CN108459467B - Red coloring composition - Google Patents

Abstract

A red coloring composition comprising a red colorant and C.I. Pigment Blue 16.

Description

red coloring composition

technical field

The present invention relates to red coloring compositions.

Background technique

Color filters are used in display devices such as liquid crystal display panels, electroluminescence panels, and plasma display panels.

JP2013-014750 A describes a coloring composition capable of producing a high-contrast color filter. In JP2005-181384, a red coloring composition for color filters is described. For the red coloring composition, by adjusting the brightness of red, it is possible to adjust the brightness of blue, green, red, etc. In the case of the chromaticity, white is adjusted to the target color temperature (K) and the target color difference (Δuv).

Contents of the invention

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. Pigment Blue 16 (C.I. Pigment Blue 16).

[2] The red coloring composition according to [1], wherein the content of C.I. Pigment Blue 16 is not less than 0.005 parts by mass and not more than 1.5 parts by mass based on 100 parts by mass of the red colorant.

[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], which is a red coloring curable composition further comprising a resin (B), a polymerizable compound (C) and a polymerization initiator (D). resin composition.

[5] A color filter formed from the red coloring composition described in [4].

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

Detailed ways

＜Red coloring composition＞

The red coloring composition of the present invention comprises a red colorant and C.I. Pigment Blue 16.

The red coloring composition may further contain coloring ingredients other than the red colorant and 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 improving agent for improving the contrast of a red color filter.

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

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

Hereinafter, each component contained in the red coloring composition of this invention is demonstrated.

(red colorant)

As a red coloring agent, a red pigment, a red dye, an orange pigment, an orange dye, etc. are mentioned. A red coloring agent may consist of 1 type, and may contain 2 or more types.

Examples of red pigments include compounds having a diketopyrrolopyrrole skeleton and compounds classified as pigments in the Dye Index (published by The Society of Dyers and Colourists).

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

As a compound which has a diketopyrrolopyrrole frame|skeleton, the compound represented by a formula (P) is mentioned.

[In formula (P), R ^a1 , R ^a2 , R ^a3 and R ^a4 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 fluorine atom, chlorine atom, bromine atom and iodine atom, preferably chlorine atom and bromine atom.

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

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

R ^a5 and R ^a6 can together form an alkanediyl group (alkanediyl) with 2 to 8 carbon atoms, and the -CH ₂ - contained in the alkanediyl group can be replaced by -NR ^a7 -, -O-, -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 methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, isopropyl group, isobutyl group, sec-butyl group, isopentyl group and the like.

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, etc.

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

Examples of -SR ^a5 include methylsulfanyl, ethylthio, propylthio, butylthio, pentylthio and the like.

Examples of -SOR ^a5 include methylsulfinyl, ethylsulfinyl, propylsulfinyl, butylsulfinyl, pentylsulfinyl and the like.

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

Examples of -NR ^a6 COR ^a5 include N-acetylamino, N-propionylamino, N-benzoylamino, N-methyl-N-acetylamino and the like.

Examples of the group in which R ^a5 and R ^a6 in -NR ^a6 COR ^a5 form a ring include groups represented by the following formula.

Examples of -CONR ^a5 R ^a6 include N-methylaminocarbonyl, N-ethylaminocarbonyl, N,N-dimethylaminocarbonyl, N,N-diethylaminocarbonyl, N,N-ethyl Methylaminocarbonyl, etc.

Examples of the group in which R ^a5 and R ^a6 in -CONR ^a5 R ^a6 form a ring include groups represented by the following formula.

Among the compounds represented by formula (P), preferably at least one of R ^a1 , R ^a2 , R ^a3 and R ^a4 is a chlorine atom or a bromine atom, more preferably at least one of R ^a1 and R ^a2 is a chlorine atom or a bromine atom atom. More preferably, R ^a1 is a chlorine atom or a bromine atom, and R ^a2 is a chlorine atom or a bromine atom.

Preferably, both R ^a3 and R ^a4 are hydrogen atoms.

Specifically, examples of the compound represented by the formula (P) include 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.

As a compound represented by formula (P), the compound represented by the following formula is also mentioned.

Examples of the above-mentioned compounds classified as pigments in the Dye Index include C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, and 176 in addition to the above-mentioned C.I. Pigment Red 254. , 177, 180, 192, 209, 215, 216, 224, 242, 255, 264, 265, etc.

Examples of red dyes include compounds classified as dyes in the above-mentioned dye index and known dyes described in Dyeing Note.

Specifically, examples of C.I. acid dyes include C.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, etc.

Examples of C.I. direct dyes include C.I. Direct Red (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 C.I. Mordant dyes include C.I. 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.

As an orange pigment, the compound classified as a pigment (Pigment) in the above-mentioned dye index is mentioned.

Specifically, C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73, etc. are mentioned.

Examples of the orange dye include the above-mentioned compounds classified as dyes in the Dye Index, and the known dyes described in the Dyeing Note above.

Specifically, examples of C.I. acid dyes include C.I. 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 C.I. Mordant dyes include C.I. Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43 , 47, 48, etc.

Examples of red dyes and orange dyes include xanthene dyes that are red or orange and contain compounds having a xanthene skeleton in their molecules; red or orange dyes that contain compounds that can form complex salts with metal atoms. The dye molecule of the group and the metal complex salt dye formed by the complex salt with the metal atom; the red or orange azo dye, etc.

Red or orange xanthene dyes partially overlap with the above-mentioned dyes, including C.I. Acid Red 51, 52, 87, 92, 94, 289, 388, C.I. Basic Red 1 (rhodamine 6G), 8 , C.I. Basic Red 10 (Rhodamine B), C.I. Solvent Red 218, C.I. Media Red 27, C.I. Reactive Red 36 (rose bengal B), Sulforhodamine G (Sulforhodamine G), Xanthene dyes described in Japanese Patent Application Laid-Open No. 2010-32999, xanthene dyes described in Japanese Patent No. 4492760, and the like.

Red or orange metal complex dyes partially overlap with the above dyes, for example, C.I. solvent orange 5, 11, 20, 40: 1, 41, 45, 54, 56, 58, 62, 70 , 81, 99, C.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. Acid Orange 74, 162, C.I. Acid Red 211, metal complex salt dyes described in JP2010-170117 and JP2011-59673.

As an azo dye which shows red or orange, the azo dye etc. which were described in JP2013-14750 A are mentioned.

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

As the red pigment, a compound having a diketopyrrolopyrrole skeleton is preferable because it is advantageous for contrast improvement of a red color filter.

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. More preferably, it is 20-100 mass parts, More preferably, it is 40-100 mass parts.

(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 16 can be used as a contrast improving agent for improving the contrast of a color filter.

In the red coloring composition of the present invention, by including a red colorant and C.I. Pigment Blue 16 together, the contrast of a red color filter can be improved.

The content of C.I. Pigment Blue 16 in the red coloring composition is not particularly limited, as long as it is within the range that makes the red coloring composition appear red, it is preferably 0.005 parts by mass or more, more Preferably it is 0.4 mass part or more, Preferably it is 1.5 mass parts or less, More preferably, it is 0.8 mass parts or less. When the content of C.I. Pigment Blue 16 is 0.005 parts by mass or more, a desired contrast-enhancing effect can be obtained. When the content of C.I. Pigment Blue 16 is 1.5 parts by mass or less, the intended red color tone will be easily obtained.

(other coloring ingredients)

The red coloring composition of the present invention may contain coloring components other than the red coloring agent and C.I. As for other coloring components, only 1 type may be used, and 2 or more types may be used 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. They may be pigments or dyes. The content of other coloring components is not particularly limited as long as it is within the range that makes the red coloring composition appear red, and is preferably 0.005 to 10 parts by mass based on 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 resin composition containing a resin (B), a polymerizable compound (C), and a polymerization initiator (D). The red colored curable resin composition may contain 1 type, or 2 or more types of resin (B). The resin (B) is preferably an alkali-soluble resin. Alkali solubility 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] and the like.

Resin [K1]: At least 1 sort(s) selected from the group which consists of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride [Hereinafter, it may be referred to as "(a)". ], and a monomer (b) having a cyclic ether structure with 2 to 4 carbon atoms and an ethylenically unsaturated bond [hereinafter, sometimes referred to as "(b)". ) copolymers.

Resin [K2]: (a), (b), and monomer (c) that can be copolymerized with (a) (however, monomer (c) is different from (a) and (b).) [hereinafter, sometimes referred to as "(c)". ] Copolymer.

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

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

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

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

As (a), specifically, there may be mentioned:

(Meth)acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid and other unsaturated monocarboxylic acids;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid Dicarboxylic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid and other unsaturated dicarboxylic acids;

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] Hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene and other carboxyl-containing bicyclic unsaturated compounds;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1, 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, bicyclo[2.2.1]hept-2-ene-5,6-dicarboxylic anhydride (nadic anhydride (himic anhydride)) and other unsaturated dicarboxylic acid anhydrides;

Unsaturation of polybasic carboxylic acids such as mono[2-(meth)acryloyloxyethyl]succinate and mono[2-(meth)acryloyloxyethyl]phthalate, etc. Mono[(meth)acryloyloxyalkyl]esters;

α-(Hydroxymethyl)(meth)acrylic acid and the like are unsaturated (meth)acrylic acid containing a hydroxyl group and a carboxyl group in the same molecule.

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, "(meth)acryl-" means at least one selected from the group consisting of "acryl-" and "methacryl-". The same applies to expressions such as "(meth)acryloyl" and "(meth)acrylate".

(b) means a cyclic ether structure having 2 to 4 carbon atoms (for example, one selected from the group consisting of oxirane ring, oxetane ring and tetrahydrofuran ring (oxolane ring) at least 1 kind) and a polymerizable compound of an ethylenically unsaturated bond. (b) is preferably a monomer having a cyclic ether structure with 2 to 4 carbon atoms and a (meth)acryloyloxy group.

As (b), monomer (b1) which has an oxirane group and an ethylenically unsaturated bond [it may be called "(b1)" hereafter is mentioned. ], a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond [hereinafter, may be referred to as "(b2)". ], a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond [hereinafter, may be referred to as "(b3)". 〕wait.

Examples of (b1) include a monomer (b1-1) having a structure obtained by epoxidizing an unsaturated aliphatic hydrocarbon [hereinafter, it may be referred to as "(b1-1)". ], a monomer (b1-2) having a structure obtained by epoxidizing an unsaturated alicyclic hydrocarbon [hereinafter, may be referred to as "(b1-2)". ].

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, 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(glycidyl Oxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tri( Glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3 , 4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene, etc.

Examples of (b1-2) include vinyl cyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE 2000; manufactured by DAICEL CORPORATION), acrylic acid 3,4-epoxycyclohexyl methyl ester (for example, CYCLOMER A400; manufactured by DAICEL CORPORATION), 3,4-epoxycyclohexyl methyl methacrylate (for example, CYCLOMER M100; manufactured by DAICEL CORPORATION), represented by formula (I) Compounds represented by formula (II), etc.

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

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

Examples of the alkyl group in which a hydrogen atom is substituted by a hydroxyl group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy -1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, or 4-hydroxybutyl, etc.

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

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

X ¹ and X ² are preferably single bonds, methylene, ethylene, *-CH ₂ -O- (* represents the bonding site with O) group, *-CH ₂ CH ₂ -O- group, more Preferred 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), preferably formula (I-1), formula (I-3), Compounds represented by formula (I-5), formula (I-7), formula (I-9), formula (I-11) to formula (I-15), more preferably include formula (I-1), Compounds represented by formula (I-7), formula (I-9), and formula (I-15).

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

The compound represented by formula (I) and the compound represented by formula (II) may be used alone or in combination of two or more. When two or more types are used in combination, the mixing ratio is preferably 5:95 to 95:5, more preferably 20:80 to 80:20, and still more preferably 50:50～80:20.

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)acryloyloxymethyl oxetane, 3-methyl-3-(meth)acryloyloxyethyl oxetane, 3-ethyl-3-(meth)acryloyloxyethyl oxetane butane.

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.

Preferable examples of (b3) include tetrahydrofurfuryl acrylate (for example, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

Specific examples of (c) include:

Methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-(meth)acrylate Ethylhexyl, Lauryl (meth)acrylate, Lauryl (meth)acrylate, Stearyl (meth)acrylate, Cyclopentyl (meth)acrylate, Cyclo(meth)acrylate Hexyl ester, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate [in this technical field, as a common name, called "Dicyclopentanyl(meth)acrylate (meth)acrylate". In addition, it may also be called "tricyclodecyl (meth)acrylate". ], tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth)acrylate [in this technical field, as a commonly used name, it is called "dicyclopentenyl (meth)acrylate (dicyclopentenyl( meth)acrylate)". ], dicyclopentanyl oxyethyl (meth) acrylate (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, vinyl (meth) acrylate Propyl ester, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate and other (meth)acrylates;

Hydroxyl-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

Diethyl maleate, diethyl fumarate, diethyl itaconate and other dicarboxylic acid diesters;

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]hept-2-ene, etc. Bicyclic unsaturated compounds;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, 3-maleimidobenzoic acid-N-succinimide ester, 4 - dicarbonyl imide derivatives such as maleimidobutyric acid-N-succinimide ester;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, (meth)acrylonitrile, vinyl chloride, vinylidene chloride, (form base) acrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

Among them, from the viewpoint of copolymerization reactivity and heat resistance, as (c), benzyl (meth)acrylate, tricyclodecanyl (meth)acrylate, styrene, and N-phenylmaleimide are preferable. , N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, etc. Moreover, as (c), benzyl (meth)acrylate and tricyclodecyl (meth)acrylate are more preferable from the viewpoint of excellent developability at the time of pattern formation.

It is preferable that the ratio of the structural unit derived from each monomer in resin [K1] is the following range among all the structural units which comprise resin [K1].

Structural unit derived from (a): 50 to 98 mol% (more preferably 55 to 90 mol%),

Structural unit derived from (b), especially structural unit derived from (b1): 2 to 50 mol% (more preferably 10 to 45 mol%).

When the ratio of the structural unit of resin [K1] is in the said range, there exists a tendency for the solvent resistance of storage stability, developability, and the obtained pattern to be excellent.

Resin [K1] can refer to the method described in the document "Experimental Method for Polymer Synthesis" (written by Takayuki Otsu, published by Kagaku Doujin Co., Ltd., first printing of the first edition, issued on March 1, 1972) and this document Citations documented in .

Concretely, the following method is enumerated: put predetermined amounts of (a) and (b), a polymerization initiator, a solvent, etc. into a reaction container, and, for example, replace oxygen with nitrogen to form a deoxidizing atmosphere, and carry out Heat and keep warm while stirring. It should be noted that the polymerization initiator, solvent, and the like used here are not particularly limited, and any polymerization initiator, solvent, and the like commonly 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.), organic peroxides (benzoyl peroxide, etc.). As a solvent, what is necessary is just to dissolve each monomer, and the solvent (E) etc. which are demonstrated later as a solvent of a red colored curable resin composition can be used.

The obtained copolymer may be used as it is after the reaction, may be used as a concentrated or diluted solution, or may be obtained as a solid (powder) by reprecipitation or the like. In particular, by using the solvent (E) described later as a solvent during the above-mentioned polymerization, the solution after the reaction can be used as it is, and the production process can be simplified.

It is preferable that the ratio of the structural unit derived from each monomer in resin [K2] is the following range among all the structural units which comprise resin [K2].

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

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

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

When the ratio of the structural unit of resin [K2] is in the said range, it exists in the tendency which is excellent in storage stability, developability, and the solvent resistance of the pattern obtained, heat resistance, and mechanical strength.

Resin [K2] can be produced by the same method as the method described as the production method of resin [K1]. Specifically, the following method can be mentioned: a predetermined amount of (a), (b) (especially (b1)) and (c), a polymerization initiator, and a solvent are charged into a reaction vessel, and the , stirring, heating and heat preservation. The obtained copolymer may be used as it is after the reaction, may be used as a concentrated or diluted solution, or may be obtained as a solid (powder) by reprecipitation or the like.

It is preferable that the ratio of the structural unit derived from each monomer in resin [K3] is the following range among all the structural units which comprise resin [K3].

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

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

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

Resin [K4] can be produced by the following method: obtain the copolymer of (a) and (c), make (b) have the cyclic ether structure of carbon number 2～4 (especially (b1) have Oxirane ring) is added to the carboxylic acid and/or carboxylic acid anhydride contained in (a). Specifically, first, the copolymer of (a) and (c) is manufactured by the method similar to the method described as the manufacturing method of resin [K1]. In this case, the ratio of the structural unit derived from each monomer is preferably within the following range in all structural units constituting the copolymer of (a) and (c).

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

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

Next, a part of the carboxylic acid and/or carboxylic acid anhydride derived from (a) in the above-mentioned copolymer and the cyclic ether structure having 2 to 4 carbon atoms in (b) (especially the cyclic ether structure in (b1) oxirane ring) to react. Specifically, after the copolymer of (a) and (c) is produced, the atmosphere in the flask is replaced from nitrogen to air, and (b) (especially (b1)), carboxylic acid or carboxylic anhydride and cyclic ether Structured reaction catalysts (such as tris(dimethylaminomethyl)phenol, etc.) , Resin [K4] can be obtained.

The usage-amount of (b), especially the usage-amount of (b1), is preferably 5-80 mol with respect to 100 mol of (a), More preferably, it is 10-75 mol. There exists a tendency for the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity to become favorable by being the said range. Since the reactivity of the cyclic ether structure is high and unreacted (b) hardly remains, (b) used for resin [K4] is preferably (b1), more preferably (b1-1).

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

Reaction conditions such as charging method, reaction temperature, and time can be appropriately adjusted in consideration of production facilities, heat generation due to polymerization, and the like. In addition, similarly to the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of production facilities, heat generation due to polymerization, and the like.

About resin [K5], as a 1st stage, it can operate similarly to the manufacturing method of above-mentioned resin [K1], and can obtain the copolymer of (b) (especially (b1)) and (c). In the same manner as above, for the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or a substance obtained in the form of a solid (powder) by reprecipitation or the like may be used. .

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 structural units constituting the above-mentioned copolymer.

Structural unit derived from (b), especially structural unit 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%).

In addition, the cyclic ether structure derived from (b) contained in the copolymer of (b) (especially (b1)) and (c) and (a ) reacts with the carboxylic acid or carboxylic anhydride that it has, and the resin [K5] can be obtained. The usage-amount of (a) reacted with the said copolymer is preferably 5-80 mol with respect to 100 mol of (b) (especially (b1)). (b1) is preferable, and (b1-1) is more preferable as (b) used for resin [K5] from the viewpoint that the reactivity of a cyclic ether structure is high and unreacted (b) does not remain easily.

Resin [K6] is resin obtained by further reacting resin [K5] with carboxylic anhydride.

The hydroxyl group generated by the reaction of the cyclic ether structure with the carboxylic acid or the carboxylic anhydride is reacted with the carboxylic anhydride.

Examples of carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, Phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, bicyclo[2.2.1]hept-2-ene-5,6-dimethyl Anhydride (Nadic anhydride), etc.

Among the resins [K1] to [K6], the resin (B) is preferably [K1] or [K2]. Resin (B) may consist of only 1 type of resin, and may contain 2 or more types of resins.

The weight average molecular weight (Mw) in terms of polystyrene of resin (B) becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000, More preferably, it is 5,000-30,000. When the weight average molecular weight (Mw) is within the above range, the solubility of the unexposed portion with respect to the developing solution is high, and the remaining film rate and hardness of the obtained pattern also tend to be high. The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1-6, more preferably 1.2-4.

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

The content of the resin (B) is preferably 5 to 50 mass %, more preferably 15 to 45 mass %, and still more preferably 25 to 40 mass % in 100 mass % of solid content of the red colored curable resin composition. When content of resin (B) exists in the said range, there exists a tendency for the solubility with respect to the developing solution of an unexposed part to become high.

(polymerizable compound (C))

The polymerizable compound (C) is not particularly limited, as long as it is a compound that can be polymerized by the action of active radicals or the like generated by the polymerization initiator (D) due to light irradiation or the like, examples of which include polymerizable ethylenic bonds Compounds with unsaturated bonds, etc. 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 examples thereof include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(methyl) Acrylates, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate Ester, tetraerythritol deca(meth)acrylate, tetraerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, ethylene glycol modified pentaerythritol tetra (Meth)acrylate, Ethylene glycol-modified dipentaerythritol hexa(meth)acrylate, Propylene glycol-modified pentaerythritol tetra(meth)acrylate, Propylene glycol-modified dipentaerythritol hexa(meth)acrylate, Caprolactone Modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like. Among these, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are preferable.

The red colored composition (red colored curable resin composition) of this invention may contain 1 type, or 2 or more types of polymerizable compounds (C). The content of the polymerizable compound (C) is preferably 20 to 150 parts by mass, more preferably 40 to 70 parts by mass, relative to 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 capable of generating active radicals, acids, etc. by the action of light or heat to initiate polymerization, and known polymerization initiators can be used.

Examples of the polymerization initiator (D) include oxime compounds such as O-acyl oxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds.

Regarding the polymerization initiator (D), two or more types may be used in combination in consideration of sensitivity, formation of a precise pattern shape, and the like. It is preferable that the polymerization initiator (D) contains an oxime compound, such as an O-acyl oxime compound, from the viewpoint of sensitivity and precision preparation of the pattern shape which has a desired line width.

The O-acyl oxime compound is a compound having a structure represented by formula (d). Hereinafter, * indicates a bonding site.

Examples of such O-acyl oxime compounds include N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy Base-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)-3-ring Amylpropan-1-one-2-imine, N-acetyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethyl Alkane-1-imine, N-acetyloxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolane Methyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetyloxy-1-[9-ethyl-6-(2-methyl Benzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methyl Benzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-one-2-imine, N-acetyloxy-1-[9-(2-ethylhexyl) -6-(2,4,6-Trimethylbenzoyl)-9H-benzo[i]carbazol-3-yl]-3-[1-(2,2,3,3-tetrafluoropropane oxy)phenyl]methaneimine, etc. Commercially available items such as IRGACURE OXE01, OXE02, and OXE03 (the above are manufactured by BASF Co., Ltd.), N-1919 (manufactured by ADEKA Corporation) can also be used. In the case of these O-acyl oxime compounds, there exists a tendency for the color filter excellent in photolithography performance to be obtained.

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

As a compound having a structure represented by formula (d4), 2-methyl-2-morpholino (morpholino)-1-(4-methylthiophenyl)propane-1-one, 2-di Methylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl] -1-[4-(4-morpholinyl)phenyl]butan-1-one and the like. Commercial items such as IRGACURE 369, 907, and 379 (the above are manufactured by BASF Co., Ltd.) can also be used.

As a compound having a structure represented by formula (d5), 2-hydroxyl-2-methyl-1-phenylpropane-1-one, 2-hydroxyl-2-methyl-1-[4-(2 -Hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one Oligomers, α,α-diethoxyacetophenone, benzil dimethyl ketal, etc.

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

Examples of biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-bis Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, see JP-A-6-75372, JP-A-6-75373, etc.), 2,2'- Bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5 ,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole Imidazole (for example, see Japanese Patent Application Publication No. 48-38403, Japanese Patent Application Publication No. 62-174204, etc.), 4,4', 5,5'-position phenyl is substituted by carboalkoxy imidazole compounds (see, for example, JP-A No. 7-10913, etc.) and the like. Among them, compounds represented by the following formulas or mixtures thereof are preferred.

Examples of triazine compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) base)-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)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethylene Base]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1, 3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc.

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

In addition, examples of the polymerization initiator (D) include benzoin, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Compounds; benzophenone, methyl phthaloylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4 '-Tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone and other benzophenone compounds; 9,10-phenanthrenequinone, 2-ethylanthraquinone, Quinone compounds such as camphorquinone; 10-butyl-2-chloroacridone, benzil, methyl benzoylformate, titanocene compounds, etc. These are preferably used in combination with a polymerization initiation adjuvant (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 further Preferably it is 0.07-0.10 mass part. When content of a polymerization initiator (D) exists in the said range, since there exists a tendency for sensitivity to improve and exposure time to shorten, the productivity of a color filter will tend to improve.

(polymerization initiation aid (D1))

The polymerization initiation adjuvant (D1) is a compound or a sensitizer for promoting polymerization of a polymerizable compound whose polymerization has been initiated by a polymerization initiator. When a polymerization initiation adjuvant (D1) is included, it can be used in combination with a polymerization initiator (D).

As a polymerization start adjuvant (D1), an amine compound, an alkoxy anthracene compound, a thioxanthone compound, a carboxylic acid compound, etc. are mentioned. Among them, thioxanthone compounds are preferable. Two or more polymerization initiation adjuvants (D1) may be used in combination.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzene Isoamyl formate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(di Methylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)bis Benzophenone and the like, among which, 4,4'-bis(diethylamino)benzophenone is preferable. Commercial items such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used.

Examples of alkoxyanthracene compounds 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, etc.

Examples of thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Chloro-4-propoxythioxanthone, etc.

Examples of the carboxylic acid compound include phenylthioglycolic acid, methylphenylthioglycolic acid, ethylphenylthioglycolic acid, methylethylphenylthioacetic acid, dimethylphenylthioglycolic acid, Oxyphenylthioglycolic acid, dimethoxyphenylthioglycolic acid, chlorophenylthioglycolic acid, dichlorophenylthioglycolic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioglycolic acid, N-naphthylglycine, naphthyloxyacetic acid, etc.

It is preferable that it is 0.1-30 mass parts with respect to 100 mass parts of total amounts of resin (B) and a polymeric compound (C), and, as for content of a polymerization start adjuvant (D1), it is more preferable that it is 1-20 mass parts. When content of a polymerization start adjuvant (D1) exists in the said range, a pattern can be formed with higher sensitivity, and there exists a tendency for the productivity of a color filter to improve.

(Solvent (E))

It is preferable that a red coloring composition contains 1 type, or 2 or more types of 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-) , ketone solvents other than ester solvents (solvents containing -CO-), alcohol solvents, aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc.

Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate , butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol Acetate and γ-butyrolactone, etc.

Examples of ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, Glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol , 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole and methyl anisole, etc.

Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropionic acid Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionate Ethyl ester, Propyl 2-methoxypropionate, Methyl 2-ethoxypropionate, Ethyl 2-ethoxypropionate, Methyl 2-methoxy-2-methylpropionate, 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 ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol Alcohol monobutyl ether acetate and dipropylene glycol methyl ether acetate, etc.

Examples of 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, etc.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin. Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene. Examples of the 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. to 180° C. at 1 atm from the viewpoint of coating properties and drying properties. Among them, the solvent (E) preferably contains propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxy propionate, ethylene glycol Alcohol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4- At least one member selected from the group consisting of methyl-2-pentanone and N,N-dimethylformamide, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl At least one selected from the group consisting of ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, and ethyl 3-ethoxypropionate.

In the red coloring composition, the content of the solvent (E) is preferably 70 to 95% by mass, 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, 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 becomes favorable, and the color density does not become insufficient when forming a color filter, so the display characteristics tend to become favorable.

(Leveling agent (F-1))

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

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

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

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule, and the like. Specifically, MEGAFACE (registered trademark) R08, MEGAFACE BL20, MEGAFACE F475, MEGAFACE F477, and MEGAFACE F443 (manufactured by DIC Corporation) etc. are mentioned.

In the red colored curable resin composition, the content of the leveling agent (F-1) is usually 0.001 mass % to 0.2 mass %, preferably 0.002 mass % to 0.1 mass %, more preferably 0.004 mass % to 0.05 mass % Mass% or less. It should be noted that the content of the above-mentioned pigment dispersant is not included in this content.

(other ingredients)

In the red colored curable resin composition of the present invention, 1 of additives such as fillers, polymer compounds other than the resin (B), antioxidants, adhesion promoters, ultraviolet absorbers, and anti-flocculants may be contained as needed. species or more than 2 species.

The total content of the red colorant and C.I. Pigment Blue 16 in the red colored curable resin composition is preferably 10 to 50 parts by mass, more preferably 100 parts by mass of the solid content of the red colored curable resin composition. It is 20-45 mass parts, More preferably, it is 30-40 mass parts.

When forming a resist pattern from a red colored curable resin composition as described later, it is preferable to adjust the total content of the red colorant and C.I. The solid content of 100 mass parts of colored curable resin compositions is 45 mass parts or less.

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

(Manufacturing method of red coloring composition)

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

In the red coloring composition, the pigment is preferably in the state of a dispersion liquid uniformly dispersed in a solvent. The particle size of the pigment is preferably uniform. The above-mentioned dispersion liquid can be obtained by mixing a pigment and a solvent. A pigment dispersant may be mixed as needed. By performing dispersion treatment by mixing a pigment dispersant, a pigment dispersion liquid in a state where a pigment is uniformly dispersed in a solvent can be obtained.

As the pigment dispersant, commercially available surfactants can be used, such as silicone-based, fluorine-based, ester-based (including polyester-based), cationic-based, anionic-based, non-ionic-based, amphoteric, polyester-based, Polyamine-based, acrylic-based, and other surfactants.

Specific examples of surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, In addition to tertiary amine-modified polyurethanes, polyethyleneimines, etc., KP (manufactured by Shin-Etsu Chemical Co., Ltd.), FLOWLEN (manufactured by Kyoeisha Chemical Co., Ltd.), SOLSPERSE (manufactured by Zeneca Chemical Co., Ltd.) are also listed as trade names. Co., Ltd.), EFKA (BASF Japan Co., Ltd.), AJISPER (registered trademark) (Ajinomoto Fine-Techno Co., Inc.), Disperbyk (BYK-Chemie Corporation) and the like. The pigment dispersant may be used alone or in combination of two or more.

When using a pigment dispersant, the usage-amount is preferably 100 mass parts or less with respect to 100 mass parts of pigments, More preferably, it is 5-50 mass parts. When the amount of the pigment dispersant used is within the above range, it tends to be easy to obtain a pigment dispersion liquid with a uniform dispersion state.

It does not specifically limit as a solvent which comprises a pigment dispersion liquid, The thing similar to the above-mentioned solvent (E) is mentioned. Among them, the solvent is preferably propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxy propionate, 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-dimethyl base formamide, 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, ethyl 3-ethoxypropionate, etc.

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

For the various pigments used in the preparation of the red coloring composition, the following treatments may be performed as necessary: rosin treatment, surface treatment using a pigment derivative having an acidic group or a basic group introduced, a pigment dispersant, etc. , Grafting treatment on the surface of the pigment with a polymer compound, etc., micronization treatment using sulfuric acid micronization method, or washing treatment with organic solvent, water, etc. to remove impurities, ion exchange method, etc. Removal treatment for removal of sexual impurities, etc.

(Manufacturing method of red colored curable resin composition)

The red colored curable resin composition of the present invention can be obtained by mixing a red colorant, C.I. Pigment Blue 16, resin (B), polymerizable compound (C), polymerization initiator (D), and optionally coloring components, Solvent (E), leveling agent (F-1), polymerization initiation adjuvant (D1), antioxidant (G), and other components were mixed and prepared.

<Color filter and its manufacturing method>

The red coloring composition of the present invention is useful as a material for obtaining a red color filter. The so-called red color filter is a product that transmits colored light whose main wavelength component is in the wavelength range of 580 to 780 nm.

The color filter may be formed from a molded product of a cured product of the red colored curable resin composition, may be a product formed as a cured product (coating film) of the red colored curable resin composition, or may be formed on a substrate as A cured product (pattern) of a red colored curable resin composition formed into a pattern.

As a method of producing the hardened|cured material of a red coloring curable resin composition in pattern form, a photolithography method, an inkjet method, a printing method, etc. are mentioned, Preferably a photolithography method is mentioned. The photolithography method is a method of applying a red colored curable resin composition to a substrate, drying it to form a composition layer, exposing the composition layer through a photomask, and performing development. In photolithography, a cured product of the composition layer can be formed as a coating film by not using a photomask and/or not performing development during exposure.

As the substrate, glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass with a silica-coated surface, polycarbonate, polymethyl methacrylate, polyparaffin, etc. can be used. A resin plate such as ethylene phthalate, silicon, a substrate obtained by forming a thin film of aluminum, silver, silver/copper/palladium alloy, etc. on the above-mentioned substrate. Other color filter layers, resin layers, transistors, circuits, etc. may be formed on these substrates.

Formation of a coating film or a pattern by photolithography can be performed using known or commonly used equipment and conditions. For example, it can be produced as follows. First, a red colored curable resin composition is applied on a substrate, and volatile components such as solvents are removed by heat drying (prebaking) and/or reduced pressure drying, and then dried to obtain a smooth composition layer . Examples of the coating method include a spin coating method, a slit coating method, a combination of a slit coating and a spin coating method (slit and spin coating method), and the like.

As temperature at the time of heat-drying, 30-120 degreeC is preferable, and 50-110 degreeC is more preferable. In addition, the heating time is preferably 10 seconds to 5 minutes, and more preferably 30 seconds to 3 minutes. When performing reduced-pressure drying, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa. The film thickness of the composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the intended color filter.

Next, the composition layer may be exposed through a photomask when forming a pattern. The pattern on this photomask is not particularly limited, and a pattern corresponding to the intended use can be used. When forming a coating film, it is not necessary to use a photomask. As a light source used for exposure, the light source which generate|occur|produces the light of the wavelength of 250-450 nm is preferable. For example, for light below 350nm, a filter capable of cutting this wavelength region can be used to cut it, or for light near 436nm, near 408nm, or near 365nm, these filters can be used. The band pass filter (band pass filter) extracted from the wavelength region selectively extracts it. Specifically, as a light source, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned.

In exposure, it is preferable to use an exposure device such as a mask aligner or a stepper in order to uniformly irradiate the entire exposure surface with parallel light rays or to accurately align the photomask and the substrate on which the composition layer is formed.

A pattern can be formed on a board|substrate by developing by making the composition layer after exposure contact a developing solution. By development, the unexposed part of the composition layer is dissolved in a developing solution and removed.

The developer is preferably, for example, an aqueous solution of a basic compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of these basic compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. In addition, the developer may contain a surfactant.

The image development method may be any of spin-on-dip immersion (puddle) method, dipping method, spray method, and the like. In addition, the substrate can be tilted at any angle during development. Water washing is preferably performed after development.

In addition, it is preferable to post-bake the obtained red pattern. The post-baking 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 the post-baking is usually preferably 3 μm or less, 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.

A red color filter with improved contrast can be formed from the red coloring composition of the present invention.

＜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 imaging devices.

Example

Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not limited to these examples. In each example, unless otherwise specified, % and parts indicating content or usage-amount are based on mass.

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

An appropriate amount of nitrogen gas was passed through a 1L flask equipped with a reflux condenser, dropping funnel, and stirrer to replace it with a nitrogen atmosphere, and 371 parts by weight of 1-methoxy-2-propyl acetate was charged, and heated to 85° C. while stirring. Next, 54 parts by weight of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate or 3,4-epoxytricyclo[5.2. 1.0 ^2,6 ] Decane-9-yl ester or their mixture 225 parts by weight, vinyltoluene (isomer mixture) 81 parts by weight, 1-methoxyl-2-propyl acetate 80 parts by weight mixed solution . On the other hand, 30 parts by weight of the polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) was dissolved in 160 parts by weight of 1-methoxy-2-propyl acetate over 5 hours. the resulting solution. After the dropwise addition of the solution was completed, it was kept at the same temperature for 4 hours, and then cooled to room temperature to obtain a copolymer with 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. things. The produced copolymer (hereinafter, this copolymer is referred to as "resin (B)") had a weight average molecular weight Mw of 10600 and a molecular weight distribution of 2.01.

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained resin (B) was performed on the following conditions by the GPC method. The ratio (Mw/Mn) of the weight average molecular weight (Mw) in terms of polystyrene to the number average molecular weight (Mn) obtained under the following conditions was defined as the molecular weight distribution.

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

Column: TSK-GELG2000HXL

Column temperature: 40°C

Solvent: THF

Flow rate: 1.0mL/min

Solid component concentration of the liquid to be measured: 0.001 to 0.01% by mass

Injection volume: 50μL

Detector: RI

Standard material for calibration: TSK STANDARD POLYSTYRENE

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

(manufactured by Tosoh Co., Ltd.)

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

The following were mixed, and the pigment was sufficiently dispersed using a bead mill to obtain a red pigment dispersion (A1) containing C.I. Pigment Red 254.

C.I. Pigment Red 254 10.8 parts

Acrylic pigment dispersant 3.8 parts

Propylene glycol monomethyl ether acetate 85.4 parts

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

The following substances were mixed, and the pigment was sufficiently dispersed using a bead mill to obtain a red pigment dispersion (A2) containing the following compound A.

R ^a1 and R ^a2 in the formula (P) are bromine atoms, and R ^a3 and R ^a4 are hydrogen atoms (hereinafter referred to as compound A) 12.0 parts

Acrylic pigment dispersant 4.2 parts

Propylene glycol monomethyl ether acetate 83.8 parts

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

The following were mixed, and the pigment was sufficiently dispersed using a bead mill to obtain a red pigment dispersion (A3) containing C.I. Pigment Red 242.

C.I. Pigment Red 242 12.0 parts

Acrylic pigment dispersant 4.0 parts

Propylene glycol monomethyl ether acetate 84.0 parts

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

The following were mixed, and the pigment was sufficiently dispersed using a bead mill to obtain a blue pigment dispersion (A4) containing C.I. Pigment Blue 16.

C.I. Pigment Blue 16 11.8 parts

Acrylic pigment dispersant 4.7 parts

Propylene glycol monomethyl ether acetate 83.5 parts

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

The following were mixed, and the pigment was sufficiently dispersed using a bead mill to obtain a blue pigment dispersion (A5) containing C.I. Pigment Blue 15:3.

C.I. Pigment Blue 15:3 12.0 parts

Acrylic pigment dispersant 3.6 parts

Propylene glycol monomethyl ether acetate 84.4 parts

<Synthesis Example 7: Preparation of Blue Pigment Dispersion (A6)>

The following were mixed and the pigment was sufficiently dispersed using a bead mill to obtain a blue pigment dispersion (A6) containing C.I. Pigment Blue 15:6.

C.I. Pigment Blue 15:6 12.0 parts

Acrylic pigment dispersant 2.0 parts

Propylene glycol monomethyl ether acetate 86.0 parts

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

(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 ), a polymerization initiator (D-1), and a leveling agent (F-1) were mixed to obtain a red colored curable resin composition.

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

The unit of the compounding quantity of each component in Table 1 is "mass part", and compounding quantity is converted into solid content, and solid content (NV) is %.

A polymerizable compound (C-1), a polymerization initiator (D-1), and a leveling agent (F-1) are as follows.

Polymerizable compound (C-1): dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., brand name "A-9550")

Polymerization initiator (D-1): a compound represented by the following formula (manufactured by BASF Co., Ltd., trade name "IRGACURE OXE03")

Leveling agent (F-1): Oligomer containing fluorine-containing group and lipophilic group (manufactured by DIC Co., Ltd., trade name "MEGAFACE F-554")

[Table 1]

(2) Production of coating film

The red colored curable resin composition was apply|coated on the 2-inch square glass substrate (Corning company make "EAGLE XG") by the spin coating method, and it prebaked at 100 degreeC for 3 minutes after that. After cooling, using an exposure machine ("TME-150RSK" manufactured by TOPCON CORPORATION), the red colored curable resin composition was applied to the above-mentioned under the air atmosphere with an exposure amount of 80mJ/ ^cm2 (based on 365nm). The substrate is irradiated with light. Then, post-baking was performed at 230° C. for 30 minutes in an oven to obtain a coating film.

(3) Film thickness measurement

About the obtained coating film, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd. product). The results are shown in Table 2.

(4) Determination of chromaticity

For the obtained coating film, the spectrum was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS Co., Ltd.), and the xy chromaticity coordinates (x, y ) and brightness Y. The results are shown in Table 2.

(5) Evaluation of Contrast Ratio (CR)

For the obtained coating film, using a contrast meter (CT-1: manufactured by Tsubosaka Electric Co., Ltd., color difference meter BM-5AS: manufactured by TOPCON CORPORATION, light source: F-10, polarizing film: manufactured by Tsubosaka Electric Co., Ltd.), The contrast was measured with the blank value being 10000. If the contrast in the coating film is high, it is considered that the contrast is also high in the pattern. The results are shown in Table 2.

[Table 2]

Table 2

From the comparison of Example 1 and Comparative Examples 1 and 2, the comparison of Example 2 and Comparative Example 3, and the comparison of Example 3 and Comparative Example 4, it can be seen that the red coloring composition comprising C.I. Compared with the red coloring composition of blue pigment (C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:6), a coating film with high contrast can be obtained.

From the above results, it can be seen that C.I. Pigment Blue 16 is useful as a contrast-enhancing agent in red color filters.

Claims (5)

1. A red coloring composition comprising a red colorant and c.i. pigment blue 16,

the red colorant contains c.i. pigment red or a compound represented by formula (P),

wherein the content of C.I. pigment blue 16 is 0.005 to 1.5 parts by mass based on 100 parts by mass of the red colorant,

in the formula (P), R ^a1 、R ^a2 、R ^a3 And R is ^a4 Independently of one another, a hydrogen atom, a halogen atom or a 1-valent substituent, at least 1 representing a halogen atom.

2. The red-coloring composition according to claim 1, wherein the red colorant comprises the compound represented by the formula (P).

3. The red-colored composition according to claim 1 or 2, which is a red-colored curable resin composition further comprising a resin (B), a polymerizable compound (C) and a polymerization initiator (D).

4. A color filter formed from the red-colored composition of claim 3.

5. A display device comprising the color filter of claim 4.