JP6911643B2 - Coloring compositions and color filters for color filters - Google Patents

Description

According to the present invention, it is possible to obtain a fine pattern with excellent chemical resistance even in a curing process of low-temperature firing, such as a color liquid crystal display device, a C-MOS (Complementary Metal Oxide Semiconductor), and a CCD (Charge Coupled Device). : A composition suitable for a color filter mounted on a solid-state image sensor represented by a charge-coupled device).

In recent years, there has been an increasing demand for color characteristics for color filters such as transmittance, that is, brightness, improvement of color purity, coating uniformity when forming filter segments, sensitivity, developability, and pattern shape. In particular, high definition is required for color filters used in solid-state image sensors used in video cameras, digital cameras, color scanners, and the like. Further, as the pixel size of the color liquid crystal display device and the solid-state image sensor is reduced by increasing the definition, there is a problem that a residue is generated when a pixel pattern is created. Regarding the above problems, for example, Patent Documents 1 to 3 disclose that a color filter having a small amount of development residue is formed by using a photosensitive composition using a copolymer containing a specific acrylic component as a resin component. However, the current situation is that these methods are not sufficient.

JP-A-2007-114604 Japanese Unexamined Patent Publication No. 2000-081508 Japanese Unexamined Patent Publication No. 2012-159566

An object of the present invention is to provide a coloring composition for a color filter, which has good alkali developer resistance, good developability, little development residue, and good dimensions by using a specific pigment and a specific binder resin. Is. Another object of the present invention is to provide a color filter using the same.

That is, the present invention is a coloring composition for a color filter containing a colorant (A), a binder resin (B), a polymerizable compound (C), a polymerization initiator (D) and a solvent (E). The colorant (A) contains at least an isoindolin-based pigment (A1), the binder resin (B) has a weight average molecular weight of 25,000 to 50,000, and the following (a) and (b) The present invention relates to a coloring composition for a color filter, which comprises a resin (B1) obtained by reacting (c) and then (d) with the copolymer of the above.
(A): A monomer having a cyclic ether skeleton having 2 to 4 carbon atoms and an ethylenically unsaturated bond (b): It has an unsaturated bond copolymerizable with (a) and is different from (a). Quantum (c): At least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (d): Polybasic acid anhydrides

The present invention also relates to the above-mentioned coloring composition for a color filter, wherein the coloring agent further contains at least one selected from the group consisting of a diketopyrrolopyrrole pigment (A2) and a halogenated phthalocyanine pigment (A3).

Further, in the present invention, the isoindoline pigment (A1) is described in C.I. I. Pigment Yellow 139 and C.I. I. The present invention relates to the above-mentioned coloring composition for a color filter, which comprises at least one selected from the group consisting of pigment yellow 185.

The present invention also relates to the above-mentioned coloring composition for a color filter in which the content of the colorant (A) in the total solid content is 45% by mass to 65% by mass.

The present invention also relates to the above-mentioned coloring composition for a color filter in which the content of the polymerizable compound (C) in the total solid content is 5% by mass to 20% by mass.

The present invention also relates to the above-mentioned coloring composition for a color filter, wherein the polymerization initiator (D) contains an oxime ester-based photopolymerization initiator.

The present invention further relates to the above-mentioned coloring composition for a color filter containing a thermosetting compound (F).

The present invention also relates to the above-mentioned coloring composition for a color filter in which the thermosetting compound (F) is an epoxy compound.

Furthermore, the present invention relates to a color filter formed by using the coloring composition for a color filter.

According to the present invention, a color filter that does not fade even when immersed in an alkaline developer by containing an isoindoline pigment and a binder resin having a weight average molecular weight of 25,000 to 50,000 and having a specific structure. Compositions for use can be provided. In addition, it is possible to provide a color filter having a small amount of residue and good developability.

Hereinafter, the requirements constituting the coloring composition for a color filter of the present invention will be described in detail. In addition, "CI" in this specification means a color index. Further, the "(meth) acryloyloxy group" represents at least one selected from the group consisting of an acryloyloxy group and a metaacryloyloxy group. Notations such as "(meth) acryloyl" and "(meth) acrylate" have the same meaning. Further, the total solid content of the coloring composition for a color filter means the total mass of the non-volatile components excluding the solvent and the like from the coloring composition for a color filter.

<Coloring composition for color filters>
The coloring composition for a color filter of the present invention is a coloring composition for a color filter containing a coloring agent (A), a binder resin (B), a polymerizable compound (C), a polymerization initiator (D) and a solvent (E). The colorant (A) contains at least an isoindoline pigment (A1), and the binder resin (B) has a weight average molecular weight of 25,000 to 50,000 and has a specific composition. It meets.
The binder resin (B) contained in the coloring composition for a color filter defined in claim 1 is further obtained with (c) after copolymerizing at least two types of monomers (a) and (b). And (d) are reacted. Since the two reactions are carried out after the copolymerization reaction, the structure of the obtained binder resin (B) becomes too complicated, and it is practically impossible or impractical to describe it by a chemical formula or a structural formula. Described in the manufacturing method.

<Colorant (A)>
The coloring composition for a color filter of the present invention is characterized by containing an isoindoline pigment (A1) as a coloring agent.

(Isoindoline pigment (A1))
The isoindoline pigment (A1) of the present invention includes C.I. I. Pigment Yellow 109, 110, 139, 173, 185 and the like, preferably C.I. I. Pigment Yellow 139 and C.I. I. Pigment Yellow 185.

<Other colorants>
The coloring composition of the present invention may contain other coloring agents other than the isoindoline pigment (A1) as the coloring agent, and organic or inorganic pigments may be used alone or in combination of two or more. can. Among the pigments, pigments having high color development and high heat resistance are preferable, and organic pigments are usually used. Further, since the color is adjusted, the dye can be contained within a range that does not reduce the heat resistance. Specific examples of organic pigments that can be used in the coloring composition of the present invention are shown below by color index numbers.

Specifically, as these organic pigments, as red pigments, for example, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151 , 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208 , 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254. , 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276 and the like. Examples of the orange pigment that works in the same manner as the red pigment include C.I. I. Pigment Orange 36, 38, 43, 51, 55, 59, 61 and other orange pigments can be used. Among these, from the viewpoint of obtaining high coloring power, C.I. I. Pigment Red 254, C.I. I. It is particularly preferred to use Pigment Red 177.

Examples of the blue pigment include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like can be mentioned. Among these, from the viewpoint of obtaining high coloring power, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, or 15: 6, more preferably C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 6.

Examples of the green pigment include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 or 58 or JP 2011-57910 Examples thereof include aluminum phthalocyanine pigments described in Japanese Patent Application Laid-Open No. 2006-290982 and the like. Among these, from the viewpoint of obtaining high coloring power, C.I. I. Pigment Green 7, 36 or 58.

Examples of the yellow pigment include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1,37,37: 1,40,41,42,43,48,53,55,61,62,62: 1,63,65,73,74,75,81,83,87,93,94, 95, 97, 100, 101, 104, 105, 108, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 174, 175, 176, 180, 181. 182, 183, 184, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208 and , A quinophthalone compound described in JP-A-2012-226110, etc. can be mentioned. Among these, from the viewpoint of obtaining high coloring power, C.I. I. Pigment Yellow 83, 117, 129, 138, 150, 154, 155, or 180, more preferably C.I. I. Pigment Yellow 83, 138, or 150.

Examples of the purple pigment include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like can be mentioned. Among these, from the viewpoint of obtaining high coloring power, C.I. I. Pigment Violet 19 or 23, more preferably C.I. I. Pigment Violet 23.

Inorganic pigments include barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, dark blue, chromium oxide green, cobalt green, amber, and titanium black. , Synthetic iron black, titanium oxide, metal oxide powder such as iron tetroxide, metal sulfide powder, metal powder and the like. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability, etc. while balancing saturation and lightness.

The coloring composition of the present application preferably further contains at least one colorant selected from the group consisting of diketopyrrolopyrrole pigments (A2) and halogenated phthalocyanine pigments (A3).

(Diketopyrrolopyrrole pigment (A2))
The diketopyrrolopyrrole pigment (A2) of the present invention includes C.I. I. Pigment Red 254, 255, 264, or 272, or C.I. I. Pigment Orange 71, 73, 81 and the like. Further, the brominated diketopyrrolopyrrole pigment described in JP-A-2011-523433 can also be preferably used. Particularly preferably C.I. I. Pigment Red 254.

(Halogenated phthalocyanine pigment (A3))
The halogenated phthalocyanine pigment (A3) of the present invention includes C.I. I. Examples thereof include aluminum phthalocyanine pigments described in Pigment Green 7, 10, 36, 37, 58, JP 2011-57910, JP 2006-290982 and the like. Particularly preferably C.I. I. Pigment greens 36 and 58.

The content of the colorant (A) of the present invention in the total solid content is preferably 45% by mass to 70% by mass, more preferably 45% by mass to 65% by mass, and further preferably 45 to 55% by mass. It is mass%. When the isoindoline pigment (A1) and the diketopyrrolopyrrole pigment (A2) are used in combination, the pigment ratio is preferably 10 to 30/70 to 90. When the isoindoline pigment (A1) and the halogenated phthalocyanine pigment (A3) are used in combination, the pigment ratio is preferably 20 to 50/50 to 80.

<Binder resin (B)>
The vanider resin (B) of the present invention has a weight average molecular weight of 25,000 to 50,000, and (c) is reacted with a copolymer obtained by copolymerizing the following (a) and (b). It is a resin containing a resin (B1) obtained by reacting (d) with the resin (B1).
(A): Cyclic ether skeleton having 2 to 4 carbon atoms and monomer having ethylenically unsaturated bond (b): Having an unsaturated bond copolymerizable with (a), what is (a-1)? Different monomer (c): At least one selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (d): Polybasic acid anhydride

[(A): Monomer having a cyclic ether skeleton having 2 to 4 carbon atoms and an ethylenically unsaturated bond]
Examples of (a) include a monomer having an oxylanyl group and an ethylenically unsaturated bond (aX), a monomer having an oxetanyl group and an ethylenically unsaturated bond (aY), a tetrahydrofuryl group and the like. Examples thereof include a monomer having an ethylenically unsaturated bond (aZ).

(Monomer having an oxylanyl group and an ethylenically unsaturated bond (aX))
Examples of (aX) include a monomer (a-1) having an epoxidized chain olefin and an ethylenically unsaturated bond, and an epoxidized cycloalkene structure and an ethylenically unsaturated bond. The monomer (a-2) having the above is mentioned.
As (aX), a monomer having an oxylanyl group and a (meth) acryloyloxy group is preferable, and (a-2) having a (meth) acryloyloxy group is more preferable.

Specific examples of (a-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, and m-vinyl. Benzyl 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 (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris ( Glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2, Examples thereof include 4,6-tris (glycidyloxymethyl) styrene, and the compounds described in JP-A-7-248625.

Examples of (a-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, celloxide 2000; manufactured by Daicel Chemical Industries, Ltd.), and 3,4-epoxycyclohexylmethyl acrylate (for example, cyclos). Ma A400; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, cyclomer M100; manufactured by Daicel Chemical Industry Co., Ltd.), a compound represented by the formula (I), the compound represented by the formula (II). ), And the like.

[In formulas (I) and (II), R ¹ and R ² independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is replaced with a hydroxy group. It may have been. X ¹ and X ² independently represent a single bond, -R ^3- , * ^{-R 3-} O-, * -R ^3- S-, * -R ^3- NH-. R ³ represents an alkanediyl group having 1 to 6 carbon atoms. * Represents a bond with O. ]

Specific examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and the like. The alkyl groups substituted with hydroxy groups include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group and 1-hydroxy-1. -Methyl ethyl group, 2-hydroxy-1-methyl ethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like can be mentioned.

Examples of R ¹ and R ² include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

The alkanediyl group includes a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-. Examples include 1,6-diyl group.

The X ¹ and X ² are preferably a single bond, a methylene group, an ethylene group, a * -CH _2- O- (* represents a bond with O) group, and a * -CH ₂ CH _2- O- group. More preferably, a single bond, * -CH ₂ CH _2- O- group can be mentioned.

Examples of the compound represented by the formula (I) include compounds represented by the formulas (I-1) to (I-15). Preferably, Formula (I-1), Formula (I-3), Formula (I-5), Formula (I-7), Formula (I-9), Formulas (I-11) to Formulas (I-15). A compound represented by any of the above can be mentioned. More preferably, a compound represented by any one of the formula (I-1), the formula (I-7), the formula (I-9) and the formula (I-15) can be mentioned.

Examples of the compound represented by the formula (II) include compounds represented by the formulas (II-1) to (II-15). Preferably, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), formula (II-11) to formula (II-15). A compound represented by any of the above can be mentioned. More preferably, a compound represented by any one of the formula (II-1), the formula (II-7), the formula (II-9) and the formula (II-15) can be mentioned.

The compound represented by the formula (I) and the compound represented by the formula (II) can be used independently. Also, they can be mixed in any ratio. When mixed, the mixing ratio is a molar ratio, preferably of formula (I): formula (II), 5:95 to 95: 5, more preferably 10:90 to 90:10, particularly preferably 20:80. ~ 80:20.

(Monomer having an oxetanyl group and an ethylenically unsaturated bond (aY))
As (aY), a monomer having an oxetanyl group and a (meth) acryloyloxy group is preferable. Examples of (a-Y) include 3-methyl-3- (meth) acryloyloxymethyloxetane, 3-ethyl-3- (meth) acryloyloxymethyloxetane, and 3-methyl-3- (meth) acryloyloxyethyl. Examples thereof include oxetane and 3-ethyl-3- (meth) acryloyloxyethyl oxetane.

(Monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond (aZ))
As (aZ), a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specific examples of (aZ) include tetrahydrofurfuryl acrylate (for example, Viscort V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate and the like.

[(B): Monomer different from (a-1) having an unsaturated bond copolymerizable with (a)]
Examples of (b) include (meth) acrylic acids such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, and tert-butyl (meth) acrylate. Alkyl esters;
(Meta) acrylic acid cyclic alkyl esters such as cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate Kind;

Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate or aralkyl esters; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconic acid; 2-hydroxyethyl (meth) acrylate, Hydroxyalkyl esters such as 2-hydroxypropyl (meth) acrylate;

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, 5,6-di (hydroxymethyl) bicyclo [2.2.1] Hept-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2. 1] Hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy -5-Methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2] .2.1] Hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-Phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyl) Bicyclounsaturated compounds such as oxycarbonyl) bicyclo [2.2.1] hept-2-ene;

N-Phenylmaleimide, N-Cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Further, as (b), a compound (b1) having at least one skeleton selected from the group consisting of a tricyclodecane skeleton and a tricyclodecene skeleton and an ethylenically unsaturated bond (hereinafter referred to as “(b1)”). In some cases).
When (b) is (b1), the film loss of the pattern due to development can be suppressed. Here, the "tricyclodecane skeleton" and the "tricyclodecene skeleton" in the present specification refer to the following structures (each having an arbitrary bond).

Specific examples of (b1) include dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate. ..

(B) can be used alone or in combination of two or more. When two or more types of (b) are used in combination, at least one type is preferably the above (b1), and the other one is the phenyl (meth) acrylate or benzyl (meth) acrylate in the above (b). Equal aralkyl esters (hereinafter, may be referred to as "(b2)")) are preferable.

In the copolymer obtained by copolymerizing (a), (b1) and (b2), the ratio of the structural units derived from each monomer copolymerizes (a), (b1) and (b2). It is preferable that it is in the following range with respect to the ratio of the copolymer obtained by the above.
Constituent unit derived from (a): 10 to 90 mol% (more preferably 30 to 80 mol%)
Constituent unit derived from (b1): 10 to 80 mol% (more preferably 10 to 60 mol%)
Constituent unit derived from (b2): 10 to 60 mol% (more preferably 10 to 40 mol%)
However, the total of (a), (b1) and (b2) shall be 100 mol% or less. When the composition ratio is in the above range, the curability tends to be better.

[(C): At least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides]
Specific examples of (c) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid, 1,4-cyclohexendicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] Bicyclounsaturated compounds containing a carboxy group such as hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride);

Unsaturated mono [(meth) acryloyloxyalkyl] esters of divalent or higher valent carboxylic acids such as monosuccinate [2- (meth) acryloyloxyethyl] and mono [2- (meth) acryloyloxyethyl] phthalates. Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used from the viewpoint of copolymerization reactivity and alkali solubility.

The amount of addition (c) is preferably 10 to 60% by mass, preferably 30 to 40% by mass, based on the charged value, with respect to the copolymer obtained by copolymerizing (a), (b1) and (b2). % Is more preferable.

[(D): Polybasic acid anhydride]
As (d), known ones can be used, and dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorendic anhydride; Examples thereof include polybasic acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, and biphenyltetracarboxylic acid anhydride. Of these, tetrahydrophthalic anhydride or succinic anhydride is preferable from the viewpoint of developability.

The addition reaction of (d) is carried out by a conventional method. The amount of (d) added is 5 to 100%, preferably 30 to 100%, of the hydroxyl groups generated when the photosensitive group is introduced. When the addition amount of (d) is less than 5%, the solubility in dilute alkali decreases.

The weight average molecular weight (Mw) of the binder resin (B1) of the present invention is in the range of 25,000 to 50,000, more preferably in the range of 25,000 to 40,000. By combining the isoindoline pigment (A1) and the binder resin (B) containing the specific binder resin (B1), discoloration does not occur even when immersed in an alkaline developer, and there is little residue. It is possible to provide a color filter having good developability and good resolution. If the molecular weight is less than 25,000, the developed pattern becomes small and the resolution becomes poor. In addition, discoloration occurs when immersed in an alkaline developer. If the molecular weight exceeds 50,000, the developability deteriorates. Further, when the isoindoline pigment (A1) is not used, the color does not fade even when immersed in an alkaline developer, but the resolution and developability are deteriorated.

As the binder resin (B), a resin other than the binder resin (B1) may be used in combination. Since the binder resin (B) has good film forming properties and various resistances, it is preferable to use the binder resin (B) in an amount of 20 parts by mass or more with respect to 100 parts by mass of the total weight of the colorant (A) by a photolithography process. Pattern shape of the formed color filter Since a good pattern can be obtained, it is more preferably 20 to 40 parts by mass.

<Polymerizable compound (C)>
(C) contains a monomer or oligomer that is cured by ultraviolet rays, heat, or the like to form a transparent resin, and these can be used alone or in combination of two or more. As for the blending amount of the monomer, the content of the coloring composition for a color filter in the total solid content is preferably 5% by mass to 20% by mass.

Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Pentaerythritol Tetra (Meta) Acrylate, 1,6-Hexanediol Diglycidyl Ether Di (Meta) Acrylate, Bisphenol A Diglycidyl Etherdi (Meta) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (Meta) acrylic acid ester, epoxy (meth) acrylate, various acrylic acid esters such as urethane acrylate and methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol tri Examples thereof include, but are not limited to, vinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, and acrylonitrile.
These polymerizable compounds (C) can be used alone or in admixture of two or more at any ratio, if necessary.

The content of the polymerizable compound (C) is preferably 10 to 50 parts by mass, and more preferably 10 to 30 parts by mass from the viewpoint of photocurability and developability, with respect to 100 parts by mass of the colorant. ..

In the coloring composition for a color filter of the present invention, the content of the polymerizable compound (C) with respect to the total solid content is preferably 5 to 20% by mass. Within the above range, a high-definition fine pixel pattern can be formed without the tapered portion of the pattern being stretched for a long time. In addition, good results can be obtained in terms of resolution and residue.

<Polymerization initiator (D)>
The colored composition of the present invention is prepared in the form of a solvent-developed or alkaline-developed colored resist material by adding a polymerization initiator or the like when the composition is cured by ultraviolet irradiation to form a filter segment by a photolithography method. can do. When the polymerization initiator (D) is used, the blending amount is preferably 0.5 to 200% by mass based on the total amount of the colorant, and 1 to 150% by mass from the viewpoint of photocurability and developability. Is more preferable.

Examples of the polymerization initiator (D) include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-Hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] Acetphenone compounds such as -1- [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one; benzoin , Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzoin compounds such as benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, 4-benzoyl- Benzopenone compounds such as 4'-methyldiphenylsulfide or 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2 , 4-Diisopropylthioxanthone, or thioxanthone compounds such as 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2, -(P-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4, 6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6-bis (trichloromethyl)- s-triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2, Triazine compounds such as 4-trichloromethyl- (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloki) Sim)], or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6) -Trimethylbenzoyl) phenylphosphine oxide, or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrene quinone, camphorquinone, ethylanthraquinone; borate compounds; A carbazole-based compound; an imidazole-based compound; or a titanosen-based compound or the like is used. Further, since the color image sensor is required to be thin, the pigment concentration in the solid content composition becomes high. Therefore, the polymerization initiator (D) is more preferably one having high sensitivity such as an oxime ester compound.

These polymerization initiators (D) can be used alone or in admixture of two or more at any ratio, if necessary.

In the coloring composition for a color filter of the present invention, in order to provide a color filter having a high development speed and a small amount of residue, the ratio I of the weight I of the polymerization initiator (D) to the weight M of the polymerizable compound (C) is I. / M is preferably 0.01 to 0.20, more preferably 0.05 to 0.10. When the I / M exceeds 0.20, the sensitivity becomes high and a large amount of residue is generated. When the I / M is less than 0.01, pattern peeling occurs due to a small amount of initiator.

<Sensitizer>
Further, the coloring composition of the present invention may contain a sensitizer. Examples of the sensitizer include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone derivatives. , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives and other polymethine dyes, acrydin derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indolin derivatives, Azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative , Naphthalocyanine derivative, Subphthalocyanine derivative, Pyrylium derivative, Thiopyrylium derivative, Tetraphyllin derivative, Anuren derivative, Spiropyran derivative, Spiroxazine derivative, Thiospiropirane derivative, Metal allene complex, Organic ruthenium complex, or Michler ketone derivative, α-Acyloxy ester , Acylphosphine oxide, methylphenylglioxylate, benzyl, 9,10-phenanthrene quinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalofenone, 3,3'or 4,4'- Examples thereof include tetra (t-butylperoxycarbonyl) benzophenone and 4,4'-diethylaminobenzophenone.

More specifically, Ogawara Nobu et al., "Dye Handbook" (1986, Kodansha), Ogawara Nobu et al., "Functional Dye Chemistry" (1981, CMC), Ikemori Chuzaburo et al., And " The sensitizers described in "Special Functional Materials" (1986, CMC) can be mentioned, but are not limited thereto. In addition, a sensitizer that absorbs light from the ultraviolet to the near infrared region can also be contained.

Two or more sensitizers may be used at an arbitrary ratio, if necessary. When the sensitizer is used, the blending amount is preferably 3 to 60% by mass, based on the total weight of the polymerization initiator (D) contained in the coloring composition (100% by mass), and is photocured. From the viewpoint of property and developability, it is more preferably 5 to 50% by mass.

<Solvent (E)>
The solvent (E) is contained in the coloring composition of the present invention in order to sufficiently disperse and permeate the coloring agent in the coloring agent carrier. Examples of the solvent (E) include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, and 1,4-. Dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexene-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3 -Methyl-1,3-butanol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene , M-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o- Diethyl benzene, o-dichlorobenzene, p-chlorotoluene, p-diethyl benzene, sec-butyl benzene, tert-butyl benzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether. , Ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotersial butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene Glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene Glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethylate , Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene Glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl Cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester and the like can be mentioned.

Among them, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate, and benzyl because the colorant of the present invention is well dispersed. It is preferable to use aromatic alcohols such as alcohol and ketones such as cyclohexanone.

As the solvent (E), one type can be used alone, or two or more types can be mixed and used. Further, since the solvent can adjust the coloring composition to an appropriate viscosity and form a filter segment having a desired uniform film thickness, 500 to 4000% by mass is based on the total weight of the coloring agent (100% by mass). It is preferable to use the amount of.

Other pigments such as the soindrin pigment (A1), the diketopyrrolopyrrole pigment (A2), and the halogenated phthalocyanine pigment (A3) contained in the colorant (A) have good dispersibility, coating uniformity, and storage. It is preferable to use a dye derivative and / or a dispersant in order to obtain a coloring composition having excellent stability and the like.

<Dye derivative>
Examples of the dye derivative include compounds in which an organic pigment, anthraquinone, acridone or triazine is introduced with a basic substituent, an acidic substituent, or a phthalimidemethyl group which may have a substituent. No. 63-305173, No. 57-15620, No. 59-40172, No. 63-17102, No. 5-9469, No. 2001-335717, No. 2003-2003. 128669, 2004-091497, 2007-156395, 2008-094873, 2008-094986, 2008-095007, 2008-195916 Those described in Japanese Patent Publication No. 4585781, etc. can be used, and these can be used alone or in combination of two or more kinds. When a dye derivative is used, one having a quinophthalone skeleton is preferable from the viewpoint of lightness and dispersibility.

Specific examples of the substituent of the dye derivative include groups represented by the following general formulas (2) to (5).

[In the general formulas (2) to (5),
X: _{Represents -SO 2-} , -CO-, -CH ₂ NHCOCH _2- , -CH _2- or direct binding.
represents an integer of n: 1-10.
R ₁ , R ₂ : independently, optionally substituted alkyl group, optionally substituted alkenyl group, optionally substituted phenyl group, or R ₁ and R ₂ integrated together. Represents a optionally substituted heterocycle containing nitrogen, oxygen or sulfur atoms. The alkyl group and alkenyl group preferably have 1 to 10 carbon atoms.
R ₃ : Represents an alkyl group which may be substituted, an alkenyl group which may be substituted, or a phenyl group which may be substituted. The alkyl group and alkenyl group preferably have 1 to 10 carbon atoms.
R ₄ , R ₅ , R ₆ , R ₇ : Independently represent a hydrogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, or a phenyl group which may be substituted. The alkyl group and alkenyl group preferably have 1 to 5 carbon atoms.
Y: -NR _8- Z-NR ₉ -or represents a direct bond.
R ₈ and R ₉ : independently represent a hydrogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, or a phenyl group which may be substituted. The alkyl group and alkenyl group preferably have 1 to 5 carbon atoms.
Z: Represents an optionally substituted alkylene group, an optionally substituted alkenylene group or an optionally substituted phenylene group. The alkyl group and alkenyl group preferably have 1 to 8 carbon atoms.
P: Represents a substituent represented by the general formula (6) or a substituent represented by the general formula (7).
Q: Represents a hydroxyl group, an alkoxyl group, a substituent represented by the general formula (6), or a substituent represented by the general formula (7). ]

[Substituents in the general formulas (6) and (7) are synonymous with the substituents in the general formulas (2) to (5). ]

Examples of the organic dye include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, and polyazo, phthalocyanine dyes, diaminodianthraquinone, anthraquinone, flavantron, anthraquinone, indantron, pyranthron, and biolantron. Anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindolin pigments, isoindolinone pigments, quinophthalone pigments, slene pigments, metal complex pigments, etc. .. Further, it may be a pigment used in a coloring composition for a color filter, which will be described later.

In addition, triazine is an alkyl group such as a methyl group or an ethyl group, an alkylamino group such as an amino group or a dimethylamino group, a diethylamino group or a dibutylamino group, a nitro group, a hydroxyl group or a methoxy group, an ethoxy group, an alkoxy such as a butoxy group. A phenyl group or a methyl group, an ethyl group, a methoxy group, an ethoxy group, an amino group, a dimethylamino group which may be substituted with a halogen or methyl group such as a group or chlorine, a methoxy group, an amino group, a dimethylamino group, a hydroxyl group or the like. , 1,3,5-triazine which may have a substituent such as a phenylamino group which may be substituted with a diethylamino group, a nitro group, a hydroxyl group or the like.

As specific examples of the dye derivatives, those shown in Tables 1 to 8 can be used, but the dye derivatives are not limited thereto. The dye derivative may be used alone or in combination of two or more.

When the coloring composition of the present invention contains two or more kinds of pigments, the coloring composition of the present invention mixes two or more kinds of pigments, and then the obtained pigment mixture is used as necessary for the above-mentioned dye derivative. At the same time, it can be produced by finely dispersing it in a pigment carrier by a known method. Further, the coloring composition of the present invention can also be produced by mixing each pigment separately finely dispersed in a pigment carrier.

Comparing the structure of the resin (B1) of the present invention with that of (meth) acrylic acid, the affinity between the basic derivative and the resin is high because the carboxylic acid is separated from the main chain. Therefore, by using the dye derivative of the present invention, the entanglement of the resin is reduced, the compatibility between the basic derivative and the resin is improved, and the developability and alkali resistance are improved.

From the viewpoint of improving the dispersibility of the colorant, the amount of the dye derivative to be blended is preferably 0.5% by mass or more, more preferably 1% by mass or more, most preferably based on the total amount of the added colorant (100% by mass). Is 3% by mass or more. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40% by mass or less, more preferably 35% by mass or less, based on the total amount of the added pigment (100% by mass).

<Dispersant>
The dispersant has a colorant-affinitive moiety having a property of adsorbing to the colorant and a moiety compatible with the colorant carrier, and adsorbs to the additive colorant to stabilize the dispersion on the colorant carrier. It works to do. Specific examples of the dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, and poly. Siloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by the reaction of poly (lower alkyleneimine) with polyester having a free carboxyl group, salts thereof, etc. Oil-based dispersants, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, water-soluble resins such as polyvinylpyrrolidone, etc. Water-soluble polymer compounds, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide-added compounds, phosphate ester-based, etc. are used, and these can be used alone or in admixture of two or more, but they are not always used. It is not limited to.

A polymer dispersant having a basic functional group is preferable because the viscosity of the dispersion becomes low and a high contrast is exhibited with a small amount of the dispersant added, and it is preferable for a nitrogen atom-containing graft copolymer or a side chain. Nitrogen atom-containing acrylic block copolymers and urethane polymer dispersants having a functional group containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocycle and the like are preferable. The resin type dispersant is preferably used in an amount of about 5 to 200% by mass with respect to the total amount of the pigment, and more preferably about 10 to 100% by mass from the viewpoint of film forming property.

Commercially available resin-type dispersants include Dsperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170 manufactured by Big Chemie Japan. , 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykuman, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, manufactured by Lubrizol Japan, Inc. 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., EFKA-46, 47, 48, 452 manufactured by BASF. 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540 , 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. Can be mentioned.

Further, as the dispersant of the present invention, a dispersant having an ester skeleton in the main chain and the side chain can also be used. Among them, a dispersant having an acidic group is preferable, and an acidic resin type dispersant having an aromatic carboxyl group is particularly preferable. Examples of such a resin-type dispersant include Patent No. 4020150, JP-A-2007-140487, International Publication No. 2007/007685, International Publication No. 2008/007776, JP-A-2010-163500 and JP-A-2010-163500. It is disclosed in Japanese Patent Publication No. 2010-223988 and the like, and exhibits excellent effects such as both fluidity and dispersibility. Of these, a dispersant obtained by reacting a polymer having a hydroxyl group at one end with an aromatic tricarboxylic acid anhydride and / or an aromatic tetracarboxylic dianhydride is most preferable.

<Thermosetting compound (F)>
The coloring composition of the present invention preferably further contains a thermosetting compound. When a color filter is produced using the coloring composition of the present invention, the inclusion of a thermosetting compound causes a reaction during firing of the filter segment to increase the crosslink density of the coating film, thereby improving the heat resistance of the filter segment. The effect of suppressing pigment aggregation during firing of the filter segment can be obtained.

Examples of the thermosetting compound include, but are limited to, epoxy compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. is not it. Epoxy compounds are preferred in the photosensitive coloring compositions of the present invention.

The epoxy compound may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of such epoxy compounds include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxy). Weight of benzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaaldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Condensates, phenols and polymers of various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadien, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), phenol Polycondensate of class and ketones (acetone, methylethyl ketone, methylisobutylketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzenedimethanol, α, α, α', α'-benzenedimethanol , Biphenyldimethanol, α, α, α', α'-biphenyldimethanol, etc.) and phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.) Examples thereof include polycondensates of bisphenols and various aldehydes, glycidyl ether-based epoxy resins obtained by glycidylizing alcohols, alicyclic epoxy resins, glycidylamine-based epoxy resins, glycidyl ester-based epoxy resins, and the like. However, the epoxy compound is not limited to these as long as it is a commonly used epoxy compound. These may be used alone or two or more kinds may be used.

Examples of commercially available products include Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P (trade names; manufactured by Yuka Shell Epoxy Co., Ltd.), Epicoat 1004, Epicoat 1256 (or more). Is a product name: Japan Epoxy Resin Co., Ltd., TECHMORE VG3101L (product name: Mitsui Chemicals Co., Ltd.), EPPN-501H, 502H (product name: Nippon Kayaku Co., Ltd.), JER 1032H60 (product name) ; Japan Epoxy Resin Co., Ltd.), JER 157S65, 157S70 (Product Name: Japan Epoxy Resin Co., Ltd.), EPPN-201 (Product Name: Nippon Kayaku Co., Ltd.), JER152, JER154 (The above are products) Name: Japan Epoxy Resin Co., Ltd., EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (the above are product names; manufactured by Nippon Kayaku Co., Ltd.), Serokiside 2021, EHPE-3150 (the above products) Name: Daicel Chemical Industry Co., Ltd.), Denacol EX-810, EX-830, EX-851, EX-611, EX-512, EX-421, EX-411, EX-321, EX-313, EX- 201, EX-111 (the above are trade names; manufactured by Nagase ChemteX Corporation) and the like can be mentioned, but the present invention is not limited thereto.

As melamine resin, Nicarac MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX- made by Sanwa Chemical Co., Ltd. Made by 750, MX-708, MX-706, MX-042, MX-035, MX-45, MX-500, MX-520, MX-43, MX-410, MX-302, and Nippon Cytec Industries. Examples include Cymel 300, 301, 303, 350, 232, 235, 236, 238, 506 and the like.
Examples of the benzoguanamine resin include Nicarac BX-4000, BX-37, BL-60 manufactured by Sanwa Chemical Co., Ltd., Super Beccamin TD-126 and 15-594 manufactured by DC Co., Ltd., and the like.

The blending amount of the thermosetting compound is preferably 0.5 to 20 parts by mass, and more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the colorant. If it is less than 0.5 parts by mass, the effect of improving solvent resistance is small, and if it is more than 20 parts by mass, a problem may occur when forming a filter segment by photolithography.

Further, the coloring composition of the present invention may contain a curing agent, a curing accelerator, or the like, if necessary, in order to assist the curing of the thermosetting compound. As the curing agent, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but the curing agent is not particularly limited thereto and can react with thermosetting compounds. Any curing agent may be used as long as it is used. Examples of the curing accelerator include amine compounds (eg, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivative bicyclic amidin compounds and salts thereof (eg, eg). Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- Ethyl-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), S-triazine derivatives (eg, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4) -Diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) Can be used. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the thermosetting compound.

<Leveling agent>
It is preferable to add a leveling agent to the coloring composition of the present invention in order to improve the leveling property of the composition on the transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure is preferable. Specific examples of the dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning Co., Ltd. and BYK-333 manufactured by Big Chemie Co., Ltd. Specific examples of dimethylsiloxane having a polyester structure include BYK-310 manufactured by Big Chemie. Dimethylsiloxane having a polyether structure and dimethylsiloxane having a polyester structure can also be used in combination. The content of the leveling agent is usually preferably 0.003 to 0.5% by mass based on the total weight of the photosensitive coloring composition (100% by mass).

A particularly preferable leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a hydrophilic group but has low solubility in water, and when added to a coloring composition, the same. It is useful to have a feature of low surface tension lowering ability and good wettability to the glass plate despite low surface tension lowering ability, and the amount of addition does not cause defects in the coating film due to foaming. Those capable of sufficiently suppressing chargeability can be preferably used. As a leveling agent having such preferable properties, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. The polyalkylene oxide unit includes a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the polyalkylene oxide unit is bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane. It may be any of the linear block copolymer types that are alternately and repeatedly bonded. Didimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. 2207, but is not limited to these.

Anionic, cationic, nonionic, or amphoteric surfactants can be added as an adjunct to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants to be added as an auxiliary to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalin sulfonate, and alkyldiphenyl ether disulfonic acid. Sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include ester.

Examples of the chaotic surfactant added as a supplement to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. Nonionic surfactants to be added as a supplement to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, and polyoxyethylene sorbitan monostearate. , Polyethylene glycol monolaurate and the like; alkyl betaines such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as alkylimidazoline, and fluorine-based and silicone-based surfactants.

Examples of the chaotic surfactant added as a supplement to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. Nonionic surfactants to be added as a supplement to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, and polyoxyethylene sorbitan monostearate. , Polyethylene glycol monolaurate and the like; alkyl betaines such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as alkylimidazoline, and fluorine-based and silicone-based surfactants.

<Manufacturing method of coloring composition>
The coloring composition of the present invention is a mixture of a colorant (A), a binder resin (B) and a solvent (E), and various dispersion means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor. Can be produced by finely dispersing using. Further, the coloring composition of the present invention can also be produced by separately mixing a coloring agent or the like finely dispersed in a binder resin and an organic solvent.

When the colorant having an average primary particle diameter of 100 nm or less is dispersed in a transparent resin using a disperser such as a sand mill in this way, it is in the state of dispersed particles composed of secondary particles in which a plurality of primary particles are gathered. As the dispersed state progresses, the dispersed particles gradually become smaller and eventually become dispersed in the state of primary particles, but the dispersed state is controlled by the size of the dispersed particles. The dispersed particles are dispersed so that the average diameter is within the range of 50 nm to 150 nm.

As the dispersion progresses, the dispersed particle size becomes smaller and the transparency increases. Therefore, the smaller the dispersed particle size is, the better. On the other hand, as the dispersion progresses and the dispersed particle size becomes smaller, the viscosity of the dispersion tends to increase and the thixotropic property tends to increase. When used as a coloring composition for a color filter, it is required to be thin-film coated and the surface of the coating film to be smooth, so that it is required to have a low viscosity and a Neutonian flow. Therefore, considering the viscosity and thixotropic property preferable for normal use, it is preferable to suppress the dispersed particle size to about 100 nm. In this way, by using a colorant having an average primary particle size of 100 nm or less and controlling the degree of dispersion so that the average particle size of the dispersed particles is within the range of 50 nm to 150 nm, the viscosity increase and thixotropic property are minimized. It is possible to obtain a pigment dispersion that is limited to a limit and has high transparency.

<Removal of coarse particles>
In the photosensitive coloring composition, it is preferable to disperse beads with zirconium oxide or inorganic glass in the manufacturing process, and beads having different diameters may be used at that time. Further, after carrying out the above-mentioned bead dispersion, coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0. It is preferable to remove coarse particles of 5 μm or more and mixed dust.

<Other additive ingredients>
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Further, an adhesion improver such as a silane coupling agent can be contained in order to improve the adhesion with the transparent substrate.

Examples of the storage stabilizer include quaternary ammonium chloride such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and phosphorous acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like. Examples thereof include organic phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 10% by mass based on the total amount of the colorant (100% by mass).

Adhesion improvers include vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, and β- (3, 4-Epylcyclohexyl) ethyltrimethoxysilane, β- (3,4-epylcyclohexyl) methyltrimethoxysilane, β- (3,4-epylcyclohexyl) ethyltriethoxysilane, β- (3,4-epylcyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino) Ethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysisilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-amino Examples thereof include aminosilanes such as propyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and silane coupling agents such as thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10% by mass, preferably 0.05 to 5% by mass, based on the total amount of the colorant in the coloring composition (100% by mass).

<Color filter>
Next, the color filter of the present invention will be described.
When used in a liquid crystal display device, the color filter of the present invention includes a filter segment formed from the coloring composition of the present invention on a substrate, and a general color filter has at least one red filter segment. , At least one green filter segment and at least one blue filter segment, or at least one magenta color filter segment, at least one cyan color filter segment, and at least one yellow color filter segment.

Each of the above filter segments can be formed by using a red coloring composition, a green coloring composition, a blue coloring composition, a yellow coloring composition, a magenta coloring composition, a cyan coloring composition, and the like. The coloring composition of the present application is preferably used for a red filter segment or a green filter segment. Further, the coloring composition forming each color filter segment can be formed by using each coloring composition containing each color pigment, the binder resin, the photopolymerizable composition and the like.

<Pigment forming red filter segment>
Examples of the red pigment for the red coloring composition forming the red filter segment include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 81: 2, 81: 3, 81: 4, 149, 166, 168, 176, 178, 179, 184, 185, 187, 200, 202, 208, 210, 221, 224, 242, 246, 254, 255, 264, 268, 269, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, the diketopyrrolopyrrole pigment described in JP 2011-523433, or the naphthol azo pigment described in JP2013-161025. Etc., but are not particularly limited to these.

Further, the red coloring composition includes C.I. I. Pigment Orange 43, 71, or 73 and other orange pigments and / or C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, Yellow pigments such as 193, 194, 198, 199, 213, or 214 can be used in combination.

<Pigment forming blue filter segment>
As a blue pigment for a blue coloring composition forming a blue filter segment,
C. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, JP-A-2004-333817, Alternatively, examples thereof include aluminum phthalocyanine pigments described in Japanese Patent No. 4893859, but the present invention is not particularly limited thereto. As the purple pigment, C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 and the like, but are not particularly limited thereto.

<Pigment forming green filter segment>
Examples of the green pigment for the blue coloring composition forming the green filter segment include C.I. I. Pigment Green 7, 10, 36, 37, 58 and other green pigments can be used. Further, for the green coloring composition, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, Yellow pigments such as 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221 can be used in combination.

<Pigment forming yellow filter segment>
Examples of the yellow pigment for the blue coloring composition forming the yellow filter segment include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, Yellow pigments such as 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221 can be used alone or in combination.

<Pigments that form magenta filter segments>
When forming a magenta color filter segment, for example, C.I. I. Pigment Violet 1, 19, C.I. I. Pigment Red 81, 122, 144, 146, 169, 177, 207 and the like, and examples thereof include, but are not limited to, purple pigments and red pigments.

<Pigment forming cyan filter segment>
Examples of the cyan coloring composition for forming the cyan filter segment include C.I. I. Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, 81 and other blue pigments can be used alone or in combination.

As the substrate, glass plates such as soda-lime glass, low-alkali borosilicate glass, and non-alkali aluminoborosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used. A transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate to drive the liquid crystal after the panel is formed. When used in a solid-state image sensor, a silicon wafer or the like is used, and the silicon wafer may be coated with a base material.

The dry film thickness of the filter segment is preferably 0.2 to 10 μm, more preferably 0.2 to 5 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate or the like may be used.

Each color filter segment is formed by the photolithography method by the following method. That is, the dry film thickness of the photosensitive coloring composition prepared as a solvent-developed or alkali-developed colored resist material is reduced to 0 by a coating method such as spray coating, spin coating, slit coating, or roll coating on a transparent substrate. Apply to a thickness of 2 to 10 μm. If necessary, the dried film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact with or without contact with the film. After that, the filter segment can be formed by immersing in a solvent or an alkaline developer, or by spraying the developer with a spray or the like to remove the uncured portion and form a desired pattern. Further, in order to promote the polymerization of the filter segments formed by the development, heating can be applied if necessary. According to the photolithography method, a filter segment having higher accuracy than the printing method can be formed.

At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide, tetramethylammonium hydroxide or the like is used as the alkaline developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developing solution. As the development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid filling) development method and the like can be applied.

In order to increase the UV exposure sensitivity, the photosensitive coloring composition is applied and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to prevent polymerization inhibition by oxygen. It is also possible to perform ultraviolet exposure after forming the above.

The color filter is bonded to the opposite substrate using a sealing agent, liquid crystal is injected from the injection port provided in the sealing portion, the injection port is sealed, and a polarizing film or a retardation film is placed on the outside of the substrate as necessary. A liquid crystal display panel is manufactured by laminating.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively. Further, "PGMAc" means propylene glycol monomethyl ether acetate.

(Weight average molecular weight of resin (Mw))
The weight average molecular weight (Mw) of the resin is polystyrene-equivalent measured using a TSKgel column (manufactured by Tosoh Corporation) and a GPC (manufactured by Tosoh Corporation, HLC-8120 GPC) equipped with an RI detector and using THF as a developing solvent. Weight average molecular weight (Mw).

<Dye derivative>

<Manufacturing of binder resin>
(Binder resin solution 1)
333 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, the atmosphere inside the flask was changed from air to nitrogen, and then the temperature was raised to 100 ° C. 70.5 g (0.40 mol) of benzyl methacrylate, 71.1 g (0.50 mol) of glycidyl methacrylate, 22.0 g (0.10 mol) of monomethacrylate of tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) ) And a solution prepared by adding 2.2 g of azobisisobutyronitrile to a mixture consisting of 164 g of propylene glycol monomethyl ether acetate was added dropwise to the flask over 2 hours from the dropping funnel, and the mixture was further stirred at 100 ° C. for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 43.0 g of methacrylic acid [0.5 mol, (100 mol% with respect to the glycidyl group of glycidyl methacrylate used in this reaction)], trisdimethylaminomethylphenol 0. 9 g and 0.145 g of hydroquinone were put into a flask, and the reaction was continued at 110 ° C. for 6 hours, and the reaction was terminated when the solid acid value reached 1 mgKOH / g. Next, 60.9 g (0.40 mol) of tetrahydrophthalic anhydride and 0.8 g of triethylamine were added and reacted at 120 ° C. for 3.5 hours to bring the solid content to 35.0% of propylene glycol monomethyl ether acetate. To obtain a binder resin solution 1 having an acid value of 80 mgKOH / g. The weight average molecular weight (Mw) was 40,000.

(Binder resin solution 2)
It was produced by the same method as the binder resin solution 1 except that the amount of azobisisobutyronitrile was changed to 2.9 g. The weight average molecular weight (Mw) of the obtained resin was 25,000.

(Binder resin solution 3)
It was produced by the same method as the binder resin solution 1 except that the amount of azobisisobutyronitrile was changed to 1.7 g. The weight average molecular weight (Mw) of the obtained resin was 50,000.

(Binder resin solution 4)
It was produced by the same method as the binder resin solution 1 except that the amount of azobisisobutyronitrile was changed to 3.2 g. The weight average molecular weight (Mw) of the obtained resin was 20,000.

(Binder resin solution 5)
It was produced by the same method as the binder resin solution 1 except that the amount of azobisisobutyronitrile was changed to 1.4 g. The weight average molecular weight (Mw) of the obtained resin was 55,000.

(Binder resin solution 6)
182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, the atmosphere inside the flask was changed from air to nitrogen, and then the temperature was raised to 100 ° C. 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, monomethacrylate of tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) 22.0 g (0.10 mol) ) And 136 g of propylene glycol monomethyl ether acetate to which 3.6 g of azobisisobutyronitrile was added was added dropwise to the flask over 2 hours from the dropping funnel, and the mixture was further stirred at 100 ° C. for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 g of glycidyl methacrylate [0.25 mol, (50 mol% with respect to the carboxyl group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol 0. 9 g and 0.145 g of hydroquinone were put into a flask, and the reaction was continued at 110 ° C. for 6 hours to adjust the solid content to 35.0% with propylene glycol monomethyl ether acetate, and the acid value was 79 mgKOH / g. Binder resin solution 6 was obtained. The weight average molecular weight (Mw) was 13,000, and the molecular weight distribution (Mw / Mn) was 2.1.

(Binder resin solution 7)
Put 570 parts of cyclohexanone in the reaction vessel and heat to 80 ° C. while injecting nitrogen gas into the vessel. At the same temperature, 23.0 parts of methacrylic acid, 23.0 parts of methyl methacrylate, 35.0 parts of benzyl methacrylate, and paracumyl. A mixture of 22.0 parts of phenolethylene oxide-modified acrylate (“Aronix M110” manufactured by Toa Synthetic Co., Ltd.), 48.0 parts of glycerol monomethacrylate, and 3.0 parts of 2,2′-azobisisobutyronitrile over 1 hour. The mixture was added dropwise to carry out a polymerization reaction. After completion of the dropping, the mixture was further reacted at 80 ° C. for 3 hours, then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour to be transparent. A resin copolymer solution was obtained.
Next, with respect to 336 parts of the obtained transparent resin copolymer solution, a mixture of 33.0 parts of 2-methacryloylethyl isocyanate, 0.4 parts of dibutyltin laurate and 130.0 parts of cyclohexanone was added at 70 ° C. to 3 parts. It was added dropwise over time to obtain a photosensitive transparent resin solution. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and the non-volatile content becomes 20% by weight in the previously synthesized photosensitive transparent resin solution. As described above, cyclohexanone was added to prepare a photosensitive resin solution. The acid value of the obtained binder resin solution 7 was 65 mgKOH / g, and the weight average molecular weight Mw was 32,000.

(Binder resin solution 8)
70.0 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable 4-neck flask, the temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then a dropping tube was used. 11.3 parts of n-butyl methacrylate, 6.1 parts of methacrylic acid, 4.3 parts of 2-hydroxyethyl methacrylate, 7.4 parts of paracumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toa Synthetic Co., Ltd.) ( A mixture of 0.4 parts of 2,2'-azobisisobutyronitrile having a weight ratio of 38.3 / 20.7 / 16.0 / 25.0) was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin having an acid value of 135 mgKOH / g and a weight average molecular weight (Mw) of 26,000. After cooling to room temperature, about 2 g of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monoethyl is prepared so that the non-volatile content is 20% by weight in the previously synthesized resin solution. Ether acetate was added to prepare a binder resin solution 8.

<Manufacturing of dispersant>
(Dispersant 1)
5.0 parts of methyl methacrylate, 55.0 parts of methacrylic acid, and 40.0 parts of ethyl acrylate were charged in a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, and replaced with nitrogen gas. The inside of the reaction vessel is heated to 80 ° C. to dissolve 0.1 part of 2,2'-azobisisobutyronitrile in 6.0 parts of 3-mercapto-1,2-propanediol and 45.3 parts of cyclohexanone. The solution was added and reacted for 10 hours. It was confirmed by solid content measurement that 95% had reacted. At this time, the weight average molecular weight was 4,000. Next, 8.8 parts of 1,2,3,4-butanetetracarboxylic dianhydride, 69.2 parts of cyclohexanone, and 1,8-diazabicyclo- [5.4.0] -7-undecene 0 as a catalyst. .2 parts were added and reacted at 120 ° C. for 7 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. After completion of the reaction, propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc) was added so that the non-volatile content was 50% by mass, and a solution of dispersant 1 having an aromatic carboxyl group was obtained.

(Dispersant 2)
A methoxypropyl acetate solution (nonvolatile content: 50% by mass) of the dispersant 2 having an aromatic carboxyl group was obtained in the same manner as in the dispersant 1 except that the raw materials and the charged amounts shown in Table 9 were used.

The abbreviations in Table 9 are shown below.
[Ethylene unsaturated monomer]
-MAA: Methacrylic acid-MMA: Methyl methacrylate-EA: Ethyl acrylate-t-BMA: tert-Butyl acrylate [Radical polymerization initiator]
-AIBN: 2,2'-azobisisobutyronitrile [organic solvent]
・ PGMAc
[Tetracarboxylic dianhydride]
Rika Co., Ltd.)
-PMA: Pyromellitic acid dianhydride (manufactured by Daicel Chemical Industries, Ltd.)
・ DBU: 1,8-diazabicyclo- [5.4.0] -7-Undesen (manufactured by Sun Appro Co., Ltd.)

<Manufacturing of isoindoline pigment (A1)>
(Isoindoline pigment (A1-1))
C. I. 100 parts of Pigment Yellow 139 (PY139) (BASF's "Irgafore Yellow 2R-CF"), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), and 6 at 70 ° C. Time kneaded. This kneaded product was put into 3000 parts of warm water and stirred for 1 hour while heating at 70 ° C. to form a slurry, which was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours, 98. A portion of the isoindoline pigment (A1-1) was obtained.

(Isoindoline pigment (A1-2))
C. I. 100 parts of Pigment Yellow 185 (PY185) (“PALIOTOL YELLOW D1155” manufactured by BASF Ltd.), 700 parts of sodium chloride, and 180 parts of diethylene glycol are charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) for 6 hours at 80 ° C. Kneaded. This mixture was poured into 2000 parts of warm water, stirred for 1 hour while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then dried at 80 ° C. for 24 hours and 95 parts of iso. Indoline pigment (A1-2) was obtained.

<Manufacturing of diketopyrrolopyrrole pigment (A2)>
(Diketopyrrolopyrrole pigment (A2-1))
C. I. Pigment Red 254 (PR254) (BASF's "Irgafore Red B-CF"), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and 6 at 60 ° C. It was kneaded for a long time and treated with salt milling. The obtained kneaded product was put into 3000 parts of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. , 98 parts of diketopyrrolopyrrole pigment (A2-1) was obtained.

<Manufacturing method of pigment dispersion>
(Pigment dispersion P-1)
The mixture having the following composition was uniformly stirred and mixed, dispersed with an Eiger mill for 4 hours using zirconia beads having a diameter of 0.8 mm, and then filtered through a 5 μm filter to prepare an isoindoline pigment dispersion P-1. ..
Isoindoline pigment (A1-1): 15.0 parts BYK-111: 5.0 parts PGMAc: 80.0 parts

(Pigment dispersions 2-11)
Pigment dispersions P2-9 were obtained in the same manner as the pigment dispersion P-1 except that the formulations shown in Table 10 were changed.

The abbreviations in Table 10 are shown below.
BYK-111: Acid group-containing dispersant (“DISPERBYK-111” manufactured by Big Chemie)
BYK-174: Dispersant for acid group-containing high molecular weight block copolymer ("DISPERBYK-174" manufactured by BIC Chemie)
BYK-2150: Dispersant for basic group-containing block copolymer ("DISPERBYK-2150" manufactured by Big Chemie)
BYK-2000: Dispersant for basic group-containing acrylic polymer ("DISPERBYK-2000" manufactured by Big Chemie)
EFKA-4300: Dispersant for basic group-containing acrylic block copolymer (BASF "Efka 4300")

Isoindoline pigment (A1-1): C.I. I. Pigment Yellow 139
Isoindoline pigment (A1-2): C.I. I. Pigment Yellow 185
Diketopyrrolopyrrole pigment (A2-1): C.I. I. Pigment Red 254
Halogenated phthalocyanine pigment (A3-1): C.I. I. Pigment Green 36
Halogenated phthalocyanine pigment (A3-2): C.I. I. Pigment Green 58
Kinoftalone pigment (AX-1): C.I. I. Pigment Yellow 138

<Manufacturing of coloring compositions for color filters>
[Example 1]
(Coloring composition for color filter)
After stirring and mixing the following mixture so as to be uniform, 1. Filtration with a 0 μm filter was performed to obtain a coloring composition for a color filter.
Pigment dispersion 1: 54.97 parts Binder resin solution 1: 9.30 parts Thermosetting compound: 0.40 parts ("EHPE3150" manufactured by Daicel Chemical Industries, Ltd .: 2,2-bis (hydroxymethyl) -1-butanol 1,2-Epoxy-4- (2-oxylanyl) cyclohexane adduct, epoxy compound)
Polymerizable compound ("Aronix M-402" manufactured by Toa Synthetic Co., Ltd .: dipentaerythritol hexaacrylate): 0.91 part ("Aronix M-309" manufactured by Toa Synthetic Co., Ltd .: trimethylolpropane triacrylate): 0.91 part Oxime Ester-based photopolymerization initiator: 0.51 part (BASF "OXE-01": 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)])
PGMAc: 33.00 copies

[Examples 2-26, Comparative Examples 1-6]
Hereinafter, the composition and the blending amount were changed to those shown in Table 11 to obtain a coloring composition for a color filter in the same manner as in Example 1.

The abbreviations in Table 11 are shown below.
EHPE3150: "EHPE3150" manufactured by Daicel Chemical Industries, 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, epoxy compound M-402: Toagosei Co., Ltd. "Aronix M-402" manufactured by Dipentaerythritol hexaacrylate M-309: "Aronix M-309" manufactured by Toagosei Co., Ltd., trimethylolpropane triacrylate)
M-350: "Aronix M-350" manufactured by Toagosei Co., Ltd., trimethylolpropane EO-modified triacrylate)
OXE-01: BASF's "OXE-01", 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)])
PGMAc: Propylene glycol monomethyl ether acetate

<Evaluation of coloring composition for color filter>
The obtained coloring composition for a color filter was tested for alkali developer resistance, developability, residue and dimensions by the following methods. The results are shown in Table 12. ⊚ is a very good level, ◯ is a good level, Δ is a practical level, and × is a level unsuitable for practical use.

(Alkaline developer resistance)
The obtained coloring composition for a color filter was rotationally coated on a glass substrate using a spin coater so that the dry film thickness was 0.9 μm, and dried at 70 ° C. for 20 minutes. Next, the dried coating film was exposed to ^{200 mJ / cm 2} with an ultra-high pressure mercury lamp ^{having an i-line illuminance of 30 mW / cm 2} through a photomask in which a 6 μm square pattern mask pattern was arranged. The pattern-exposed coating film was washed with pure water after developing an unexposed portion using a 2% by mass potassium hydroxide aqueous solution. Then, the water droplets were blown off with high-pressure air, the substrate was naturally dried, and the substrate was post-baked on a hot plate at 170 ° C. for 10 minutes to form a pattern on the glass substrate. The spectral transmittance of the patterned portion of the glass substrate was measured using a microscopic photometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). Then, TMAH (tetramethylammonium hydroxide) was immersed in an aqueous solution dissolved in water at a concentration of 1.0% by weight to promote the spectral transmittance again. The change in transmittance at 400 nm before and after immersion in the TMAH aqueous solution was evaluated. The evaluation ranks are as follows.
⊚: less than 0.5% 〇: 0.5% or more, less than 1.0% Δ: 1.0% or more, less than 5.0% ×: 5.0% or more

(Developability)
The obtained coloring composition for a color filter was rotationally coated on a glass substrate using a spin coater so that the dry film thickness was 0.9 μm, and dried at 70 ° C. for 20 minutes. 2 ml of a 2 mass% potassium hydroxide aqueous solution was added dropwise to the coating film, and the time until the coating thickness was dissolved and disappeared was measured to evaluate the developing speed of the coloring composition. The evaluation ranks are as follows.
⊚: less than 10 seconds 〇: 10 seconds or more, less than 15 seconds Δ: 15 seconds or more, less than 30 seconds ×: 30 seconds or more

(Residue)
A resist solution for a flattening film (HL-18s: manufactured by Nippon Steel Chemical Co., Ltd.) was applied onto a 6-inch silicon wafer by a spin coating method, and heat-treated on a hot plate at 100 ° C. for 6 minutes as a prebake. Further, the coating film was cured in an oven at 170 ° C. for 1 hour to form a 1.0 μm flattening film, and a wafer with the flattening film was obtained. Next, the obtained resist material was applied onto a silicon wafer with a flattening film with a spin coater, and heat-treated on a hot plate at 100 ° C. for 1 minute as a prebake. The film thickness after prebaking was adjusted to 0.9 μm. Then, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), pattern exposure at ^{1000 to 5000 J / m 2 is performed through a photomask for forming 1.0 μm square pixels at a wavelength of 365 nm.} Was done. The coating film after exposure was paddle-developed with an organic alkaline developer for 1 minute. After the paddle was developed, it was rinsed with pure water in a spin shower for 20 seconds, and then washed with pure water for 20 seconds. After that, the water droplets remaining on the wafer are blown off with high-pressure air, the substrate is naturally dried, a square pixel pattern is formed, and the surface of the unexposed part washed away by development is surfaced with a scanning electron microscope (Hitachi High-Tech Corporation "S". -3000N ") was used for observation, and the alkali developability was determined by the presence or absence of a residue.
◯: No residue in 1 minute of development time Δ: Slight residue in 1 minute of development time ×: Residue in 1 minute of development time

(Resolution)
A test substrate was prepared by the same procedure as the above-mentioned developability test, and the pattern size of 1.0 μm square in the resist pattern after development was observed using a scanning electron microscope (“S-3000N” manufactured by Hitachi High-Tech). , Evaluated on a 3-point scale based on the following criteria.
◯: Pattern size is 0.9 μm or more and less than 1.4 μm Δ: Pattern size is 1.4 μm or more and less than 3.0 μm ×: Pattern size is 3.0 μm or more

The coating film obtained with the coloring composition for a color filter of the example was good in all of alkali developer resistance, developability, residue and dimensions. In particular, a diketopyrrolopyrrole pigment (A2), an epoxy resin and a resin 1 having a molecular weight of 40,000 are used, and the content of the colorant (A) in the total solid content is 48.5%, which is the total solid. Examples 2 to 7, 9, 13 to 14 and 20 in which the content of the polymerizable compound (C) in the minutes was 10.7% were good. Further, all of Examples 15 to 16 using the halogenated phthalocyanine pigment (A3) were equivalent to those of Example 2. Example 1 composed of only the isoindoline pigment (A1) had a practical level of alkali developer resistance as compared with Example 2, but the result was inferior. Example 10 using the resin 2 having a molecular weight of 25,000 had a practical level of alkali developer resistance as compared with Example 2, but the result was inferior. In Examples 8, 12 and 17 in which no derivative was used, the alkaline developer resistance and developability were inferior to those in Example 2, although they were at a practical level. Example 11 using the resin 3 having a molecular weight of 50,000 was inferior to Example 2 in terms of developability and residue at a practical level. Example 22, in which the amount of the polymerizable compound (C) / solid content was 5.0% as compared with Example 2, the alkaline developer resistance was at a practical level, but the result was inferior. The result of Example 24, in which the amount of the polymerizable compound (C) / solid content was 4.0%, which was further smaller than that of Example 2, was further inferior. In Example 23, in which the amount of the polymerizable compound (C) / solid content was 20.0% as compared with Example 2, the alkali developer resistance was at a practical level, but the result was inferior. Although the amount of the polymerizable compound (C) / solid content is 25.0%, which is higher than that of Example 2, the alkali developer resistance and resolution of Example 25 are at a practical level as compared with Example 2. The result was inferior. Compared to Example 18, the content of the colorant (A) in the total solid content is 64.0%. In Example 19, the alkali developer resistance and developability are at a practical level as compared with Example 18. Some results were inferior. Example 21, in which the content of the colorant (A) in the total solid content is 67.0%, which is higher than that in Example 18, is inferior in alkaline developer resistance, developability and residue at a practical level. It became. In Example 20, the content of the colorant (A) in the total solid content was 40.0%, which was smaller than that in Example 18, although the resolution was at a practical level, the result was inferior. In Example 26 to which no epoxy resin was added, the alkali developer resistance was inferior to that in Example 2, although the resistance to the alkaline developer was at a practical level.

In Comparative Example 1, since the binder resin 4 having a molecular weight of less than 25,000 was used, the resistance to the alkaline developer was poor. In Comparative Example 2, since the binder resin 5 having a molecular weight of 55,000 was used, the resistance to the alkaline developer was good, but the developability and the residue were poor. In Comparative Examples 3 to 5, since the binder resin specified in the present application was not used, the alkali developer resistance was poor. Comparative Example 5 also had poor developability. In Comparative Example 6, since a pigment other than the isoindoline-based pigment was used, a residue was generated. In addition, resolution was not possible unless the dimensions were 3.0 μm or more.

From the above results, the colorant (A) contains at least the isoindoline pigment (A1), the binder resin (B) has a weight average molecular weight of 25,000 to 50,000, and the above-mentioned (a). The coloring composition for a color filter, which is a specific resin obtained by reacting the copolymer of) and (b) with (c) and then (d), is excellent in alkali developer resistance, developability, and residue, and is good. Dimensions can be obtained.
Further, by using the coloring composition for a color filter of the present invention, it was possible to produce a color filter having excellent alkali developer resistance, developability and residue, and having good dimensions.

Claims (8)

A coloring composition for a color filter containing a colorant (A), a binder resin (B), a polymerizable compound (C), a polymerization initiator (D) and a solvent (E).
The colorant (A) contains at least an isoindoline pigment (A1), and the colorant (A) contains at least an isoindoline pigment (A1).
The binder resin (B), the weight average molecular weight 25,000～50,000 and the copolymer below the (a) and (b), made by reacting (c) then (d) Contains resin (B1) ,
The isoindoline pigment (A1) is C.I. I. Pigment Yellow 139 and C.I. I. A coloring composition for a color filter, which comprises at least one selected from the group consisting of Pigment Yellow 185.
(A): A monomer having a cyclic ether skeleton having 2 to 4 carbon atoms and an ethylenically unsaturated bond (b): It has an unsaturated bond copolymerizable with (a) and is different from (a). Quantum (c): At least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (d): Polybasic acid anhydrides The coloring composition for a color filter according to claim 1, wherein the coloring agent further comprises at least one selected from the group consisting of a diketopyrrolopyrrole pigment (A2) and a halogenated phthalocyanine pigment (A3). The coloring composition for a color filter according to claim 1 or 2 , wherein the content of the colorant (A) in the total solid content is 45% by mass to 65% by mass. The coloring composition for a color filter according to any one of claims 1 to 3 , wherein the content of the polymerizable compound (C) in the total solid content is 5% by mass to 20% by mass. The coloring composition for a color filter according to any one of claims 1 to 4 , wherein the polymerization initiator (D) contains an oxime ester-based photopolymerization initiator. The coloring composition for a color filter according to any one of claims 1 to 5 , further comprising a thermosetting compound (F). The coloring composition for a color filter according to claim 6 , wherein the thermosetting compound (F) is an epoxy compound. A color filter formed by using the coloring composition for a color filter according to any one of claims 1 to 7.