red without changing the chromaticity of blue, green, and red, it is possible to adjust the color temperature (K) and color difference (△ uv) for white color filters. Red coloring composition.

The present invention provides a red coloring composition, a color filter, and a display device shown below.

[1] A red coloring composition comprising a red colorant and C.I. (color index) pigment blue 16.

[2] The red coloring composition according to [1], wherein the content of C.I. Pigment Blue 16 is 0.005 part by mass or more and 1.5 parts by mass or less based on 100 parts by mass of the red colorant.

[3] The red coloring composition according to [1] or [2], wherein the red colorant contains a compound having a diketopyrrolopyrrole skeleton.

[4] The red coloring composition according to any one of [1] to [3], which further contains red coloring and hardening properties of the resin (B), the polymerizable compound (C), and the polymerization initiator (D).组合 物。 Composition.

[5] A color filter formed of the red coloring composition according to [4].

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

<Red coloring composition>

The red coloring composition of the present invention includes a red colorant and C.I. Pigment Blue 16. The red coloring composition may further include a red colorant and a coloring component other than C.I. Pigment Blue 16.

In the red coloring composition of the present invention, C.I. Pigment Blue 16 can be used as a contrast enhancer for improving the contrast of red color filters.

The red coloring composition may further contain a resin (B), a polymerizable compound (C), and a polymerization initiator (D). Hereinafter, a red coloring composition containing a red colorant, C.I. Pigment Blue 16, resin (B), a polymerizable compound (C), and a polymerization initiator (D) is sometimes referred to as a "red coloring curable composition".

In addition, in this specification, the compound which is an example of each component is illustrated, and it may use individually or in combination of multiple types, unless otherwise stated.

Hereinafter, each component contained in the red coloring composition of the present invention will be described.

(Red colorant)

Examples of the red colorant include a red pigment, a red dye, an orange pigment, an orange dye, and the like. The red colorant may be made of one kind or may contain two or more kinds.

The red pigment includes, for example, a compound having a diketopyrrolopyrrole skeleton and a compound classified as a pigment in the color index (published by the Society of Dyes).

The structure of the diketopyrrolopyrrole skeleton is represented by the following formula.

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

[In the formula, R ^a1 , R ^a2 , R ^a3, and R ^a4 each independently represent a hydrogen atom, a halogen atom, or a monovalent substituent, and at least one of them represents a halogen atom. ]

Examples of the halogen atom in R ^a1 , R ^a2 , R ^a3 and R ^a4 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom and a bromine atom are preferred.

Monovalent substituents in R ^a1 , R ^a2 , R ^a3 and R ^a4 , such as cyano, -CF ₃ , -R ^a5 , -OR ^a5 , -SR ^a5 , -SOR ^a5 , -S (O) ₂ R ^a5 , -S (O) ₂ R ^a5 , -NR ^a6 COR ^a5 , -CONR ^a5 R ^a6 , -CONH ₂ .

R ^a5 represents an alkyl group, phenyl group or naphthyl group having 1 to 5 carbon atoms, and -CH ₂ -contained in the alkyl group may be replaced by -NR ^a7- , -O-, -S-, -SO-, or -S ( O) ₂ -substituted.

R ^a6 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and -CH ₂ -contained in the alkyl group may be replaced by -NR ^a7- , -O-, -S-, -SO-, or -S (O) ₂ -Replace.

R ^a5 and R ^a6 together may form an alkanediyl group having 2 to 8 carbon atoms, and -CH ₂ -contained in the alkanediyl group may be -NR ^a7- , -O-, -S-, -SO-, or -S (O) ₂ -substituted.

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 methyl, ethyl, n-propyl, n-butyl, n-pentyl, isopropyl, isobutyl, second butyl, and isopentyl.

Examples of the alkanediyl group having 2 to 8 carbon atoms include ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, butane-1,3 -Diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, and the like.

Examples of -OR ^a5 include methoxy, ethoxy, propoxy, butoxy, and pentyloxy.

Examples of -SR ^a5 include methylsulfanyl, ethylsulfanyl, propylsulfanyl, butylsulfanyl, and pentylsulfanyl.

Examples of -SOR ^a5 include methylsulfinamilide, ethylsulfinamilide, propylsulfinamido, butylsulfinamido, pentylsulfinamido, and the like.

Examples of -S (O) ₂ R ^a5 include methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, and pentylsulfonyl.

Examples of the -NR ^a6 COR ^a5 include an N-ethylamino group, an N-propylamino group, an N-benzylamino group, an N-methyl-N-ethylamino group, and the like.

In -NR ^a6 COR ^a5 , a group in which R ^a5 and R ^a6 form a ring includes, for example, a group represented by the following formula.

Examples of -CONR ^a5 R ^a6 include N-methylaminocarbonyl, N-ethylaminocarbonyl, N, N-dimethylaminocarbonyl, N, N-diethylaminocarbonyl, N, N- Ethylmethylaminocarbonyl and the like.

In -CONR ^a5 R ^a6 , a group in which R ^a5 and R ^a6 form a ring includes, for example, a group represented by the following formula.

Among the compounds represented by formula (P), R ^a1 , R ^a2 , R ^a3, and R ^a4 are preferred, and at least one of R ^a1 and R ^a2 is a chlorine atom or a bromine atom. Furthermore, it is preferable that R ^a1 is a chlorine atom or a bromine atom and R ^a2 is a chlorine atom or a bromine atom.

^Both R ^a3 and R ^a4 are preferably hydrogen atoms.

Specifically, the compound represented by the formula (P) may be, for example, CI Pigment Red 254 in which R ^a1 and R ^a2 are both chlorine atoms, and R ^a3 and R ^a4 are both hydrogen atoms.

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

In addition to the above-mentioned CI Pigment Red 254, the compounds classified as pigments in the above color index may include CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 255, 264, 265, etc.

Examples of the red dye include compounds classified as dyes in the above-mentioned color index and conventional dyes described in Dyeing Notes (Seiransha).

Specifically, the CI acid dye may be, for example, CI 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, 206,211,215,216,217,227,274,277,280,281,195,308,312,315,316,339,341,345,346,349,382,383,394,401,412, 417, 418, 422, 426, etc.

Examples of CI direct dyes include 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, etc.

Examples of CI mordant dyes include CI mordant 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, etc.

The orange pigment is, for example, a compound classified as a pigment in the above-mentioned color index.

Specifically, for example, C.I. pigment tangerine 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73, and the like.

Orange dyes include, for example, compounds classified as dyes in the aforementioned color index and conventional dyes described in coloring notes.

Specifically, the CI acid dye may be, for example, CI acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173, etc.

Examples of C.I. direct dyes include C.I. direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107, and the like.

Examples of CI mordant dyes include CI mordant orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47 , 48 and so on.

The red dye and orange dye may be, for example, an xanthracene dye exhibiting a red or orange color, containing a compound having an xantene skeleton in the molecule, exhibiting a red or orange color, and containing a metal atom in the molecule Dysallated dye molecules, metal salt dyes whose metal atoms are salted, red or orange azo dyes, etc.

Although xanthracene dyes exhibiting red or orange color partially overlap with the above dyes, for example, CI acid orange 51, 52, 87, 92, 94, 289, 388, CI basic red 1 (rhodamine 6G; Rhodamine 6G), 8, CI Basic Red 10 (Rhodamine B), CI Solvent Red 218, CI Mordant Red 27, CI Reactive Red 36 (Rose Red B), Sulfa Rhodamine G, Japanese Patent Laid-Open No. 2010-32999 The xanthene dyes described in Japanese Patent Publication No. 4 and the xanthene dyes described in Japanese Patent No. 4492760, and the like.

Red or orange metal cross-salt dyes, although some of the same as the above dyes, but for example, CI solvent orange 5, 11, 20, 40: 1, 41, 45, 54, 56, 58, 62, 70, 81, 99, CI 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, CI Acid Orange 74, 162, CI Acid Red 211, JP2010-170117 and JP2011-59673.

Examples of the azo dye exhibiting a red or orange color include the azo dye described in JP 2013-14750.

The red colorant is preferably a red pigment and / or a red dye, and more preferably a red pigment from the viewpoint of improving the contrast obtained by the red coloring composition.

The red pigment is advantageous in improving the contrast of a red color filter, and is preferably a compound having a diketopyrrolopyrrole skeleton.

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 relative to 100 parts by mass of the total amount of the red colorant. It is preferably 20 to 100 parts by mass, and more preferably 40 to 100 parts by mass.

(C.I.Pigment Blue 16)

The red coloring composition of the present invention contains C.I. Pigment Blue 16 as a blue pigment. C.I. Pigment Blue can be used as a contrast enhancer for improving the contrast of red color filters.

By including the red colorant and C.I. Pigment Blue 16, the red coloring composition of the present invention can improve the contrast of the red color filter.

The content of CI Pigment Blue 16 in the red coloring composition is not particularly limited as long as it is a range in which the red coloring composition exhibits red. It is preferably 0.005 parts by mass or more, and more preferably 0.4 part by mass relative to 100 parts by mass of the red colorant. It is preferably 1.5 parts by mass or less, and more preferably 0.8 parts by mass or less. As long as the content of C.I. Pigment Blue 16 is 0.005 parts by mass or more, a desired effect of improving contrast can be obtained. As long as the content of C.I. Pigment Blue 16 is 1.5 parts by mass or less, the desired red hue is easily obtained.

(Other coloring ingredients)

The red coloring composition of the present invention may further include a red colorant and a coloring component other than C.I. Pigment Blue 16 in a range in which the red coloring composition exhibits a desired red color. Other coloring components may be used individually by 1 type, and may use 2 or more types together. Examples of other coloring components include blue colorants other than C.I. Pigment Blue 16, yellow colorants, green colorants, purple colorants, brown colorants, and black colorants. Pigments or dyes may be used. The content of the other coloring components is not particularly limited as long as the red coloring composition exhibits a red color, and is preferably 0.005 to 10 parts by mass relative to 100 parts by mass of the total amount of the red colorant and C.I. Pigment Blue 16.

(Resin (B))

The red colored composition of the present invention may be a red colored curable composition containing a resin (B), a polymerizable compound (C), and a polymerization initiator (D). The red colored curable composition may contain one or two or more resins (B). The resin (B) is preferably an alkali-soluble resin. The alkali-soluble property refers to a property of a developing solution dissolved in an aqueous solution of a basic 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 anhydrides (a) [hereinafter referred to as "(a)"] and a cyclic ether structure having 2 to 4 carbon atoms and ethylene A copolymer of a monomer (b) (hereinafter, referred to as "(b)") which is unsaturatedly bonded.

Resin [K2]: copolymerization of (a), (b) and monomer (c) (but different from (a), (b)) which may be copolymerized with (a) [hereinafter referred to as "(c)"] Thing.

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 then reacting a carboxylic anhydride.

(a) Specifically, unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, o-, m-, p-vinyl benzoic acid, etc .; maleic acid, fumaric acid, etc. Diacid, citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5 Unsaturated dicarboxylic acid such as 1,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexenedicarboxylic acid, etc. Carboxylic 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-methyl Carboxyl bicyclo [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, and other bicyclic unsaturated compounds containing carboxyl groups; maleic anhydride, citraconic acid 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- Unsaturated dicarboxylic anhydrides such as dicarboxybicyclo [2.2.1] heptan-2-ene anhydride (humic anhydride); succinate mono [2- (meth) acryloxyethyl] ester, o-benzene Unsaturated mono [(meth) acryloxyalkyl] ester of divalent polyvalent carboxylic acids such as mono [2- (meth) acryloxyethyl] dicarboxylic acid; α- (hydroxy Unsaturated (meth) acrylic acid having a hydroxyl group and a carboxyl group in the same molecule such as (meth) (meth) acrylic acid.

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

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

(b) a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring (oxetane ring)) And ethylenically unsaturated polymerizable compounds. (b) A monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acrylic fluorenyloxy group is preferred.

(b) For example, a monomer (b1) (hereinafter referred to as "(b1)") having an ethylene oxide group and an ethylenically unsaturated bond, and an oxetanyl group and an ethylenically unsaturated bond can be mentioned. Monomer (b2) [hereinafter referred to as "(b2)"] and monomer (b3) [hereinafter referred to as "(b3)"] having a tetrahydrofuranyl group and an ethylenically unsaturated bond, and the like.

(b1) For example, a monomer (b1-1) (hereinafter referred to as "(b1-1)") having a structure having an unsaturated aliphatic hydrocarbon epoxy group, and having an unsaturated alicyclic hydrocarbon epoxy group (B1-2) [hereinafter referred to as "(b1-2)"].

(b1-1) Examples thereof include glycidyl (meth) acrylate, beta-methyl glycidyl (meth) acrylate, beta-ethyl glycidyl (meth) acrylate, and glycidyl Vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl 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 (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 (glycidoxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (cyclo Oxypropoxymethyl) styrene and the like.

(b1-2) For example, vinylcyclohexene monooxide, 1,2-epoxy 4-vinylcyclohexane (e.g. Celloxide2000; manufactured by Daicel Chemical Industry Co., Ltd.), and acrylic acid 3,4-cyclo Oxycyclohexyl methyl ester (e.g. Cyclomer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxy cyclohexyl methyl methacrylate (e.g. Cyclomer M100; Daicel Chemical Industries (owned)), A compound represented by I), a compound represented by formula (II), and the like.

[In the formula (I) and the formula (II), R ^a and R ^b independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group. X ¹ and X ² each independently 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 bonding target 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 hydroxyl group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, and 1-hydroxy- 1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.

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

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

X ¹ and X ^{2 are} preferably a single bond, a methylene group, an ethylidene group, * -CH ₂ -O- (* represents a bonding hand with O), * -CH ₂ CH ₂ -O- group, more preferably It is a single bond, * -CH ₂ CH ₂ -O- group.

Specific examples of the compound represented by formula (I) include compounds represented by formula (I-1) to formula (I-15), and preferred examples include formula (I-1), formula (I-3), The compounds represented by formula (I-5), formula (I-7), formula (I-9), formula (I-11) to formula (I-15) are more preferably, for example, formula (I-1), Compounds represented by formula (I-7), formula (I-9), and formula (I-15).

Examples of the compound represented by formula (II) include compounds represented by formula (II-1) to formula (II-15), and preferred examples include formula (II-1), formula (II-3), and formula (II). -5), compounds represented by formula (II-7), formula (II-9), formula (II-11) to formula (II-15), more preferably, for example, formula (II-1), formula (II) -7), a compound represented by the formula (II-9), or a 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 two or more kinds are used in combination, the mixing ratio is represented by formula (I): formula (II) [mole ratio], preferably 5:95 to 95: 5, more preferably 20:80 to 80:20, and even more 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) acryloxy group.

Preferred examples of (b2) include, for example, 3-methyl-3- (meth) acryloxymethyloxetane, and 3-ethyl-3- (meth) acryloxymethyl. Oxetane, 3-methyl-3- (meth) propenyloxyethyloxetane, 3-ethyl-3- (meth) propenyloxyethyloxetane alkyl.

The monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond is preferably a monomer having a tetrahydrofuranyl group and a (meth) acryloxy group.

Preferred examples of (b3) include tetrahydrofuran acrylate (for example, BISCOAT V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), and tetrahydrofuran methacrylate.

Specific examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, second butyl (meth) acrylate, and Tributyl ester, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate Ester, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] dec-18-ester [In this technical field, Called "dicyclopentyl (meth) acrylate" as a common name. In addition, there are also known as "tricyclodecyl (meth) acrylate"], tricyclo [5.2.1.0 ^2,6 ] decene-8-ester [in this technical field, " (Diyl) cyclopentenyl acrylate "as the common name. ], Dicyclopentyloxyethyl (meth) acrylate, isoamyl (meth) acrylate, adamantyl (meth) acrylate, propynyl (meth) acrylate, phenyl (meth) acrylate, (Meth) acrylates such as naphthyl (meth) acrylate and benzyl (meth) acrylate; hydroxyl-containing groups such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate (Meth) acrylic acid esters; diethyl dimaleate, diethyl fumarate, diethyl itaconic acid, etc. diethyl dicarboxylates; 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] 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] Bicyclic unsaturated compounds such as hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene; N-benzene Methyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide, 3-maleimide benzoic acid N-succinimide, 4-male Dicarbamidines such as iminobutyric acid N-succinimide Amine derivatives; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, (meth) acrylonitrile, vinyl chloride, Vinylidene chloride, (meth) acrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among them, from the viewpoint of copolymerization reactivity and heat resistance, (c) is preferably benzyl (meth) acrylate, tricyclodecyl (meth) acrylate, styrene, and N-phenylmaleamidine. Imine, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like. In addition, since the developability is good when the pattern is formed, (c) is more preferably benzyl (meth) acrylate and tricyclodecyl (meth) acrylate.

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

Building blocks from (a); 50 to 98 mol% (more preferably 55 to 90 mol%), building blocks from (b), especially building blocks from (b1); 2 to 50 mol% (More preferably 10 to 45 mole%).

When the ratio of the structural unit of the resin [K1] is in the above range, the storage stability, developability, and solvent resistance of the obtained pattern tend to be good.

For the resin [K1], please refer to the method described in the "Experimental Method of Polymer Synthesis" (Otsu Takayuki Publications Co., Ltd., 1st edition, 1st issue, March 1, 1972) and the references cited in the document Literature to make.

Specifically, for example, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like can be put into a reaction container, and for example, a method of heating and holding the mixture while stirring in a deoxygenated environment by replacing nitrogen with oxygen. The polymerization initiator, solvent, and the like used herein are not particularly limited, and any one generally used in the art may be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.), organic peroxides (peroxide Benzamidine oxide, etc.). The solvent may be any one that can dissolve each monomer, and a solvent such as a solvent (E) described later can be used as the solvent for the red colored curable resin composition.

The obtained copolymer may be used directly after the reaction, a concentrated or diluted solution, or a solid (powder) obtained by a method such as reprecipitation. In particular, by using a solvent (E) described later as a solvent during the polymerization, the solution after the reaction can be used directly, and the production steps can be simplified.

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

Tectonic units from (a); 4 to 45 mole% (more preferably 10 to 30 mole%), tectonic units from (b), especially from (b1); 2 to 95 mole% (More preferably 5 to 80 mole%), a building block derived from (c); 1 to 65 mole% (more preferably 5 to 60 mole%).

When the ratio of the structural unit of the resin [K2] is in the above range, storage stability, developability, solvent resistance, heat resistance, and mechanical strength of the obtained pattern tend to be good.

Resin [K2] can be manufactured by the same method as the method described as the manufacturing method of resin [K1]. Specifically, for example, a predetermined amount of (a), (b) (especially (b1)) and (c), a polymerization initiator, a solvent, and the like may be placed in a reaction container, and stirred, heated, and held in a deoxidizing environment. Methods. The obtained copolymer may be used directly as a solution after the reaction, a concentrated or diluted solution may be used, or it may be obtained as a solid (powder) by a method such as reprecipitation.

In the resin [K3], the ratio from each structural unit is preferably in the following range among all the structural units constituting the resin [K2].

Tectonic units from (a); 2 to 55 mol% (more preferably 10 to 50 mol%), tectonic units from (c); 45 to 98 mol% (more preferably 50 to 90 mol%) ).

Resin [K3] can be manufactured by the same method as the method described as the manufacturing method of resin [K1].

The resin [K4] can be obtained by the copolymer of (a) and (c), the cyclic ether structure having 2 to 4 carbon atoms in (b), and particularly the ethylene oxide cycloaddition in (b1). It is produced from the carboxylic acid and / or carboxylic anhydride which (a) has. Specifically, first, the copolymer of (a) and (c) was produced by the same method as the method described as the production method of the resin [K1]. In this case, the ratio derived from each structural unit is preferably within the following range among all the structural units constituting the copolymers (a) and (c).

Tectonic units from (a); 5 to 50 mol% (more preferably 10 to 45 mol%), tectonic units from (c); 50 to 95 mol% (more preferably 55 to 90 mol%) ).

Then, a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the above-mentioned copolymer has a cyclic ether structure having 2 to 4 carbon atoms in (b), and particularly the ethylene oxide in (b1). Alkanes. Specifically, following the production of the copolymer of (a) and (c), the environment in the flask was replaced with nitrogen to air, and the reaction between (b) (especially (b1)), carboxylic acid or carboxylic anhydride, and a cyclic ether structure was performed. Catalysts (for example, ginsyl (dimethylaminomethyl) phenol) and polymerization inhibitors (for example, hydroquinone) are placed in flasks and reacted at 60 to 130 ° C for 1 to 10 hours, thereby obtaining Resin [K4].

The used amount of (b), especially the used amount of (b1), is preferably 5 to 80 moles, more preferably 10 to 75 moles, with respect to (a) 100 moles. By setting it as this range, there exists a tendency for the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity to become favorable. Since the cyclic ether structure has high reactivity and does not easily leave unreacted (b), (b) used as the resin [K4] is preferably (b1), and more preferably (b1-1).

The usage-amount of the said reaction catalyst is 0.001 to 5 mass% with respect to the total amount of (a), (b) (especially (b1)), and (c). The usage-amount of the said polymerization inhibitor is 0.001 to 5 mass% with respect to the total amount of (a), (b), and (c).

The reaction conditions such as the method of placing, the reaction temperature, and the time can be appropriately adjusted in consideration of manufacturing equipment and the amount of heat generated by polymerization. In addition, in the same manner as the polymerization conditions, considering the manufacturing equipment, the amount of heat generated by polymerization, and the like, the method of placing and the reaction temperature can be appropriately adjusted.

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

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

Tectonic units from (b), especially from (b1); from 5 to 95 mole% (more preferably from 10 to 90 mole%), from (c); from 5 to 95 mole% (More preferably 10 to 90 mol%).

In addition, under the same conditions as the method for producing the resin [K4], the cyclic ether structure derived from (b) and ((b) (especially (b1)) and (c)) and ( a) The reaction of the carboxylic acid and / or carboxylic anhydride possessed can obtain a resin [K5]. The amount of (a) to be reacted with the above copolymer is preferably 5 to 80 moles relative to 100 moles of (b) (especially (b1)). Since the cyclic ether structure has high reactivity and it is difficult to leave unreacted (b), (b) used for the resin [K5] is preferably (b1), more preferably (b1-1).

The resin [K6] is a resin in which the carboxylic anhydride is reacted with the resin [K5]. The carboxylic acid anhydride is reacted with a hydroxyl group generated by a reaction of a cyclic ether structure with a carboxylic acid or a carboxylic acid anhydride.

Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydroophthalic anhydride Phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (Humic anhydride) and the like.

Among the resins [K1] to [K6], the preferable resin as the resin (B) is [K1] or [K2]. The resin (B) may be composed of one resin or may include two or more resins.

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 above range, the solubility of the unexposed portion in the developing solution is high, and the residual film rate 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 measured value of the amount (mg) of potassium hydroxide required for the acid value to neutralize 1 g of the resin can be obtained by, for example, titration with an aqueous potassium hydroxide solution.

The content of the resin (B) is 100% by mass of the solid content of the red colored curable resin composition, preferably 5 to 50% by mass, more preferably 15 to 45% by mass, and even more preferably 25 to 40% by mass. When the content of the resin (B) is within the above range, the solubility of the unexposed portion in the developing solution tends to be high.

(Polymerizable compound (C))

The polymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by living radicals generated from the polymerization initiator (D) by light irradiation or the like, and examples thereof include compounds having a polymerizable ethylenically unsaturated bond Wait. 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, for example, trimethylolpropane tri (meth) acrylate, neopentaerythritol tri (methyl) ) Acrylate, neopentaerythritol tetra (meth) acrylate, dinepentaerythritol penta (meth) acrylate, dinepentaerythritol hexa (meth) acrylate, trinepentaerythritol octa (a) Base) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (formaldehyde) Base) propylene ethoxyethyl) isocyanurate, ethylene glycol modified neopentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, Propylene glycol-modified neopentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and the like. Among them, dipentaerythritol penta (meth) acrylate and dinepentaerythritol hexa (meth) acrylate are preferred.

The red colored composition (red colored curable resin composition) of the present invention may contain one or more polymerizable compounds (C). The content of the polymerizable compound (C) is preferably 20 to 150 parts by mass, and more preferably 40 to 70 parts by mass based on 100 parts by mass of the resin (B) in the red colored curable resin composition.

(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 to initiate polymerization, and a conventional polymerization initiator can be used.

Examples of the polymerization initiator (D) include oxime compounds such as O-fluorenyl oxime compounds, benzoalkyl ketone compounds, biimidazole compounds, triazine compounds, and fluorenyl phosphine oxide compounds.

The polymerization initiator (D) may be used in combination of two or more in consideration of sensitivity, formability of a precise pattern shape, and the like. The polymerization initiator (D) is advantageous in precisely producing a pattern shape having a sensitivity and a desired line width, and an oxime compound including an O-fluorenyl oxime compound is preferable.

The O-fluorenyl oxime compound is a compound having a structure represented by formula (d). In the following, * indicates a bonding target.

Examples of such O-fluorenyl oxime compounds include N-benzyloxy-1- (4-phenylhydrothiophenyl) butane-1-one-2-fluorenimine and N-benzylhydrazone. Oxy-1- (4-phenylhydrothiophenyl) octane-1-one-2-fluorenimine, N-benzyloxy-1- (4-phenylhydrothiophenyl) 3-Cyclopentylpropane-1-one-2-fluorenimine, N-ethoxyl-1- [9-ethyl-6- (2-methylbenzylhydrazone) -9H-carbazole -3-yl] ethane-1-fluorenimine, N-acetoxy-1--1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2, 4-dioxolylmethyloxy) benzylidene} -9H-carbazol-3-yl] ethane-1-fluorenimine, N-ethoxymethyl-1- [9-ethyl -6- (2-methylbenzyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-fluorenimine, N-benzyloxy-1- [9 -Ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-fluorenimine, N-ethoxyl-1- [ 9- (2-ethylhexyl) -6- (2,4,6-trimethylbenzyl) -9H-benzo [i] carbazol-3-yl] -3- [1- (2 , 2,3,3-tetrafluoropropoxy) phenyl] methanimine and the like. Commercially available products such as Irgacure OXE01, OXE02, OXE03 (above BASF (stock)) and N-1919 ((stock) ADEKA) can also be used. When such an O-fluorenyl oxime compound is used, there is a tendency that a color filter having excellent lithographic performance can be obtained.

The benzoyl ketone compound is a compound having a structure represented by formula (d4) or a structure represented by formula (d5). ＊ indicates the object to be bonded. In such structures, the benzene ring may have a substituent.

Examples of the compound having a structure represented by the formula (d4) include 2-methyl-2-morpholinyl-1- (4-methylhydrothiophenyl) propane-1-one and 2-dimethyl. Amino-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 (made by the above BASF (stock)) can also be used.

Examples of the compound having a structure represented by formula (d5) 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, etc. Oligomers, α, α-diethoxyacetophenone, benzyldimethylketal, etc.

In terms of sensitivity, the benzoalkyl ketone compound is preferably a compound having a structure represented by formula (d4).

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorobenzene) Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (refer to, for example, Japanese Unexamined Patent Publication No. 6-75372, Japanese Unexamined Patent Publication No. 6-75373), 2,2'-bis (2-chlorobenzene Phenyl) -4,4 ', 5,5'-tetrakis (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetrakis ( Dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (trialkoxyphenyl) biimidazole 48-38403, Japanese Patent Publication No. 62-174204, etc.), and imidazole compounds in which 4,4 ', 5,5'-phenyl groups are substituted with carbonylalkoxy groups (see, for example, Japanese Patent Application Laid-Open No. 7-10913 and many more. Among them, a compound represented by the following formula or a mixture of these is preferred.

Examples of triazine compounds include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperyl-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) vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl] -1,3 , 5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5-triazine and the like.

Examples of the fluorenylphosphine oxide compound include 2,4,6-trimethylbenzylfluorenyldiphenylphosphine oxide and the like.

In addition, the polymerization initiator (D) may be benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like; benzophenone, o-benzidine Methyl benzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetrakis (3butyl peroxide (Carbonyl) benzophenone compounds such as benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone and other quinone compounds; 10 -Butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, Titanocene compound and the like. These can be used in combination with a polymerization initiation aid (D1) (especially an amine) described later.

The content of the polymerization initiator (D) is preferably 0.03 to 0.25 parts by mass, more preferably 0.05 to 0.15 parts by mass, and even more preferably 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). 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 decrease and the exposure time tends to be shortened. Therefore, the productivity of the color filter tends to be improved.

(Polymerization Initiation Aid (D1))

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

Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thiaxanthone compounds, and carboxylic acid compounds. Among these, a xanthone compound is preferable.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylamino Isoamyl benzoate, 2-dimethylamino ethyl benzoate, 2-ethylhexyl 4-dimethylamino benzoate, N, N-dimethyl-p-toluidine, 4,4'- Bis (dimethylamino) benzophenone (commonly known as Michler's Ketone), 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethyl Methylmethylamino) benzophenone and the like, and among them, 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, 2-ethyl-9, 10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

Examples of the xanthone 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 phenylhydrothioacetic acid, methylphenylhydrothioacetic acid, ethylphenylhydrothioacetic acid, methylethylphenylhydrothioacetic acid, and dimethylphenylhydrothioacetic acid. Acetic acid, methoxyphenylhydrothioacetic acid, dimethoxyphenylhydrothioacetic acid, chlorophenylhydrothioacetic acid, dichlorophenylhydrothioacetic acid, N-phenylglycine, phenoxyacetic acid , Naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like.

The content of the polymerization initiation aid (D1) is preferably from 0.1 to 30 parts by mass, more preferably from 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 initiation aid (D1) is in the above range, a pattern can be formed with higher sensitivity, and the productivity of a color filter tends to be improved.

(Solvent (E))

The red coloring composition preferably contains one or more solvents (E).

Examples of the solvent (E) include ester solvents (solvents containing -COO-), ether solvents other than ester solvents (solvents containing -O-), ether ester solvents (solvents containing -COO- and -O-), and esters. Ketone solvents (solvents containing -CO-) other than solvents, alcohol solvents, aromatic hydrocarbon solvents, amidine solvents, dimethyl sulfene, 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, isoamyl acetate, and propyl Butyl ester, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, cyclic Hexanol 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 diethylene glycol. Alcohol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, Tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol Dibutyl ether, anisole, phenyl ether and methyl anisole.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-methoxypropionate. , Ethyl 3-methoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate , Propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy Ethyl-2-methylpropanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and dipropylene glycol methyl ester Ether acetate and the like.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-heptanone , 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 xylene. Examples of the amidine solvent include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

The solvent (E) is preferably an organic solvent having a boiling point of 120 ° C. or higher and 180 ° C. or lower from the point of coating properties and drying properties. The solvent (E) contains a solvent selected from the group consisting of propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, and ethylene glycol monomethyl ether. Ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone And at least one selected from the group consisting of N, N-dimethylformamide, and selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, and acetic acid At least one of 3-methoxybutyl ester, 3-methoxy-1-butanol, and ethyl 3-ethoxypropionate is more preferable.

The content of the solvent (E) in the red coloring composition is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass. In other words, the solid content of the red coloring 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 when the color filter is formed, the color density is not insufficient, and the display characteristics tend to be improved.

(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 (without fluorine atom) a polysiloxane-based surfactant, a fluorine-based surfactant, and a polysiloxane-based surfactant having a fluorine atom. These may have a polymerizable group in a side chain.

Examples of the polysiloxane-based surfactant include a surfactant having a siloxane bond in the molecule. Specifically, for example, Toray Silicone DC3PA, Toray SiliconeSH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade names: Toray. Dow Corning (stock)), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (made by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (made by Japan Momentive Performance Materials) Wait.

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Specifically, for example, Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30 , Megafac RS-718-K (manufactured by DIC), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Electric Corporation), Surflon (registered trademark) S381, Surflon S382 , Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Institute).

Examples of the polysiloxane-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, for example, Megafac (registered trademark) R08, MegafacBL20, MegafacF475, MegafacF477, and Megafac F443 (manufactured by DIC (stock)) can be mentioned.

The content of the leveling agent (F-1) is contained in the red colored curable resin composition, and 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 or less, and more preferably 0.004% by mass. Above 0.05 mass%. The content does not include the content of the pigment dispersant.

(Other ingredients)

The red colored curable resin composition of the present invention may contain one or more fillers, polymer compounds other than the resin (B), antioxidants, adhesion promoters, ultraviolet absorbers, and Additives such as coagulants.

The total content of the red colorant and the CI pigment blue 16 in the red colored curable resin composition is preferably 10 to 50 parts by mass, more preferably 20 to 100 parts by mass of the solid content of the red colored curable resin composition. To 45 parts by mass, more preferably 30 to 40 parts by mass.

As described later, from the standpoint of ease of forming the photoresist pattern when the photoresist pattern is formed from the red colored curable resin composition, the total content of the red colorant and CI Pigment Blue 16 is greater than that of the red colored curable resin composition. The solid content is preferably 100 parts by mass and preferably 45 parts by mass or less.

In addition, in this specification, "a solid content of a red coloring curable resin composition" means all components other than a solvent (E) among the components contained in a red coloring curable resin composition.

(Manufacturing method of red coloring composition)

The red coloring composition of the present invention can be prepared by mixing optional components such as a red colorant, C.I. Pigment Blue 16, and a solvent (E).

In the red coloring composition, the pigment is preferably in a state of a dispersion liquid uniformly dispersed in a solvent. The pigment preferably has a uniform particle size. The dispersion liquid can be obtained by mixing a pigment and a solvent. If required, pigment dispersants can also be mixed. A pigment dispersion in a state where the pigment is uniformly dispersed in a solvent can be obtained by performing a dispersion treatment by mixing a pigment dispersant.

As the pigment dispersant, a commercially available surfactant can be used, and examples thereof include polysiloxane, fluorine, ester (including polyester), cationic, anionic, nonionic, amphoteric, polyester, and polymer. Surfactants such as amines and acrylics.

Specific examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitol fatty acid esters, fatty acid modified polyesters, and tertiary amine modification In addition to polyurethane, polyethylenimine, etc., for example, trade names are KP (Shinyue Chemical Industry Co., Ltd.), Floren (Kyoeisha Chemical Co., Ltd.), Solsperse (Zeneca (Co. EFKA (made by BASF Japan), Ajisper (registered trademark) (made by Ajinomoto Fine Techno), Disperbyk (made by Big Chemie), and the like. The pigment dispersant may be used singly or in combination of two or more kinds.

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 based on 100 parts by mass of the pigment. When the amount of the pigment dispersant used is within the above range, there is a tendency that a pigment dispersion liquid in a uniformly dispersed state is easily obtained.

The solvent constituting the pigment dispersion liquid is not particularly limited, and examples thereof include the same solvent as the solvent (E). Among them, the solvent is preferably propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethyl ether. Diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide, etc. , More preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 3 -Ethyl ethoxypropionate and the like.

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

Various pigments used in the preparation of the red coloring composition may be subjected to rosin treatment, surface treatment using a pigment derivative having an acidic group or a basic group introduced therein, a pigment dispersant, etc., as required, and polymer compounds, etc. The resulting grafting treatment on the pigment surface, a micronization treatment by a sulfuric acid micronization method, or a cleaning treatment by an organic solvent or water to remove impurities, an ion exchange method by an ionic impurity, etc. Removal processing.

(Manufacturing method of red colored curable resin composition)

The red colored curable resin composition of the present invention can be mixed with a red colorant, CI Pigment Blue 16, resin (B), polymerizable compound (C), and polymerization initiator (D), and optionally any coloring component, The solvent (E), the leveling agent (F-1), the polymerization initiation aid (D1), the antioxidant (G), and other components are prepared.

〈Color filter and manufacturing method thereof〉

The red coloring composition of the present invention can be used as a material for obtaining a red color filter. The so-called red color filter refers to a light that transmits color having a wavelength component mainly in a wavelength range of 580 to 780 nm.

The color filter may be formed as a molded body of a cured 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, or may be formed as a pattern on a substrate A hardened product (pattern) of a red colored curable resin composition.

The method for producing a cured product of the patterned red colored curable resin composition may be, for example, a lithography method, an inkjet method, a printing method, and the like, and is preferably a lithography method, for example. The lithography method is a method in which a red colored curable resin composition is coated on a substrate and dried to form a composition layer. The composition layer is exposed through a photomask to develop the composition. In the lithography method, a hardened material of the composition layer can be formed as a coating film by using no photomask and / or no development during exposure.

For the substrate system, for example, glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, and soda lime glass coated with silicon oxide, polycarbonate, polymethyl methacrylate, and polyterephthalic acid can be used. Resin plates such as ethylene glycol, silicon, and the above-mentioned base plate are formed with aluminum, silver, silver / copper / palladium alloy films, and the like. On such substrates, other color filter layers, resin layers, transistors, circuits, etc. may also be formed.

The formation of a coating film or a pattern by a lithography method can be performed under a conventional or conventional apparatus and conditions, and can be produced, for example, as follows. First, a red colored curable resin composition is coated on a substrate, and volatile components such as solvents are removed by drying (pre-baking) and / or drying under reduced pressure, and dried 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 heating and drying is preferably 30 to 120 ° C, and more preferably 50 to 110 ° C. The heating time is preferably from 10 seconds to 5 minutes, and more preferably from 30 seconds to 3 minutes. When performing drying under reduced pressure, it is preferable to perform 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 intended color filter.

Then, when the composition layer is patterned, it is exposed through a photomask. The pattern on the photomask is not particularly limited, and a pattern corresponding to the intended use can be used. It is not necessary to use a photomask when forming a coating film. The light source used for the exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light below 350 nm can be cut off by using a filter that cuts the wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively cut by using a band-pass filter that obtains the wavelength range. Get. Specifically, the light source may be, for example, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, or the like.

Since the exposure system irradiates the parallel light uniformly on the exposure surface, or the mask can be correctly aligned with the substrate on which the composition layer is formed, it is preferable to use an exposure device such as a mask alignment machine and a stepper.

By exposing the exposed composition layer to a developing solution and developing it, a pattern is formed on the substrate. By developing, the unexposed part of the composition layer is dissolved in the developing solution and removed.

The developing solution is preferably an aqueous solution of a basic compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethylammonium hydroxide, and the like. The concentration of such an alkaline compound in an aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. The developing solution may also contain a surfactant.

The imaging method may be any of a liquid holding method, a dipping method, and a spraying method. Furthermore, the substrate can be tilted at any angle during development. After development, washing with water is preferred.

Moreover, it is preferable to perform the subsequent baking on the obtained red 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.

The film thickness of the coating film and the pattern after the 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 it is usually 1 μm or more and may be 1.5 μm or more.

The red coloring composition of the present invention can form a red color filter with improved contrast.

<Display Device>

The color filter of the present invention can be used as a red color filter used in display devices (liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging elements.

    [Example]    

Hereinafter, the present invention will be described more specifically by showing examples and comparative examples, but the present invention is not limited to these examples. In the examples, the content and% used are expressed in terms of% and parts. Unless otherwise specified, they are based on weight.

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

In a 1-liter flask equipped with a reflux cooler, a dropping funnel and a stirrer, an appropriate amount of nitrogen was flowed in instead of a nitrogen atmosphere, and 371 parts by weight of 1-methoxy-2-propyl acetate was placed, and heated to 85 ° C while stirring. . Then, 54 parts by weight of acrylic acid, 225 parts by weight of a mixture of 3,4-epoxytricyclo [5.5.2.1.0 ^2,6 ] dec-8 or 9-based ester, and vinyl were added dropwise over 4 hours. A mixed solution of 81 parts by weight of toluene (isomer mixture) and 80 parts by weight of 1-methoxy-2-propyl acetate. On the other hand, it took 5 hours to dropwise dissolve 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. The solution. After the dropwise addition was completed, the solution was kept at the same temperature for 4 hours, and then cooled to room temperature to obtain a copolymer having 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. The weight average molecular weight Mw of the produced copolymer (hereinafter, this copolymer is referred to as "resin (B)") was 10,600, and the molecular weight distribution was 2.01.

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

Device; HLC-8120GPC (Tosoh (shares) system)

Column; TSK-GELG2000HXL

Column temperature; 40 ℃

Solvent; THF

Flow rate; 1.0mL / min

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

Injection volume; 50 μL

Sensor; RI

Calibration reference materials; TSK standard polystyrene F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh)

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

Mixed

Using a bead mill, the pigment was sufficiently dispersed to obtain a red pigment dispersion liquid (A1) containing CI Pigment Red 254.

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

Mixed

83.8 parts of propylene glycol monomethyl ether acetate was used to sufficiently disperse the pigment 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 Liquid (A3)>

Mixed

Using a bead mill, the pigment was sufficiently dispersed to obtain a red pigment dispersion liquid (A3) containing CI Pigment Red 242.

<Synthesis Example 5: Preparation of blue pigment dispersion liquid (A4)>

Mixed

Using a bead mill, the pigment was sufficiently dispersed to obtain a blue pigment dispersion liquid (A4) containing CI Pigment Blue 16.

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

Mixed

Using a bead mill, the pigment was sufficiently dispersed to obtain a blue pigment dispersion liquid (A5) containing CI Pigment Blue 15: 3.

<Synthesis Example 7: Preparation of blue pigment dispersion liquid (A6)>

Mixed

Using a bead mill, the pigment was sufficiently dispersed to obtain a blue pigment dispersion liquid (A6) containing CI Pigment Blue 15: 6.

<Examples 1 to 3 and Comparative Examples 1 to 5>

(1) Preparation of red colored curable resin composition

Resin (B), red pigment dispersions (A1) to (A3), blue pigment dispersions (A4) to (A6), polymerizable compound (C-1), polymerization initiator (D-1), The leveling agent (F-1) was mixed in a dosage form so as to be the blending amount described in Table 1, to obtain a red colored curable resin composition.

Moreover, in each Example and a comparative example, propylene glycol monomethyl ether acetate was mixed so that it might become the solid content (NV) shown in Table 1.

The unit of the blending amount of each component in Table 1 is "mass parts", the blending amount is a converted 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): dinepentaerythritol hexaacrylate ‧ dinepentaerythritol 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): fluorinated group / lipophilic group-containing oligomer (manufactured by DIC (stock), trade name "Megafac F-554")

(2) Production of coating film

A red colored hardening resin composition was applied on a 2-inch-square glass substrate ("Eagle XG" manufactured by Corning Corporation) by a spin coating method, and then pre-baked at 100 ° C for 3 minutes. After cooling, the substrate coated with the red colored curable resin composition was exposed to 80 mJ / cm ² (365 nm as the standard using an exposure machine ("TME-150RSK" manufactured by Topcon)) in an atmospheric environment using an exposure machine. ) For light irradiation. Then, it was baked at 230 ° C. for 30 minutes in an oven to obtain a coating film.

(3) Measurement of film thickness

About the obtained coating film, the film thickness was measured using the film thickness measuring device (DEKTAK3; made by Japan Vacuum Technology Co., Ltd.). The results are shown in Table 2.

(4) Measurement of chromaticity

About the obtained coating film, the colorimeter (OSP-SP-200; manufactured by Olympus) was used to measure the spectrometer, and the characteristic parameters of the C light source were used to measure the xy chromaticity coordinates (x, y) in the XYZ color system of CIE. ) And brightness Y. The results are shown in Table 2.

(5) Evaluation of comparison (CR)

As for the obtained coating film, a contrast meter (CT-1; manufactured by Husaka Electric Co., Ltd., BM-5AS; Topcon (stock), light source; F-10, polarizing film; manufactured by Husaka Electric (stock)) The blank value is 10000, and the comparison is determined. As long as the contrast of the coating film is high, the pattern is also high contrast. The results are shown in Table 2.

From the comparison between Example 1 and Comparative Examples 1 and 2, the comparison between Examples and Comparative Example 3, and the comparison between Example 3 and Comparative Example 4, it is known that the red coloring composition containing CI Pigment Blue 16 is more than other blue colors. The red coloring composition of the pigment (CI Pigment Blue 15: 3, CI Pigment Blue 15: 6) can also obtain a high-contrast coating film.

From these results, it was found that C.I. Pigment Blue 16 can be used as a contrast enhancer in red color filters.

Claims (6)

    A red coloring composition comprising a red colorant and C.I. Pigment Blue 16.         The red coloring composition according to item 1 of the scope of patent application, wherein the content of C.I. Pigment Blue 16 is 0.005 parts by mass or more and 1.5 parts by mass or less with respect to 100 parts by mass of the red colorant.         The red coloring composition according to item 1 or 2 of the scope of the patent application, wherein the red colorant contains a compound having a diketopyrrolopyrrole skeleton.         The red coloring composition according to any one of claims 1 to 3 in the scope of the patent application, which further includes red coloring and hardening properties of the resin (B), the polymerizable compound (C), and the polymerization initiator (D).组合 物。 Composition.         A color filter is formed by the red coloring composition described in item 4 of the scope of patent application.         A display device includes the color filter described in item 5 of the scope of patent application.