JP2018105911A - Coloring composition for color filters and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition for color filters having few development residues and excellent color separability, and a color filter prepared therewith.SOLUTION: A coloring composition for color filters contains a colorant (A), a binder resin (B) with an acid value of 70-200 mgKOH/g or less, a polymerizable compound having an acidic group (C1) or a polyfunctional photocurable compound having an alkyleneoxy group having 2 or more carbon atoms (C2), a polymerization initiator (D), and a solvent (E).SELECTED DRAWING: None

Description

  The present invention relates to a color filter mounted on a solid-state imaging device represented by a color liquid crystal display device, a C-MOS (Complementary Metal Oxide Semiconductor), a CCD (Charge Coupled Device), and the like. About.

A color filter used in a color liquid crystal display device is arranged on a transparent substrate such as a glass substrate so that two or more kinds of fine band-like filter segments having different hues are parallel (stripe-shaped) or cross each other. Or two or more kinds of fine filter segments having different hues are arranged in order in each of the vertical and horizontal directions. The filter segments have small dimensions of several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.
In addition, solid-state image sensors such as C-MOS and CCD each have a color filter provided with additive mixed primary color filter segments such as blue, green, red, magenta, cyan, and yellow on the light receiving element. Generally, color separation is performed. In recent years, both the color liquid crystal display device and the solid-state image sensor have a tendency to reduce the area per pixel due to the increase in the number of pixels. As a result, it is required to reduce the thickness of the color filter mounted on the image sensor and to increase the concentration of the coloring component.

  The color filter manufacturing method includes a dyeing method using a dye as a color material, a dye dispersion method, a pigment dispersion method using a pigment as a color material, a printing method, and an electrodeposition method. Among these, the dyeing method or the dyeing and dispersing method has a disadvantage that the heat resistance and the light resistance are slightly inferior because the dye is a dye. Therefore, a pigment having excellent heat resistance and light resistance is used as the color material of the color filter, and the pigment dispersion method is often used as the manufacturing method because of the accuracy and stability of the forming method.

  In the pigment dispersion method, a color resist is formed by mixing and blending a photosensitive agent or an additive in a pigment in which pigment particles, which are pigments, are dispersed in a transparent resin, and this color resist is applied onto a substrate by a coating device such as a spin coater. In this method, a color filter is produced by forming a coating film by the above, performing selective exposure through a mask with an aligner or a stepper, patterning by alkali development and thermosetting, and repeating this operation.

  In recent years, there has been an increasing demand for color characteristics for color filters, such as transmittance, brightness, color purity, coating uniformity when forming filter segments, sensitivity, developability, and pattern shape. Especially for color filters used in solid-state image sensors used in video cameras, digital cameras, color scanners, etc., high definition, high brightness, and high color reproducibility are required, and the transmittance is high. There is a need for a color filter having excellent color reproducibility and color separation.

JP 2006-267992 A JP 2008-040404 A JP 2006-104243 A JP 2008-038061 A JP 2007-114604 A JP 2000-081508 A

  In addition, as the definition becomes higher, the pixel size of the color liquid crystal display device and the solid-state image sensor is also reduced. In order to achieve downsizing of pixels, the demand for developability is also increasing. Due to the poor developability, problems such as the generation of residue when a pixel pattern is created have also emerged. For example, Patent Documents 5 and 6 propose that a color filter with less development residue is formed by using a photosensitive composition using a copolymer containing a specific acrylic component as a resin component. However, these methods are not sufficient at present.

  Therefore, the present invention makes it possible to control the spectral characteristics required for a color filter by using a specific pigment, binder resin, polymerizable compound, polymerization initiator, etc. An object is to provide an excellent coloring composition for a color filter and a color filter using the same.

That is, the present invention is a color filter coloring composition comprising a colorant (A), a binder resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E), The colorant (A) contains a quinacridone pigment, the binder resin (B) has an acid value of 70 to 200 mgKOH / g, and the following (B1-1), (B1-2), and (B1-3) A photosensitive resin (B1) that is at least one selected from the group consisting of: a polymerizable compound (C1) in which the polymerizable compound (C) has an acidic group; and a polyfunctional light having an alkyleneoxy group having 2 or more carbon atoms The present invention relates to a coloring composition for a color filter comprising at least one selected from curable compounds (C2).
Binder resin (B1-1)
Resin obtained by reacting (c-1) with the copolymer obtained by copolymerizing the following (a-1) and (b-1) and then reacting (d) (a-1): Monomer having a cyclic ether skeleton having 2 to 4 carbon atoms and an ethylenically unsaturated bond (b-1): a monomer having an unsaturated bond copolymerizable with (a-1) and different from (a) (C-1): at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (d): a polybasic acid anhydride binder resin (B1-2)
Resin obtained by reacting (c-2) with a copolymer obtained by copolymerizing the following (a-2) and (b-2) (a-2): unsaturated carboxylic acid and unsaturated carboxylic acid At least one selected from the group consisting of acid anhydrides (b-2): a monomer having an unsaturated bond copolymerizable with (a-2) and different from (a-2) (c-2) ): Monomer binder resin (B1-3) having a C2-C4 cyclic ether skeleton and an ethylenically unsaturated bond
Obtained by reacting the isocyanate group of (d-3) with the side chain hydroxyl group of the copolymer obtained by copolymerizing the following (a-3), (b-3) and (c-3) Resin (a-3): Ethylenically unsaturated monomer having a hydroxyl group (b-3): Unsaturated monobasic acid having a carboxyl group, which is a monomer different from (a-3) (c- 3): Monomer having an unsaturated bond copolymerizable with (a-3) and (b-3) and different from (a-3) and (b-3) (d-3): Isocyanate Ethylenically unsaturated monomer having a group

In the present invention, the quinacridone pigment is C.I. I. It is a pigment red 122, It is related with the said coloring composition for color filters characterized by the above-mentioned.

In the present invention, the photosensitive resin (B1) contains (B1-1) and / or (B1-2), and (b-1) and / or (b-2) contains a tricyclodecane skeleton and The present invention relates to the above-mentioned coloring composition for a color filter, comprising a compound having at least one skeleton selected from a tricyclodecene skeleton and an ethylenically unsaturated bond.

In the present invention, the photosensitive resin (B1) contains (B1-3), and (a-3) is hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate , Poly (alkyleneoxy) (meth) acrylate, and poly (alkyleneoxycarbonyl) (meth) acrylate.
The present invention also relates to the color filter coloring composition, wherein the photosensitive resin (B1) is 30 to 80 parts by weight in 100 parts by weight of the binder resin (B).

In the present invention, the polyfunctional photocurable compound (C2) having an alkyleneoxy group having 2 or more carbon atoms has an alkyleneoxy group having 3 or more photocurable functional groups and having 2 or 3 carbon atoms. The present invention relates to a coloring composition for a color filter having a group.

In the present invention, the polyfunctional photocurable compound (C2) having an alkyleneoxy group having 2 or more carbon atoms contains at least one selected from a pentaerythritol derivative, a dipentaerythritol derivative, and a trimethylolpropane derivative. It is related with the said coloring composition for color filters characterized by the above-mentioned.

In the present invention, the polyfunctional photocurable compound (C2) having an alkyleneoxy group having 2 or more carbon atoms is at least one selected from compounds represented by the general formulas (i), (ii), and (iii). The present invention relates to the coloring composition for a color filter, which comprises a seed.

Formula _{(i) X-C- [CH} 2 -O- (Y) n -Z 1] 3
General formula (ii) C— [CH ₂ —O— (Y) _n —Z ₁ ] ₄
General formula (iii)

[In General Formulas (i), (ii) and (iii), X is independently an alkyl group having 2 to 10 carbon atoms, Y is an alkyleneoxy group having 1 to 10 carbon atoms, Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ and Z _{6 each} represents a hydrogen atom, an acryloyl group or a methacryloyl group. In general formula (i), the sum total of an acryloyl group and a methacryloyl group is three, n represents the integer of 0-10 each independently, and the sum total of n in a molecule | numerator is an integer of 1-30. In general formula (ii), the sum total of acryloyl group and methacryloyl group is four, n represents the integer of 0-10 each independently, and the sum total of n in a molecule | numerator is an integer of 1-40. In general formula (iii), the sum total of the acryloyl group and the methacryloyl group is 5 or 6, each n independently represents an integer of 0 to 10, and the sum of n in the molecule is an integer of 1 to 60. is there. ]

In addition, the present invention relates to the coloring composition for a color filter, which further contains a pigment derivative (F) and / or a dispersant (G).
The present invention also relates to the color filter coloring composition, wherein the polymerization initiator (D) is an oxime ester photopolymerization initiator.

In the color filter, the ratio I / M between the weight I of the polymerization initiator (D) and the weight M of the polymerizable compound (C) is 0.01 to 0.20. The present invention relates to a coloring composition.

In the color filter, the ratio M / P of the weight M of the polymerizable compound (C) and the weight P of the binder resin (B) is 0.30 to 0.50. The present invention relates to a coloring composition.

The present invention further relates to the coloring composition for a color filter, further comprising a thermosetting compound (H).

The present invention also relates to the color filter coloring composition, wherein the thermosetting compound (H) is an epoxy compound or a melamine compound.

Moreover, this invention relates to the color filter formed using the said coloring composition for color filters.

According to the present invention, by combining the pigment, the binder resin, the polymerizable compound, and the polymerization initiator, it is possible to provide a color filter having a high development speed and few residues.

Hereinafter, the present invention will be described in detail. In this specification, “CI” means a color index.

<Colorant (A)>
The coloring composition for a color filter of the present invention is characterized by containing a quinacridone pigment as a colorant.
(Quinacridone pigment (A))
As the quinacridone pigment (A) of the present invention, commercially available quinacridone-based magenta organic pigments can be used alone or in admixture of two or more, and dyes, natural pigments and inorganic pigments can be used in combination. Can do. The quinacridone-based magenta color pigment may be refined by salt milling, acid pasting, or the like.

  Quinacridone-based magenta color pigments have better resistance to heat, light, solvents, etc. than magenta-colored pigments other than quinacridone-based pigments, and there are almost no changes in color or structure due to differences in the environment in which the pigment is placed. However, it is excellent in all of the points that it can be produced at low cost and that the process of pigment production and the like is stable. In particular, the color index number is C.I. I. The pigment of the pigmentlet 122 is a color filter that is mounted on a color imaging device that includes magenta, cyan, and yellow filter segments that have a wavelength range of light that passes through the pigment and a wavelength range of light that the pigment absorbs. It is preferable to use at least one of these pigments.

The concentration of the component of the quinacridone pigment (A) is preferably 20 to 70% by weight, more preferably 40 to 50% by weight in the solid content.

(Other colorants)
About the other coloring agent of this invention, an organic or inorganic pigment can be used individually or in mixture of 2 or more types. Among the pigments, pigments having high color developability and high heat resistance are preferable, and organic pigments are usually used. Below, the specific example of the organic pigment which can be used for the coloring composition of this invention is shown with a color index number.

Specific examples of these organic pigments include red pigments such as 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, 17 9, 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 orange pigments that work in the same way as red pigments include C.I. I. Orange pigments such as CI Pigment Orange 36, 38, 43, 51, 55, 59, 61 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 preferable to use Pigment Red 177.

  Examples of blue pigments 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. 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, and 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. Among these, since high coloring power is obtained, C.I. I. Pigment Green 7, 36 or 58.

  Examples of yellow pigments 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, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208, and the like. Among these, from the viewpoint of obtaining high coloring power, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, or 185, more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, or 185.

  Examples of purple pigments 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. 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 bean (red iron (III) oxide), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, amber, titanium black. Examples thereof include metal oxide powders such as synthetic iron black, titanium oxide, and iron tetroxide, metal sulfide powders, and metal powders. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness.

The coloring composition of the present invention can contain a dye within a range that does not decrease heat resistance for color matching.

From the viewpoint of obtaining sufficient color reproducibility, the preferable concentration of the pigment component is 10% by weight or more, more preferably 15% by weight or more, based on the total nonvolatile components of the colored composition of the present invention (100% by weight). Yes, and most preferably 20% by weight or more. Further, since the stability of the photosensitive coloring composition is improved, the preferable concentration of the pigment component is 90% by weight or less, more preferably 80% by weight or less, and most preferably 70% by weight or less.

<Binder resin (B)>
The vanider resin (B) of the present invention contains a photosensitive resin (B1). The photosensitive resin (B1) is characterized by containing at least one of the following (B1-1), (B1-2), and (B1-3). The binder resin (B1-1) is obtained by reacting (c-1) with a copolymer obtained by copolymerizing the following (a-1) and (b-1) and then reacting (d-1). It is a resin obtained.
(A-1): a monomer having a cyclic ether skeleton having 2 to 4 carbon atoms and an ethylenically unsaturated bond (b-1): having an unsaturated bond copolymerizable with (a-1), ( Monomer (c-1) different from a-1): at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (d-1): polybasic acid anhydrides

  Examples of (a-1) include a monomer (a-1X) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(a-1X)”), an oxetanyl group, and an ethylenically unsaturated group. A monomer (a-1Y) having a bond (hereinafter sometimes referred to as “(a-1Y)”), a monomer (a-1Z) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter referred to as “(a -3) ").

As (a-1X), for example, a monomer (a-11) having a structure obtained by epoxidizing a chain olefin and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(a-11)”), And a monomer (a-12) having a structure obtained by epoxidizing a cycloalkene and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(a-12)”).
As (a-1X), a monomer having an oxiranyl group and a (meth) acryloyloxy group is preferable, and (a-12) having a (meth) acryloyloxy group is more preferable. Here, in the present specification, the “(meth) acryloyloxy group” represents at least one selected from the group consisting of an acryloyloxy group and a methacryloyloxy group. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

Specific examples of (a-11) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, 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 ( Glycidyl oxime Chill) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4, Examples thereof include 6-tris (glycidyloxymethyl) styrene and compounds described in JP-A-7-248625.

Examples of (a-12) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl acrylate (for example, cyclone). Mer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), a compound represented by formula (I), formula (II) ) And the like.

[In Formula (I) and Formula (II), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group. May be substituted.
X ¹ and X ² each independently represent a single bond, —R ³ —, * —R ³ —O—, * —R ³ —S—, or * —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, and a tert-butyl group.
Examples of the alkyl group substituted with a hydroxy group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, and a 1-hydroxy-1 -Methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like can be mentioned.
R1 and R2 are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

Examples of the alkanediyl group include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- Examples include 1,6-diyl group.
X ¹ and X ² are preferably a single bond, a methylene group, an ethylene group, * —CH ₂ —O— (* represents a bond to O), or * —CH ₂ CH ₂ —O— group. More preferably, a single bond and a * —CH ₂ CH ₂ —O— group are mentioned.

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

  Examples of the compound represented by the formula (II) include compounds represented by the formula (II-1) to the formula (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) The compound represented by either of these is mentioned. More preferably, a compound represented by any one of formula (II-1), formula (II-7), formula (II-9), and formula (II-15) can be mentioned.

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

(A-1Y) is preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group. Examples of (a-1Y) include 3-methyl-3- (meth) acryloyloxymethyl oxetane, 3-ethyl-3- (meth) acryloyloxymethyl oxetane, and 3-methyl-3- (meth) acryloyloxyethyl. Examples include oxetane and 3-ethyl-3- (meth) acryloyloxyethyl oxetane.

  (A-1Z) is more preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group. Specific examples of (a-1Z) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

Examples of (b-1) include (meth) such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, and tert-butyl (meth) acrylate. Acrylic acid alkyl esters;
Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.02,6] decan-8-yl (meth) acrylate (in this technical field, dicyclopentanyl as a common name (Meth) acrylate)), (meth) acrylic acid cyclic alkyl esters such as dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate;

  Aryl (meth) acrylates or aralkyl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate; 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. .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 (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene Bicyclo unsaturated compounds;

  N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;

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

In addition, (b-1) is 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) ”).
When (b-1) is (b1), film loss due to development can be suppressed. Here, the “tricyclodecane skeleton” and the “tricyclodecene skeleton” in this specification refer to the following structures (respectively, the bond is an arbitrary position).

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

(B-1) can be used alone or in combination of two or more.

When (b-1) is used in combination of two or more, at least one is preferably the above b1, and the other is aralkyl such as phenyl (meth) acrylate and benzyl (meth) acrylate in the above b. Esters are preferred (hereinafter sometimes referred to as “(b2)”).

In the copolymer obtained by copolymerizing (a-1), (b1) and (b2), the ratio of the structural units derived from each monomer is (a-1), (b1) and (b2). ) Is preferably in the following range with respect to the ratio of the copolymer obtained.
Structural unit derived from (a-1): 10 to 90 mol% (more preferably 30 to 80 mol%)
Structural unit derived from (b1): 10 to 80 mol% (more preferably 10 to 60 mol%)
Structural unit derived from (b2): 10 to 60 mol% (more preferably 10 to 40 mol%)
However, the sum of (a-1), (b1) and (b2) is 100 mol% or less. When the component ratio is in the above range, the curability tends to be better.

Specific examples of (c-1) 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 and 1,4-cyclohexene dicarboxylic 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 Bicyclounsaturated compounds containing a carboxy group such as [2.2.1] hept-2-ene, 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 polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] 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 added amount of (c-1) is preferably 10 to 60% by mass with respect to the copolymer obtained by copolymerizing (a-1), (b1) and (b2) in terms of charged values. 30-40 mass% is more preferable.

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 biphenyl tetracarboxylic acid anhydride. Of these, tetrahydrophthalic anhydride or succinic anhydride is preferable from the viewpoint of developability.

The addition reaction of (d) is performed by a conventional method. The addition amount of (d) is 5 to 100%, preferably 30 to 100%, of the hydroxyl group formed upon introduction of the photosensitive group. When the added amount of (d) is less than 5%, the solubility in a dilute alkali decreases.

The binder resin (B1-2) is a resin obtained by reacting (c-2) with a copolymer obtained by copolymerizing the following (a-2) and (b-2).
(A-2): at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (b-2): having an unsaturated bond copolymerizable with (a-2), Monomer (c-2) different from a-2): a monomer having a C2-C4 cyclic ether skeleton and an ethylenically unsaturated bond

Specific examples of (a-2) 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 and 1,4-cyclohexene dicarboxylic 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 Bicyclounsaturated compounds containing a carboxy group such as [2.2.1] hept-2-ene, 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 polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] 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.

Examples of (b-2) include (meth) methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and the like. Acrylic acid alkyl esters;
Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.02,6] decan-8-yl (meth) acrylate (in this technical field, dicyclopentanyl as a common name It is said to be (meth) acrylate.
), (Meth) acrylic acid cyclic alkyl esters such as dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate;

Aryl (meth) acrylates or aralkyl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 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. .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 (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene Bicyclo unsaturated compounds;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;

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

(B-2) is a compound (b2-1) 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 “( b2-1) ").
When (b-2) is (b2-1), pattern loss due to development can be suppressed.

Specific examples of (b2-1) include dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate. Can be mentioned.

(B-2) can be used alone or in combination of two or more.

When (b-2) is used in combination of two or more, at least one is preferably the above b1, and the other one is aralkyl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate ( Hereinafter, it may be referred to as “(b2-2)”)).

In the copolymer obtained by copolymerizing (a-2), (b2-1) and (b2-2), the proportion of the structural units derived from each monomer is (a-2), (b2 It is preferable that it exists in the following ranges with respect to the ratio of the copolymer obtained by copolymerizing -1) and (b2-2).
Structural unit derived from (a-2): 5 to 80 mol% (more preferably 20 to 60 mol%)
Structural unit derived from (b2-1): 5 to 80 mol% (more preferably 5 to 20 mol%)
Structural unit derived from (b2-2): 0 to 90 mol% (more preferably 10 to 70 mol%)
However, the sum of (a-2), (b2-1) and (b2-2) is 100 mol% or less. When the component ratio is in the above range, the curability tends to be better.

Examples of (c-2) include a monomer (c2-1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(c2-1)”), an oxetanyl group, and an ethylenically unsaturated group. A monomer (c2-2) having a bond (hereinafter sometimes referred to as “(c2-2)”), a monomer (c2-3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter referred to as “(c2 -3) ").

As (c2-1), for example, a monomer (c2-11) having a structure obtained by epoxidizing a chain olefin and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(c2-11)”), And a monomer (c2-12) having a structure obtained by epoxidizing a cycloalkene and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(c2-12)”).
As (c2-1), a monomer having an oxiranyl group and a (meth) acryloyloxy group is preferable, and (c-12) having a (meth) acryloyloxy group is more preferable. Here, in the present specification, the “(meth) acryloyloxy group” represents at least one selected from the group consisting of an acryloyloxy group and a methacryloyloxy group. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

Specific examples of (c2-11) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, 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 ( Glycidyloxy Methyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4, Examples thereof include 6-tris (glycidyloxymethyl) styrene and compounds described in JP-A-7-248625.

Examples of (c2-12) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl acrylate (for example, cyclohexane). Mer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.) a compound represented by formula (I), formula (II) And the compounds represented by formula (I-1) to (I-15). Preferably Formula (I-1), Formula (I-3), Formula (I-5), Formula (I-7), Formula (I-9), Formula (I-11) to Formula (I-15) Or a compound represented by any one of the formulas (II-1) to (II-15).

(C2-2) is preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group. Examples of (c2-2) include 3-methyl-3- (meth) acryloyloxymethyloxetane, 3-ethyl-3- (meth) acryloyloxymethyloxetane, and 3-methyl-3- (meth) acryloyloxyethyl. Examples include oxetane and 3-ethyl-3- (meth) acryloyloxyethyl oxetane.

(C2-3) is more preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group. Specific examples of (c2-3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

The addition amount of (c2-2) is preferably 10 to 60% by mass with respect to the copolymer obtained by copolymerizing (a-2), (b1) and (b2) in terms of charged values. 15-40 mass% is more preferable.

The binder resin (B1-3) is obtained by reacting the isocyanate group of (d-3) with a copolymer obtained by copolymerizing the following (a-3), (b-3) and (c-3). This is a resin obtained.
(A-3): an ethylenically unsaturated monomer having a hydroxyl group (b-3): an unsaturated monobasic acid having a carboxyl group, which is a monomer different from (a-3) (c-3) ): A monomer having an unsaturated bond copolymerizable with (a-3) and (b-3) and different from (a-3) and (b-3) (d-3): an isocyanate group Ethylenically unsaturated monomer having

Examples of (a-3) include hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, Alternatively, hydroxyalkyl methacrylates such as cyclohexanedimethanol mono (meth) acrylate may be used, and these may be used alone or in combination of two or more. In addition, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, polyγ-valerolactone, polyε-caprolactone, and / or Polyester mono (meth) acrylate, poly (alkyleneoxy) (meth) acrylate, and poly (alkyleneoxycarbonyl) (meth) acrylate to which poly-12-hydroxystearic acid is added can also be used. In particular, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, poly (alkyleneoxy) (meth) acrylate, and poly (alkyleneoxycarbonyl) (meth) acrylate are preferred.

Examples of (b-3) include acrylic acid, methacrylic acid, crotonic acid, vinyl acetic acid, acryloxypropionic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl. , Halogen, nitro, cyano-substituted monocarboxylic acid, and the like, but not limited thereto, two or more kinds can be used in combination.

Examples of (c-3) include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, and methacrylamide. , Vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, ethylenically unsaturated monomers having an epoxy group, such as glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate 2-glycidoxyethyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and 3,4-epoxycyclohexyl (meth) acrylate, alkyl (meth) acrylates such as methyl (meth) Acrylate, ethyl (meta Acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, (meth) acrylic acid cyclic alkyl esters such as cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) Acrylate, tricyclo [5.2.1.02,6] decan-8-yl (meth) acrylate (referred to in the art as dicyclopentanyl (meth) acrylate), dicyclo Pentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, aryl (meth) acrylate or aralkyl esters such as phenyl (meth) acrylate, benzyl (meth) acrylate, hydroxyalkyl esters such as diethyl maleate Dicarboxylic acid diesters such as diethyl fumarate and diethyl itaconate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, bicyclounsaturated compounds such as 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- 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] F To-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept 2-ene, dicarbonylimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl- Examples thereof include 6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, and N- (9-acridinyl) maleimide, but the present invention is not limited thereto, and two or more kinds can be used in combination.

Examples of (d-3) include 2- (meth) acryloyloxyethyl isocyanate or 1,1-bis [methacryloyloxy] ethyl isocyanate, but are not limited to these and are used in combination of two or more. You can also

In order to disperse the quinacridone pigment, the weight average molecular weight (Mw) of the binder resin (B) is preferably in the range of 10,000 to 100,000, more preferably in the range of 8,000 to 30,000. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

The photosensitive resin (B1) of the present invention has an acid value of 70 to 200 mgKOH / g. From the viewpoints of dispersibility, stability, developability, and heat resistance of quinacridone pigments, a carboxyl group that functions as a colorant-adsorbing group and an alkali-soluble group during development, and an aliphatic group that functions as an affinity group for the colorant carrier and solvent And the balance of the aromatic groups are important for the dispersibility of the pigment, the developer permeability in the coating film, the developer solubility of the uncured part, and the durability. It is preferable to use a resin having an acid value of 70 to 150 mgKOH / g. When the acid value is less than 70 mgKOH / g, the solubility in the developer is poor and it is difficult to form a fine pattern. If it exceeds 200 mgKOH / g, pattern peeling may occur and a fine pattern may not remain.

The binder resin (B) is preferably used in an amount of 30 parts by weight or more with respect to 100 parts by weight of the total weight of the quinacridone pigment because the film formability and various resistances are good, and the colorant concentration is high. Since good color characteristics can be expressed, it is preferably used in an amount of 500 parts by weight or less. More preferably, it is 100-400 weight part, More preferably, it is 160-320 weight part. The chromaticity region can be expanded by such a composition ratio of the pigment. Further, in order to obtain good developability and no residue, the photosensitive resin (B1) is preferably 30 to 80 parts by weight with respect to 100 parts by weight of the binder resin (B).

<Polymerizable compound (C)>
The polymerizable compound (C) includes monomers or oligomers that are cured by ultraviolet rays or heat to generate a transparent resin, and these can be used alone or in combination of two or more. The amount of the monomer is preferably 5 to 400% by weight based on the total weight of the colorant (100% by weight), and more preferably 10 to 300% by weight from the viewpoint of photocurability and developability. preferable.

  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 ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Luether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

<Polymerizable compound having acidic group (C1)>
In the photopolymerizable compound (C), a polymerizable compound having an acidic group is preferable in terms of developability. Examples of the polymerizable compound (C1) having an acid group include, for example, an esterified product of a free hydroxyl group-containing poly (meth) acrylate of a polyhydric alcohol and (meth) acrylic acid and a dicarboxylic acid; a polycarboxylic acid; Examples include esterified products with monohydroxyalkyl (meth) acrylates. Specific examples include trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate and the like monohydroxy oligoacrylates or monohydroxy oligomethacrylates And monoesterified products containing free carboxyl groups with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarbaryl acid), butane-1,2,4 -Tricarboxylic acids, such as benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid And a free carboxyl group-containing oligoester product of monohydroxy monoacrylate or monohydroxy monomethacrylate such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc. be able to.
These polymerizable compounds (C1) can be used singly or in combination of two or more in any ratio as necessary.

Moreover, the compound represented by following General formula (2) can also be used preferably.

General formula (2):
(H ₂ C═C (R ⁴ ) COO) _m —X ₃ — (OCOCH (R ⁴ ) CH ₂ S (R ⁵ ) COOH) _n

[In General Formula (2), R ⁴ is a hydrogen atom or a methyl group, R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms, and X ₃ is an (m + n) -valent carbon number 3 to 60. Organic group, m represents an integer of 2 to 18, and n represents an integer of 1 to 3. ]

Here, the compound represented by the general formula (2) can be easily obtained by, for example, the following method.
(1) A method in which a compound giving an organic group represented by X ₃ is esterified with acrylic acid and acrylated, and then a mercapto compound is added to the obtained compound.
(2) After the compound providing an organic group represented by X ₃ modified with a polyisocyanate compound, after acrylated acrylate compound having a hydroxyl group in the resulting compound, adding a mercapto compound to the compound obtained How to make.
(3) A method in which a compound giving an organic group represented by X ₃ is esterified with acrylic acid to be acrylated, then modified with a polyisocyanate compound, and a mercapto compound is added to the obtained compound.

Examples of the compound giving an organic group represented by X ₃ include pentaerythritol, pentaerythritol-modified caprolactone, pentaerythritol-modified polyisocyanate, dipentaerythritol, dipentaerythritol-modified caprolactone, dipentaerythritol poly Mention may be made of isocyanate-modified products.

  Examples of the mercapto compound include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, mercaptosuccinic acid, and the like.

  The content of the polymerizable compound (C1) having an acid group is preferably 5 to 500 parts by weight and more preferably 20 to 300 parts by weight with respect to 100 parts by weight of the binder resin. By making it 5 parts by weight or more, the pixel strength or the smoothness of the pixel surface becomes better, and when it is 500 parts by weight or less, the alkali developability is excellent, so that the residue in the region other than the part where the pixels are formed And no film residue.

<Polyfunctional photocurable compound (C2) having an alkyleneoxy group having 2 or more carbon atoms>
In the photopolymerizable compound (C), a polyfunctional photocurable compound having an alkyleneoxy group having 2 or more carbon atoms is preferable from the viewpoint of developability. Hereinafter, the alkyleneoxy group may be referred to as “AO group”. As a form of the polyfunctional photocurable compound in the present invention, (C2-1) a polyfunctional photocurable compound having one or more AO groups having 2 or more carbon atoms and having no acidic functional group, (C2-2) There are two forms of polyfunctional photocurable compounds having one or more acidic functional groups and one or more AO groups having 2 or more carbon atoms. In the polymerizable compound (C2) of the present invention, the above (C2-1) and (C2-2) may be used in combination.

  As the polyfunctional photocurable compound (C2) in the present invention, it is preferable to use a compound having a relatively small molecular size. In particular, it is preferable to use a compound having a polystyrene equivalent weight average molecular weight of less than 3,000.

  The reaction form of the photocurable functional group of the polyfunctional photocurable compound (C2) is not limited, and may be any of a photo radical reaction, a photo cation reaction, and a photo anion reaction. Is preferably a photoradical reactive group such as photoradical polymerization or photoradical dimerization, and particularly preferably a group containing an ethylenically unsaturated bond such as a (meth) acryloyl group. An acryloyl group and a methacryloyl group are preferable, and an acryloyl group is more preferable.

The polyfunctional photocurable compound (C2) in the present invention preferably has three or more photocurable functional groups and an AO group having 2 or 3 carbon atoms. By having an AO group having 2 or 3 carbon atoms, hydrophilicity is improved and solubility in an aqueous alkaline developer is also improved. Therefore, polyfunctional light having an AO group having 2 or more carbon atoms even if the amount of a component that does not have curing reactivity and is not alkali-soluble, such as a colorant or a photopolymerization initiator, is increased in the photocurable composition. Addition of the curable compound (C2) increases alkali solubility, so that excellent alkali developability is obtained.

The polyfunctional photocurable compound (C2) having an AO group having 2 or more carbon atoms of the present invention preferably contains at least one selected from the group of pentaerythritol derivatives, dipentaerythritol derivatives and trimethylolpropane derivatives. . The photocurable functional group of the compound increases the crosslink density and provides excellent curability.

In order to increase the crosslinking density, it is better that the number of photocurable functional groups of the polyfunctional photocurable compound (C2) is large.
Moreover, from the viewpoint of the crosslinking density, the number of the photocurable functional groups in the polyfunctional photocurable compound (C2) having an AO group having 2 or more carbon atoms is preferably 3 or more, and 3 to 30. Is more preferable, and 3 to 15 is particularly preferable. Moreover, from the viewpoint of the crosslinking density, the number of photocurable functional groups in the polyfunctional photocurable compound (C2) having an acidic functional group is preferably 3 or more.

  The polyfunctional photocurable compound (C2) in the present invention is preferably at least one selected from the group of compounds represented by formulas (i) to (iii).

In addition, the specific composition described in general formula (i) is (1) to (19) below.

_{[CH 2 = CHCO- (OC 3} H 6) n -OCH 2] 3 -CCH 2 CH 3 (1)
_{[CH 2 = CHCO- (OC 2} H 4) n -OCH 2] 3 -CCH 2 CH 3 (2)
_{[CH 2 = CHCO- (OC 3} H 6) n -OCH 2] 3 -CCH 2 CH 3 (3)
_{[CH 2 = CHCO- (OC 4} H 8) n -OCH 2] 3 -CCH 2 CH 3 (4)
_{[CH 2 = CHCO- (OC 5} H 10) n -OCH 2] 3 -CCH 2 CH 3 (5)
_{[CH 2 = CHCO- (OC 6} H 12) n -OCH 2] 3 -CCH 2 CH 3 (6)
_{[CH 2 = CHCO- (OC 7} H 14) n -OCH 2] 3 -CCH 2 CH 3 (7)
_{[CH 2 = CHCO- (OC 8} H 16) n -OCH 2] 3 -CCH 2 CH 3 (8)
_{[CH 2 = CHCO- (OC 9} H 18) n -OCH 2] 3 -CCH 2 CH 3 (9)
_{[CH 2 = CHCO- (OC 10} H 20) n -OCH 2] 3 -CCH 2 CH 3 (10)
_{[CH 2 = CHCO- (OC 2} H 4) n -OCH 2] 3 -CCH 2 C 2 H 5 (11)
_{[CH 2 = CHCO- (OC 2} H 4) n -OCH 2] 3 -CCH 2 C 3 H 7 (12)
_{[CH 2 = CHCO- (OC 2} H 4) n -OCH 2] 3 -CCH 2 C 4 H 9 (13)
_{[CH 2 = CHCO- (OC 2} H 4) n -OCH 2] 3 -CCH 2 C 5 H 11 (14)
_{[CH 2 = CHCO- (OC 2} H 4) n -OCH 2] 3 -CCH 2 C 6 H 13 (15)
_{[CH 2 = CHCO- (OC 2} H 4) n -OCH 2] 3 -CCH 2 C 7 H 15 (16)
_{[CH 2 = CHCO- (OC 2} H 4) n -OCH 2] 3 -CCH 2 C 8 H 17 (17)
_{[CH 2 = CHCO- (OC 2} H 4) n -OCH 2] 3 -CCH 2 C 9 H 19 (18)
_{[CH 2 = CHCO- (OC 2} H 4) n -OCH 2] 3 -CCH 2 C 10 H 21 (19)
In general formulas (1) to (19), n represents an integer of 1 to 2.

Specific compositions described in the general formula (ii) are the following (20) to (29).

_{[CH 2 = CHCO- (OCH 2} ) n -OCH 2] 4 -C (20)
_{[CH 2 = CHCO- (OC 2} H 4) n -OCH 2] 4 -C (21)
_{[CH 2 = CHCO- (OC 3} H 6) n -OCH 2] 4 -C (22)
_{[CH 2 = CHCO- (OC 4} H 8) n -OCH 2] 4 -C (23)
_{[CH 2 = CHCO- (OC 5} H 10) n -OCH 2] 4 -C (24)
_{[CH 2 = CHCO- (OC 6} H 12) n -OCH 2] 4 -C (25)
_{[CH 2 = CHCO- (OC 7} H 14) n -OCH 2] 4 -C (26)
_{[CH 2 = CHCO- (OC 8} H 16) n -OCH 2] 4 -C (27)
_{[CH 2 = CHCO- (OC 9} H 18) n -OCH 2] 4 -C (28)
_{[CH 2 = CHCO- (OC 10} H 20) n -OCH 2] 4 -C (29)
In general formulas (20) to (29), n represents an integer of 1 to 2.

Specific compositions described in the general formula (iii) are (30) to (19) below.

_{[[CH 2 = CHCO- (OCH} 2) n -OCH 2] 3 -C] 2 -O (30)
_{[[CH 2 = CHCO- (OC} 2 H 4) n -OCH 2] 3 -C] 2 -O (31)
_{[[CH 2 = CHCO- (OC} 3 H 6) n -OCH 2] 3 -C] 2 -O (32)
_{[[CH 2 = CHCO- (OC} 4 H 8) n -OCH 2] 3 -C] 2 -O (33)
_{[[CH 2 = CHCO- (OC} 5 H 10) n -OCH 2] 3 -C] 2 -O (34)
_{[[CH 2 = CHCO- (OC} 6 H 12) n -OCH 2] 3 -C] 2 -O (35)
_{[[CH 2 = CHCO- (OC} 7 H 14) n -OCH 2] 3 -C] 2 -O (36)
_{[[CH 2 = CHCO- (OC} 8 H 16) n -OCH 2] 3 -C] 2 -O (37)
_{[[CH 2 = CHCO- (OC} 9 H 18) n -OCH 2] 3 -C] 2 -O (38)
_{[[CH 2 = CHCO- (OC} 10 H 20) n -OCH 2] 3 -C] 2 -O (39)
In general formulas (30) to (39), n represents an integer of 1 to 2.

  As a commercial item of the polyfunctional photocurable compound represented by the formulas (1) to (39), for example, three SR-494 isobutyleneoxy chains which are tetrafunctional acrylates having four ethyleneoxy chains manufactured by Sartomer Examples thereof include TPA-330, which is a trifunctional acrylate, and Aronix M310, M321, M350, and M360 manufactured by Toagosei Co., Ltd.

The content of the polymerizable compound (C) in the colored composition of the present invention is preferably 2 to 50% by weight, more preferably 2 to 30% by weight, based on the total solid content of the composition. Furthermore, 2 to 15% by weight is more preferable.
If the content is within the above range, the content of the pigment can be further increased without impairing the effects of the present invention, and the pattern can be further thinned and further refined. In the polymerizable compound (C) of the present invention, the above (C1) and (C2) may be used in combination.

  In order to provide a color filter having a high development speed and a small amount of residue, the coloring composition for a color filter of the present invention has a ratio M / M of the weight M of the polymerizable compound (C) and the weight P of the binder resin (B). P is preferably 0.30 to 0.50, more preferably 0.30 to 0.40. When M / P exceeds 0.0.50, pattern peeling occurs due to too much polymerizable compound. When M / P is less than 0.30, a residue is generated due to too little polymerizable compound.

<Polymerization initiator (D)>
The colored composition of the present invention is prepared in the form of a solvent development type or alkali development type colored resist material by adding a polymerization initiator or the like when the composition is cured by ultraviolet irradiation and a filter segment is formed by a photolithographic method. can do. The blending amount when using the polymerization initiator (D) is preferably 0.5 to 200% by weight based on the total amount of the colorant, and 1 to 150% by weight from the viewpoint of photocurability and developability. It is more preferable that

As the polymerization initiator (D), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] Acetophenone compounds such as -1- [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Is a benzoin compound such as benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone Thioxanthone compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p- Toxiphenyl) -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- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl Triazine compounds such as-(4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoylo Oxime)], or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6 Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; A carbazole compound; an imidazole compound; or a titanocene compound is used. In addition, since the color imaging element is required to be thin, the pigment concentration in the solid content composition becomes high. Therefore, these polymerization initiators (D) are more preferably highly sensitive ones such as oxime ester compounds.

These polymerization initiators (D) can be used alone or in combination of two or more at any ratio as required.

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

<Sensitizer>
Furthermore, the coloring composition of the present invention can contain a sensitizer. Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) benzophen Non, 4,4′-diethylaminobenzophenone and the like.

More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

Two or more kinds of sensitizers may be used in any ratio as required. The amount of the sensitizer used is preferably 3 to 60% by weight based on the total weight (100% by weight) of the polymerization initiator (D) contained in the colored composition, and is photocured. Is more preferably 5 to 50% by weight from the viewpoint of the property and developability.

<Solvent (E)>
In the coloring composition of the present invention, the solvent (E) sufficiently disperses and penetrates the coloring agent in the coloring agent carrier so that the dry film thickness is 0.2 to 5 μm on a substrate such as a glass substrate. It is contained to make it easier to apply and form filter segments.

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, 1,4- Dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3 -Methyl-1,3-butanediol, 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-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, 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 monotertiary 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 monoethyl ether , 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, Chill isobutyl ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

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

A solvent (E) can be used individually by 1 type or in mixture of 2 or more types. Moreover, since the solvent can adjust the coloring composition to an appropriate viscosity and can form a filter segment with a desired uniform film thickness, the total weight of the colorant is 100% by weight (500% to 4000% by weight). It is preferable to use it in the quantity.

  The quinacridone-based magenta color pigment can be dispersed well by introducing a specific substituent into the quinacridone-based pigment and using a dye derivative (F) and / or a dispersant (G). It becomes possible to produce a magenta colored composition having excellent properties. There are two main reasons. The first is that the quinacridone dye derivative is compatible with the quinacridone magenta color pigment. The second is a pigment dispersant used when dispersing the quinacridone magenta color pigment in the pigment carrier. It is a point which does not aggregate between each other.

<Dye derivative (F)>
Examples of the dye derivative (F) include compounds in which a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent is introduced into an organic pigment, quinacridone, anthraquinone, acridone or triazine, For example, JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-2001-335717 JP-A 2003-128669, JP-A 2004-091497, JP-A 2007-156395, JP-A 2008-094773, JP-A 2008-094986, JP-A 2008-095007, Described in Japanese Unexamined Patent Application Publication No. 2008-195916 and Japanese Patent No. 4585781. It can be used which are, they may be used alone or in combination of two or more. When a pigment derivative is used, one having a quinophthalone skeleton is preferable from the viewpoints of brightness and dispersibility.

The blending amount of the pigment derivative (F) is preferably 0.5% by weight or more, more preferably 1% by weight, based on the total amount of the added colorant (100% by weight) from the viewpoint of improving the dispersibility of the added colorant. Above, most preferably 3% by weight or more. Further, from the viewpoint of heat resistance and light resistance, the total amount of the additive pigment is preferably 40% by weight or less, more preferably 35% by weight or less, based on the total amount (100% by weight).

<Dispersant (G)>
The dispersant (G) has a colorant affinity part having a property of adsorbing to the added colorant and a part compatible with the colorant carrier. It works to stabilize dispersion. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct, phosphoric ester or the like is used, they may be used alone or in combination, it is not necessarily limited thereto.

Among the above-mentioned dispersants, a polymer dispersant having a basic functional group is preferable because the viscosity of the dispersion is lowered and a high contrast is exhibited with a small addition amount, and a nitrogen atom-containing graft copolymer or side chain is preferable. Nitrogen atom-containing acrylic block copolymers and urethane polymer dispersants having functional groups including tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles and the like are preferred.
The resin-type dispersant is preferably used in an amount of about 5 to 200% by weight relative to the total amount of the pigment, and more preferably about 10 to 100% by weight from the viewpoint of film formability.

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 SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS or Bykumen. 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., manufactured by BASF EFKA-46, 47, 48, 452, 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, 1 01,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

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

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include 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 end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane 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 thereto.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Method for producing colored composition>
The coloring composition of the present invention is a mixture of a quinacridone pigment (A), a binder resin (B) and a solvent (E). It can be produced by finely dispersing using means. Moreover, the coloring composition of this invention can also be manufactured by mixing what disperse | distributed the coloring agent etc. finely in binder resin and the organic solvent separately.

In this way, when the colorant refined to an average primary particle size of 100 nm or less is dispersed in a transparent resin using a dispersing machine such as a sand mill, it is in a state of dispersed particles composed of secondary particles in which a plurality of primary particles are collected. Dispersed, the dispersed particles gradually become smaller with the progress of the dispersed state, and finally 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 in the range of 50 nm to 150 nm.

As the dispersion proceeds, the dispersed particle diameter becomes smaller and the transparency increases, so the smaller the dispersed particle diameter is better. On the other hand, when the dispersion progresses and the dispersed particle size becomes small, the viscosity of the dispersion increases and the thixotropic property tends to increase. When used as a coloring composition for a color filter, it is required that a thin film is applied and the surface of the coating film is smooth, so that it has a low viscosity and a Newtonian flow. For this reason, it is preferable to suppress the dispersed particle size to about 100 nm in consideration of the viscosity and thixotropic property preferable for normal use. Thus, 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 in the range of 50 nm to 150 nm, the increase in viscosity and thixotropic property are minimized. It is possible to obtain a pigment dispersion that is limited to a high transparency.

<Removal of coarse particles>
The coloring composition of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

<Thermosetting compound (H)>
It is preferable that the photosensitive coloring composition of the present invention further contains a thermosetting compound in combination with the binder resin (B). When producing a color filter using the photosensitive coloring composition of the present invention, by including a thermosetting compound, it reacts at the time of firing the filter segment to increase the cross-linking density of the coating film, thereby improving the heat resistance of the filter segment. And the effect that the pigment aggregation at the time of filter segment baking is suppressed is acquired.

Examples of the thermosetting compound include an epoxy compound, a benzoguanamine compound, a rosin-modified maleic acid compound, a rosin-modified fumaric acid compound, a melamine compound, a urea compound, and a phenol compound, but the present invention is limited to this. is not. In the photosensitive coloring composition of the present invention, an epoxy compound and a melamine compound are preferably used.

The epoxy compound may be a low molecular 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 Benzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Condensates, phenols and various diene compounds (dicyclopentadiene, terpenes, Polymers with nylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc., phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.) ), Polyphenols and aromatic dimethanols (benzenedimethanol, α, α, α ′, α′-benzenedimethanol, biphenyldimethanol, α, α, α ′, α′-biphenyldimene) Methanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, alcohols Etc. glycidylated Glycidyl ether epoxy resins, alicyclic epoxy resins, glycidyl amine-based epoxy resin, glycidyl ester type epoxy resins, but are not limited to these would normally epoxy compound used. These may be used alone or in combination of two or more.

As a commercial item, for example, Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P (above are trade names; manufactured by Yuka Shell Epoxy Co., Ltd.), Epicoat 1004, Epicoat 1256 (or more) Is a trade name; manufactured by Japan Epoxy Resin Co., Ltd., TECHMORE VG3101L (trade name; manufactured by Mitsui Chemicals, Inc.), EPPN-501H, 502H (trade name; manufactured by Nippon Kayaku Co., Ltd.), JER 1032H60 (trade 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 Name: Japan Epoxy Resin Co., Ltd.) EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (above are trade names; manufactured by Nippon Kayaku Co., Ltd.), Celoxide 2021, EHPE-3150 (above are trade names: manufactured by Daicel Chemical Industries, 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; Nagase ChemteX Co., Ltd.) and the like, but are not limited thereto.

  The compounding amount of the epoxy compound is preferably 0.5 to 300 parts by weight, and more preferably 1.0 to 50 parts by weight with respect to 100 parts by weight of the colorant. If the amount is less than 0.5 part by weight, the effect of improving heat resistance is small. If the amount is more than 300 parts by weight, a problem may occur when forming a filter segment by photolithography.

As melamine resins, Nikarak MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX manufactured by Sanwa Chemical Co., Ltd. -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 Cymel 300, 301, 303, 350, 232, 235, 236, 238, 506, and the like.
Examples of the benzoguanamine resin include Nikalac BX-4000, BX-37, BL-60 manufactured by Sanwa Chemical Co., Ltd., Superbecamine TD-126, 15-594 manufactured by DIC Corporation, and the like.

The blending amount of the melamine compound is preferably 0.5 to 300 parts by weight and more preferably 1.0 to 50 parts by weight with respect to 100 parts by weight of the colorant. If the amount is less than 0.5 part by weight, the effect of improving heat resistance is small. If the amount is more than 300 parts by weight, a problem may occur when forming a filter segment by photolithography.

Moreover, in order to assist hardening of a thermosetting compound, the coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited, and can react with thermosetting compounds. Any curing agent may be used as long as it is. Examples of the curing accelerator include amine compounds (for example, 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 amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- D Ru-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. As content of the said hardening accelerator, 0.01-15 weight part is preferable with respect to 100 weight part of thermosetting compounds.

<Other additive components>
The colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition with time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10% by weight based on the total amount of the colorant (100% by weight).

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

<Color filter>
Next, the color filter of the present invention will be described. The color filter of this invention comprises the filter segment formed using the coloring composition of this invention. Examples of the color filter include those having a plurality of color filter segments among red, blue, green, yellow, cyan, and magenta color filter segments.

The colored composition of the present invention is mainly used for forming a magenta color filter segment, and the filter segments of the other colors are conventionally used red color composition, green color composition, blue color composition, yellow color composition. Or a cyan coloring composition. The colored composition of each color other than the colored composition of the present invention can be formed using each colored composition containing each color pigment, the binder resin, the photopolymerizable composition, and the like.

<Pigment forming magenta filter segment>
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 are exemplified, but not limited thereto.

<Pigment forming red filter segment>
As a red pigment for a red coloring composition forming a red filter segment,
C. 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, a diketopyrrolopyrrole pigment described in JP 2011-523433 A, or a naphthol azo pigment described in JP 2013-161025 A However, it is not particularly limited to these.

The red coloring composition includes C.I. I. Pigment orange 43, 71, 73 or the like 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, 181 182,185,187,188,193,194,198,199,213, or may be used in combination of a yellow pigment 214, and the like.

<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 2004-333817, Examples thereof include aluminum phthalocyanine pigments described in Japanese Patent No. 4893859, but are not particularly limited thereto.
Examples of purple pigments include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 or the like, but not 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. Green pigments such as CI Pigment Green 7, 10, 36, 37, and 58 can be used. The green coloring composition includes 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, Yellow pigments such as 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221 can be used in combination.

<Pigment forming yellow filter segment>
Examples of yellow pigments for blue coloring compositions that form yellow filter segments 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, Yellow pigments such as 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221 can be used alone or in combination.

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

<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 comprises a filter segment formed of the photosensitive coloring composition of the present invention on a substrate, and a general color filter is at least one red color. It comprises a filter segment, at least one green filter segment, and at least one blue filter segment, or comprises at least one magenta filter segment, at least one cyan filter segment, and at least one yellow filter segment.

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, 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 in order to drive the liquid crystal after forming the panel. When used for a solid-state imaging device, 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.

The formation of each color filter segment by photolithography is performed by the following method. That is, the photosensitive coloring composition prepared as a solvent developing type or alkali developing type colored resist material has a dry film thickness of 0. 0 on a transparent substrate by a coating method such as spray coating, spin coating, slit coating or roll coating. It apply | coats so that it may become 2-10 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film.

Thereafter, the filter segment can be formed by immersing in a solvent or an alkaline developer, or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern. Furthermore, in order to accelerate the polymerization of the filter segment formed by development, heating can be performed as necessary. According to the photolithography method, a filter segment with higher accuracy than the printing method can be formed.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or 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 due to oxygen. After forming, UV exposure can also be performed.

The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

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 weight” and “% by weight”, respectively. “PGMAc” means propylene glycol monomethyl ether acetate.

<Production Example of Dye Derivative (F)>
To 100 parts of chlorosulfonic acid, 10 parts of unsubstituted quinacridone is added at 10 to 20 ° C., stirred at 40 to 50 ° C. for 3 hours, poured into 1000 parts of ice water, filtered, washed with water, and quinacridone monosulfonate. Of water cake. The water cake of this chlorosulfonated product was added to 300 parts of ice water and reslurried, 20 parts of N, N-diethylaminopropylamine was added, and the mixture was stirred at 10 ° C. or lower for 4 hours, filtered and washed with water. Then, this water cake was added to 300 parts of 0.5% aqueous sodium carbonate solution, stirred for 1 hour, filtered, washed with water until neutral and dried, and 16 parts of quinacridone dye having the structure of the following general formula (12) Derivative A was obtained.

Formula (12)

<Preparation of acrylic resin solution>
A separable four-necked flask was equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirring device, charged with 70.0 parts of cyclohexanone, heated to 80 ° C. and purged with nitrogen in the reaction vessel. 13.3 parts of butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), 2, 2 A mixture of 0.4 parts of '-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution having a solid content of 30% and a weight average molecular weight of 26000.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20%. An acrylic resin solution was prepared.

<Production Example of Dispersant (G)>
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 50.0 parts of methyl methacrylate and 50.0 parts of 2-methoxyethyl acrylate, and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and 6.0 parts of 3-mercapto-1,2-propanediol and 0.1 part of 2,2′-azobisisobutyronitrile were added to propylene glycol monomethyl ether acetate 45. The solution dissolved in 4 parts was added and reacted for 10 hours. It was confirmed that 95% had reacted by solid content measurement. At this time, the weight average molecular weight was 4000. Next, 9.7 parts of pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.), 31.7 parts of PGMAc, and 1,8-diazabicyclo- [5.4.0] -7-undecene 0.2 as a catalyst An additional portion was added and reacted at 120 ° C. for 7 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. After completion of the reaction, propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 60% by weight, and a solution of a dispersant G1 having an acid value of 43 mgKOH / g and a weight average molecular weight of 9,500 was obtained.

<Production Example of Colorant (A)>
A mixture having the following composition was stirred and mixed uniformly, then dispersed with an Eiger mill for 4 hours using zirconia beads having a diameter of 0.8 mm, and then filtered with a 5 μm filter to prepare a magenta color pigment dispersion.
Quinacridone-based magenta pigment C.I. I. Pigment Red 122
("Hosta Palm Pink E" manufactured by Clariant) 11.7 parts Quinacridone pigment dispersant A 1.3 parts Dispersant G1 solution 10.8 parts Acrylic resin solution 2.5 parts Propylene glycol monomethyl ether acetate 73.7 parts

<Example of production of red pigment dispersion>
A mixture having the following composition was stirred and mixed uniformly, then dispersed with an Eiger mill for 4 hours using zirconia beads having a diameter of 0.8 mm, and then filtered with a 5 μm filter to prepare a red pigment dispersion.
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254
("IRGAZIN RED 2030" manufactured by BASF) 13.0 parts Dispersant G1 solution 10.8 parts Acrylic resin solution 2.5 parts Propylene glycol monomethyl ether acetate 73.7 parts

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

(Binder resin solution 1)
After introducing 333 g of propylene glycol monomethyl ether acetate into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introducing tube, and changing the atmosphere in the flask from air to nitrogen, 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 having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) ) And 3.6 g of azobisisobutyronitrile added to a mixture of 164 g of propylene glycol monomethyl ether acetate was added dropwise to the flask from the dropping funnel over 2 hours, and stirring was continued at 100 ° C. for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, 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,. 9 g and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 110 ° C. for 6 hours. When the solid content acid value reached 1 mgKOH / g, the reaction was terminated. 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 obtain a binder resin solution 1 having an acid value of 80 mgKOH / g. The weight average molecular weight (Mw) was 12,000, and the molecular weight distribution (Mw / Mn) was 2.1.

(Binder resin solution 2)
After introducing 182 g of propylene glycol monomethyl ether acetate into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, and changing the atmosphere in the flask from air to nitrogen, 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, 22.0 g (0.10 mol) of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) ) And propylene glycol monomethyl ether acetate (136 g) in a solution obtained by adding 3.6 g of azobisisobutyronitrile to the flask from the dropping funnel over 2 hours, and further stirring 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, 0.5%. 9 g and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 110 ° C. for 6 hours to obtain a binder resin solution 2 having an acid value of 79 mgKOH / g. The weight average molecular weight (Mw) was 13,000, and the molecular weight distribution (Mw / Mn) was 2.1.

(Binder resin solution 3)
560 parts of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 34.0 parts of methacrylic acid, 23.0 parts of methyl methacrylate, 23.0 parts of n-butyl methacrylate at the same temperature. , 22.0 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toa Gosei Co., Ltd.), 47.0 parts of glycerol monomethacrylate, and 4.0 parts of 2,2′-azobisisobutyronitrile. The polymerization reaction was performed dropwise over 1 hour. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 55 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin copolymer solution was obtained.
Next, a mixture of 32.0 parts of 2-methacryloylethyl isocyanate, 0.4 parts of dibutyltin laurate, and 120.0 parts of cyclohexanone was added at 3O <0> C to 338 parts of the obtained transparent resin copolymer solution. It dripped over time and the photosensitive transparent resin solution was obtained. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution is sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The previously synthesized photosensitive transparent resin solution has a non-volatile content of 20% by weight. Thus, cyclohexanone was added to prepare a photosensitive resin solution. The obtained (Binder resin solution 3) had an acid value of 98 mgKOH / g and a weight average molecular weight Mw of 21,000.

(Binder resin solution 4)
570 parts of cyclohexanone is placed in a reaction vessel and heated 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, paracumyl A mixture of 22.0 parts of phenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toa Gosei Co., Ltd.), 48.0 parts of glycerol monomethacrylate, and 3.0 parts of 2,2'-azobisisobutyronitrile is taken over 1 hour. The polymerization reaction was carried out dropwise. After completion of the dropwise addition, 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. A resin copolymer solution was obtained.
Next, 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 3O <0> C to 336 parts of the obtained transparent resin copolymer solution. It dripped over time and the photosensitive transparent resin solution was obtained. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution is sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The previously synthesized photosensitive transparent resin solution has a non-volatile content of 20% by weight. Thus, cyclohexanone was added to prepare a photosensitive resin solution. The obtained binder resin solution 4 had an acid value of 65 mgKOH / g and a weight average molecular weight Mw of 32,000.

(Binder resin solution 5)
520 parts of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 7.0 parts of methacrylic acid, 7.0 parts of methyl methacrylate, 63.0 parts of 2-hydroxyethyl methacrylate at the same temperature. Then, a mixture of 66.0 parts of glycerol monomethacrylate and 4.0 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 70 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin copolymer solution was obtained.
Next, with respect to 220 parts of the obtained transparent resin copolymer solution, a mixture of 56.0 parts of 2-methacryloylethyl isocyanate, 0.4 part of dibutyltin laurate, and 220.0 parts of cyclohexanone was added at 70 ° C. at 3 ° C. It dripped over time and the photosensitive transparent resin solution was obtained. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution is sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The previously synthesized photosensitive transparent resin solution has a non-volatile content of 20% by weight. Thus, cyclohexanone was added to prepare a photosensitive resin solution. The obtained (Binder resin solution 5) had an acid value of 13 mgKOH / g and a weight average molecular weight Mw of 20000.

(Binder resin solution 6)
480 parts of cyclohexanone is put in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 32.0 parts of methacrylic acid, 224.0 parts of methyl methacrylate, 16.0 parts of n-butyl methacrylate at the same temperature, 29.0 parts of benzyl methacrylate, 19.0 parts of lactylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), 15.0 parts of glycerol monomethacrylate, 2,2′-azobisisobutyronitrile 4 0.0 part of the mixture was added dropwise over 1 hour to carry out the polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 80 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin copolymer solution was obtained.
Next, with respect to 445 parts of the obtained transparent resin copolymer solution, a mixture of 14.0 parts of 2-methacryloylethyl isocyanate, 0.4 part of dibutyltin laurate and 55.0 parts of cyclohexanone was added at 70 ° C. It dripped over time and the photosensitive transparent resin solution was obtained. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution is sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The previously synthesized photosensitive transparent resin solution has a non-volatile content of 20% by weight. Thus, cyclohexanone was added to prepare a photosensitive resin solution. The resulting binder resin solution 6 had an acid value of 125 mg KOH / g weight average molecular weight Mw of 21,000.

(Binder resin solution 7)
Place 800 parts of propylene glycol monomethyl ether acetate in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube and stirrer in a separable four-necked flask, and heat to 120 ° C while injecting nitrogen gas into the vessel. 60 parts paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 40 parts methacrylic acid, 40 parts methyl methacrylate, 60 parts 2-hydroxyethyl methacrylate, and 2,2′-azobisiso A mixture of 4.0 parts of butyronitrile was added dropwise over 2 hours. After dropping, the mixture was further reacted at 80 ° C. for 4 hours, and then 45 parts of 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko KK) was added and further reacted at 60 ° C. for 8 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content was 20% by weight in the previously synthesized resin solution. The binder resin solution 7 was prepared by adding acetate. The acid value was 106 mgKOH / g, and the weight average molecular weight was 25000.

(Binder resin solution 8)
207 parts of cyclohexanone was charged into a reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. From the tube, 37.5 parts of methacrylic acid, 27.5 parts of methyl methacrylate, 5.0 parts of n-butyl methacrylate, 18.0 parts of 2-hydroxyethyl methacrylate and 1.33 of 2,2′-azobisisobutyronitrile Part of the mixture was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 12.0 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropping, the reaction was further continued for 1 hour to obtain an acrylic resin solution.
After cooling to room temperature, sample about 2 parts of the resin solution, heat dry at 180 ° C for 20 minutes, measure the nonvolatile content, and add cyclohexanone to the previously synthesized resin solution so that the nonvolatile content is 20 wt% Thus, a binder resin solution 8 was prepared. The acid value was 220 mgKOH / g, and the weight average molecular weight (Mw) was 17,600.

<Photopolymerizable monomer (C)>
Abbreviations are shown below.
(Polymerizable compound corresponding to general formula (i))
Polymerizable compound C1-1 having an acidic group:
Monoesterified product of dipentaerythritol pentaacrylate and succinic acid, dipentaerythritol hexaacrylate, and mixture of dipentaerythritol pentaacrylate (“TO-1382” manufactured by Toagosei Co., Ltd.)
Polyfunctional photocurable compounds C2-1 and C2-2 having an alkyleneoxy group having 2 or more carbon atoms
: Trimethylolpropane EO modified triacrylate (acrylic monomer having EO modified group
_{[CH 2 = CHCO- (OC 2} H 4) n -OCH 2] 3 -CCH 2 CH 3
(N≈2: “Aronix M-360” manufactured by Toa Gosei Co., Ltd.)
(N≈1: “Aronix M-350” manufactured by Toa Gosei Co., Ltd.)

A multifunctional photocurable compound having a number 2 or more alkyleneoxy group having a carbon C2-3,4: trimethylolpropane PO-modified triacrylate _{[CH 2 = CHCO- (OC 3} H 6) n -OCH 2] 3 - CCH ₂ CH ₃
(N≈2: “Aronix M-310” manufactured by Toagosei Co., Ltd.)
(N≈1: “Aronix M-321” manufactured by Toa Gosei Co., Ltd.)
(Polymerizable compound corresponding to general formula (ii))
C2-5 which is a polyfunctional photocurable compound having an alkyleneoxy group having 2 or more carbon atoms: Ethoxylated (4) pentaerythritol tetraacrylate (“SR-494” manufactured by Sakai Kogyo Co., Ltd.)
Dipentaerythritol hexaacrylate ("DPHA" manufactured by Daicel Chemical Industries)
(Polymerizable compound corresponding to general formula (iii))
A multifunctional photocurable compound having a number 2 or more alkyleneoxy group having a carbon C2-6: Example Compound _{1: [[CH 2 = CHCO-} (OC 2 H 4) n -OCH 2] 3 -C] 2 - O (total of n is 6)
C2-7 which is a polyfunctional photocurable compound having an alkyleneoxy group having 2 or more carbon atoms: Exemplified compound 2: [[CH ₂ ═CHCO— (OC ₂ H ₄ ) _n —OCH ₂ ] ₃ —C] ₂ — O (total of n is 12)
C2-8 which is a polyfunctional photocurable compound having an alkyleneoxy group having 2 or more carbon atoms: Exemplified compound 3: [[CH ₂ ═CHCO— (OC ₃ H ₆ ) _n —OCH ₂ ] ₃ —C] ₂ — O (total of n is 6)
A multifunctional photocurable compound having a number 2 or more alkyleneoxy group having a carbon C2-9: Example Compound _{4: [[CH 2 = CHCO-} (OC 3 H 6) n -OCH 2] 3 -C] 2 - O (total of n is 12)
Dipentaerythritol hexaacrylate ("Aronix M-402" manufactured by Toa Gosei Co., Ltd.)

[Example 1]
After stirring and mixing the following mixture uniformly, 1. It filtered with a 0 micrometer filter and obtained the coloring composition for color filters (R-1).
Magenta pigment dispersion: 67.6 parts Binder resin solution 1: 3.2 parts Polymerizable compound C1-1 having an acidic group
(“TO-1382” manufactured by Toagosei Co., Ltd.): 1.1 parts polyfunctional photocurable compound C2-1 having an alkyleneoxy group having 2 or more carbon atoms
("Aronix M-350" manufactured by Toagosei Co., Ltd.): 1.1 parts oxime ester photoinitiator 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)]
("OXE-01" manufactured by BASF): 0.2 part PGMAc: 26.9 parts

[Example 2]
The polyfunctional photocurable compound 1 having an alkyleneoxy group having 2 or more carbon atoms of [Example 1] is trimethylol which is C2-3 which is also a polyfunctional photocurable compound having an alkyleneoxy group having 2 or more carbon atoms. A color filter coloring composition (R-2) was obtained using the same method as in Example 1 except that it was changed to propane PO-modified triacrylate (“Aronix M-310” manufactured by Toagosei Co., Ltd.).

[Example 3]
The polyfunctional photocurable compound 1 having an alkyleneoxy group having 2 or more carbon atoms of [Example 1] is also trimethylol which is C2-4 which is a polyfunctional photocurable compound having an alkyleneoxy group having 2 or more carbon atoms. A colored filter composition (R-3) was obtained in the same manner as in Example 1 except that the propane PO-modified triacrylate (“Aronix M-321” manufactured by Toagosei Co., Ltd.) was used.
[Example 4]
The binder resin solution 1 of [Example 3] is the binder resin solution 2, and the polyfunctional photocurable compound C2-3 having an alkyleneoxy group having 2 or more carbon atoms is also used as the polyfunctional light having an alkyleneoxy group having 2 or more carbon atoms. A coloring composition for a color filter using the same method as in Example 3 except that it is changed to trimethylolpropane EO-modified triacrylate (“Aronix M-360” manufactured by Toagosei Co., Ltd.) which is C2-2 which is a curable compound. A product (R-4) was obtained.

[Example 8]
After stirring and mixing the following mixture uniformly, 1. It filtered with a 0 micrometer filter and obtained the coloring composition for color filters (R-8).
Magenta pigment dispersion: 67.6 parts Binder resin solution 6: 0.7 parts Epoxy compound
("Denacol EX-611" manufactured by Daicel Chemical Industries, Ltd.) 1.0 part polymerizable compound C1-1 having an acidic group
(“TO-1382” manufactured by Toagosei Co., Ltd.): 1.1 parts polyfunctional photocurable compound C2-1 having an alkyleneoxy group having 2 or more carbon atoms (“Aronix M-350” manufactured by Toagosei Co., Ltd.): 1 part photopolymerization initiator ("OXE-01" manufactured by BASF): 0.2 part PGMAc: 28.4 parts

[Example 9]
A colored composition for color filter (R-9) was used in the same manner as in Example 8 except that the epoxy compound of [Example 8] was changed to a melamine compound ("Nicalak MW-30" manufactured by Sanwa Chemical Co., Ltd.). )

[Example 18]
After stirring and mixing the following mixture uniformly, 1. It filtered with a 0 micrometer filter and obtained the coloring composition for color filters (R-18).
Magenta color pigment dispersion: 67.6 parts Binder resin solution 6: 5.7 parts Polymerizable compound C1-1 having an acidic group
(“TO-1382” manufactured by Toagosei Co., Ltd.): 1.1 parts polyfunctional photocurable compound C2-1 having an alkyleneoxy group having 2 or more carbon atoms (“Aronix M-350” manufactured by Toagosei Co., Ltd.): 1 part 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one ("Irgacure 907" manufactured by BASF): 0.2 part PGMAc: 28.4

[Examples 5-7, 10-17, 19-23, Comparative Examples 1-5
Hereinafter, it changed into the composition and the compounding quantity which are shown to Tables 1-4, and it carried out similarly to said R-1-4, and obtained the coloring composition (R-5-7, 10-16, 18-28) for color filters. .

<Evaluation of coloring composition for color filter>
About the coloring composition for color filters (R-1 to 28) obtained in the Examples and Comparative Examples, tests on developability and residue were performed by the following methods. In addition, (double-circle) is a very favorable level, (circle) is a favorable level, (triangle | delta) is a practical use level, and x is a level unsuitable for practical use. Further, in the residue evaluation, the pattern peeling is a level that is not suitable for practical use. The results are shown in Table 5.

(Developability)
The color filter coloring compositions obtained in Examples 1 to 23 and Comparative Examples 1 to 5 were spin-coated on a glass substrate using a spin coater so that the dry film thickness was 1.0 μm. Dry at 20 ° C. for 20 minutes.
2 ml of a 2% by weight aqueous potassium hydroxide solution was dropped onto the coating film, and the time until the coating thickness was dissolved was measured to evaluate the development rate of the colored composition. The rank of evaluation is as follows.
◎: Less than 10 seconds ○: 10 seconds or more, less than 15 seconds △: 15 seconds or more, less than 30 seconds ×: 30 seconds or more

(Residue)
The color filter coloring compositions obtained in Examples and Comparative Examples were spin-coated on a glass substrate using a spin coater so that the dry film thickness was 1.0 μm, and dried at 70 ° C. for 20 minutes. .
Next, the coated film after drying was exposed to 200 mJ / cm ² with an ultrahigh pressure mercury lamp having an illuminance of 30 mW / cm ² of i-line through a photomask in which a square pattern mask pattern of 6 μm was arranged.

  The pattern-exposed coating film was developed with a 2% by weight potassium hydroxide aqueous solution and then washed with pure water after developing an unexposed portion. Thereafter, water droplets were blown with high-pressure air, the substrate was naturally dried, and post-baked with a hot plate at 230 ° C. for 30 minutes to form a pattern on the glass substrate.

The colored composition pattern for a color filter produced by the above-described pattern peelability evaluation was cut out by glass cutting, and observed with a scanning electron microscope (S-4800, manufactured by Hitachi, Ltd.) at a magnification of 15,000 times. Evaluation was performed according to the following evaluation criteria.
○: No residue is found on the pattern with a line width of 6 μm. Δ: A slight residue is found on the pattern with a line width of 6 μm, but there is no problem in practical use. Pattern peeling: A pattern with a line width of 6 μm is peeled off, which is a practical problem.

  The coating film obtained with the coloring composition for color filter of [Example 1] to [Example 23] had both good pattern peelability and pattern formability. Example 6 using the binder resin 6 having an acid value of 125 mgKOH / g was particularly good.

  For [Comparative Example 1], the binder resin 4 having an acid value of 65 mgKOH / g is used, and for [Comparative Example 2], the binder resin 5 having an acid value of 13 mgKOH / g is used. Any residue was bad. Regarding [Comparative Example 3], since the binder resin 8 having an acid value of 220 mgKOH / g was used, the developability was very good, but pattern peeling occurred and no fine pattern remained. About [Comparative example 4], since Aronix M402 which is a polyfunctional photocurable compound which has neither an acidic group nor an alkyleneoxy group is used, the residue was bad. Regarding [Comparative Example 5], since no quinacridone pigment was used, the residue was bad.

From the above results, it contains a colorant, a binder resin having an acid value of 70 to 200 mgKOH / g or less, a polymerizable compound having an acidic group, and a polyfunctional photocurable compound having an alkyleneoxy group having 2 or more carbon atoms. The coloring composition for a color filter is excellent in developability and residue.

Claims (15)

A color composition for a color filter comprising a colorant (A), a binder resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E), wherein the colorant (A) Contains a quinacridone pigment, the binder resin (B) has an acid value of 70 to 200 mgKOH / g, and at least one selected from the following (B1-1), (B1-2), and (B1-3) A polymerizable compound (C1) having a photosensitive resin (B1), wherein the polymerizable compound (C) has an acidic group, and a polyfunctional photocurable compound (C2) having an alkyleneoxy group having 2 or more carbon atoms A coloring composition for color filters, comprising at least one selected from the group consisting of:
Binder resin (B1-1)
A resin obtained by reacting (c-1) with a copolymer obtained by copolymerizing the following (a-1) and (b-1), and then reacting (d) (a-1) : A monomer having a cyclic ether skeleton having 2 to 4 carbon atoms and an ethylenically unsaturated bond (b-1): having an unsaturated bond copolymerizable with (a-1), and (a-1) Are different monomers (c-1): at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (d): polybasic acid anhydride binder resins (B1-2)
Resin obtained by reacting (c-2) with a copolymer obtained by copolymerizing the following (a-2) and (b-2) (a-2): unsaturated carboxylic acid and unsaturated At least one selected from the group consisting of carboxylic anhydrides (b-2): a monomer having an unsaturated bond copolymerizable with (a-2) and different from (a-2) (c- 2): Monomer binder resin (B1-3) having a C2-C4 cyclic ether skeleton and an ethylenically unsaturated bond
Obtained by reacting the isocyanate group of (d-3) with the side chain hydroxyl group of the copolymer obtained by copolymerizing the following (a-3), (b-3) and (c-3) Resin (a-3): Ethylenically unsaturated monomer having a hydroxyl group (b-3): Unsaturated monobasic acid having a carboxyl group, which is a monomer different from (a-3) (c- 3): Monomer having an unsaturated bond copolymerizable with (a-3) and (b-3) and different from (a-3) and (b-3) (d-3): Isocyanate Ethylenically unsaturated monomer having a group Quinacridone pigments are C.I. I. The coloring composition for a color filter according to claim 1, which is CI Pigment Red 122. The photosensitive resin (B1) contains (B1-1) and / or (B1-2), and (b-1) and / or (b-2) is selected from a tricyclodecane skeleton and a tricyclodecene skeleton The coloring composition for color filters according to claim 1, comprising a compound having at least one kind of skeleton and an ethylenically unsaturated bond. Photosensitive resin (B1) contains (B1-3), (a-3) is hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, poly (alkyleneoxy) The coloring composition for a color filter according to any one of claims 1 to 3, wherein the coloring composition is at least one selected from the group consisting of (meth) acrylates and poly (alkyleneoxycarbonyl) (meth) acrylates. The coloring composition for a color filter according to any one of claims 1 to 4, wherein the photosensitive resin (B1) is 30 to 80 parts by weight in 100 parts by weight of the binder resin (B). The polyfunctional photocurable compound (C2) having an alkyleneoxy group having 2 or more carbon atoms has 3 or more photocurable functional groups and an alkyleneoxy group having 2 or 3 carbon atoms. The coloring composition for a color filter according to any one of claims 1 to 5. The polyfunctional photocurable compound (C2) having an alkyleneoxy group having 2 or more carbon atoms contains at least one selected from a pentaerythritol derivative, a dipentaerythritol derivative and a trimethylolpropane derivative. The coloring composition for color filters of any one of -6. The polyfunctional photocurable compound (C2) having an alkyleneoxy group having 2 or more carbon atoms contains at least one selected from the compounds represented by the general formulas (i), (ii) and (iii) The coloring composition for a color filter according to any one of claims 1 to 7.

Formula _{(i) X-C- [CH} 2 -O- (Y) n -Z 1] 3
General formula (ii) C— [CH ₂ —O— (Y) _n —Z ₁ ] ₄
General formula (iii)

[In General Formulas (i), (ii) and (iii), X is an alkyl group having 2 to 10 carbon atoms, Y is each independently an alkyleneoxy group having 1 to 10 carbon atoms, Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ and Z _{6 each} represents a hydrogen atom, an acryloyl group or a methacryloyl group. In general formula (i), the sum total of an acryloyl group and a methacryloyl group is three, n represents the integer of 0-10 each independently, and the sum total of n in a molecule | numerator is an integer of 1-30. In general formula (ii), the sum total of acryloyl group and methacryloyl group is four, n represents the integer of 0-10 each independently, and the sum total of n in a molecule | numerator is an integer of 1-40. In general formula (iii), the sum total of the acryloyl group and the methacryloyl group is 5 or 6, each n independently represents an integer of 0 to 10, and the sum of n in the molecule is an integer of 1 to 60. is there. ] The coloring composition for a color filter according to any one of claims 1 to 8, further comprising a pigment derivative (F) and / or a dispersant (G). The coloring composition for a color filter according to any one of claims 1 to 9, wherein the polymerization initiator (D) is an oxime ester photopolymerization initiator. 11. The ratio I / M between the weight I of the polymerization initiator (D) and the weight M of the polymerizable compound (C) is 0.01 to 0.20. The coloring composition for color filters as described in above. The ratio M / P between the weight M of the polymerizable compound (C) and the weight P of the binder resin (B) is 0.30 to 0.50, according to any one of claims 1 to 11, The coloring composition for color filters as described. Furthermore, the thermosetting compound (H) is contained, The coloring composition for color filters of any one of Claims 1-12 characterized by the above-mentioned. The coloring composition for a color filter according to claim 13, wherein the thermosetting compound (H) is an epoxy compound or a melamine compound. The color filter formed using the coloring composition for color filters of any one of Claims 1-14.