JP7363388B2 - Green colored composition, photosensitive green colored composition, color filter, and liquid crystal display device - Google Patents

Description

The present invention relates to a green coloring composition and a photosensitive green coloring composition used for manufacturing color filters used in color liquid crystal display devices, color solid-state image sensors, organic EL display devices, quantum dot display devices, electronic paper, etc. The present invention relates to a color filter having a filter segment formed using the same, and a color liquid crystal display device.

A color filter is formed by arranging two or more types of fine band-shaped filter segments with different hues in parallel (in stripes) or across each other on a transparent substrate such as a glass substrate, or Two or more types of fine filter segments having different values are arranged in order in each of the vertical and horizontal directions. The filter segments have small dimensions ranging from several microns to several hundred microns, and are neatly arranged in a predetermined arrangement for each hue.

Currently, the mainstream method for manufacturing color filters is a method called a pigment dispersion method, which uses pigments with excellent resistance such as light resistance and heat resistance as colorants. In addition, in the pigment dispersion method, a color filter is manufactured by the following method. First, a photosensitive coloring composition (pigment resist) made by dispersing a pigment in a photosensitive transparent resin solution is applied to a transparent substrate such as glass. After drying to remove the solvent from the coating, the coating is exposed in a pattern corresponding to the filter segments of a certain color. Next, the unexposed areas of this coating film are removed by development, and then, if necessary, a treatment such as heating is performed. As a result, a filter segment pattern of the first color is obtained. Then, by performing a similar operation to this, filter segment patterns of other colors are formed to complete a color filter.

High-resolution color filters formed by fine pixels are required to have even higher quality in terms of pixel shape and solvent resistance. A photosensitive coloring composition is disclosed that can produce pixels without pattern defects in pixel portions by combining functional monomers.
Further, Patent Document 2 discloses a photosensitive coloring composition that can produce pixels with high solvent resistance by using a specific resin-type dispersant.

Japanese Patent Application Publication No. 2012-247590 Japanese Patent Application Publication No. 2017-058652

The present invention uses a resin-type dispersant with a specific structure and performance to create a green coloring composition that has a viscosity suitable for coating and has excellent viscosity stability, a fast development speed, and viscosity stability. It is an object of the present invention to provide a photosensitive green coloring composition having excellent properties, less foreign matter, and excellent solvent resistance, as well as a color filter and a color liquid crystal display device formed using the photosensitive green coloring composition.

（但し、一般式（２）において、Ｒ^５及びＲ^６はそれぞれ独立に、水素原子、水酸基、炭素数１～２０の直鎖、分岐鎖又は環状のアルキル基、ビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは－Ｏ－Ｒ^１１を表し、Ｒ^１１は、炭素数１～２０の直鎖、分岐鎖又は環状のアルキル基、ビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは炭素数１～４のアルキレン基を介した（メタ）アクリロイル基を表す。但し、Ｒ^５及びＲ^６の少なくとも一つは炭素原子を含む。
一般式（３）において、Ｒ^７は、炭素数１～２０の直鎖、分岐鎖又は環状のアルキル基、ビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは－Ｏ－Ｒ^１１を表し、 Ｒ^１１は、炭素数１～２０の直鎖、分岐鎖又は環状のアルキル基、ビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは炭素数１～４のアルキレン基を介した（メタ）アクリロイル基を表す。
一般式（４）において、Ｒ⁸、Ｒ⁹、及びＲ¹⁰はそれぞれ独立に、水素原子、酸性基又はそのエステル基、置換基を有してもよい炭素数１～２０の直鎖、分岐鎖又は環状のアルキル基、置換基を有してもよいビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは－Ｏ－Ｒ¹²を表し、Ｒ¹²は、置換基を有してもよい炭素数１～２０の直鎖、分岐鎖又は環状のアルキル基、置換基を有してもよいビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは炭素数１～４のアルキレン基を介した（メタ）アクリロイル基を表し、Ｘは、塩素原子、臭素原子、又はヨウ素原子を表す。） The present invention is a green colored composition containing a phthalocyanine pigment (A), a resin-type dispersant (B), and a binder resin (C), wherein the phthalocyanine pigment contains an aluminum phthalocyanine pigment (A1) and a halogenated contains one or more pigments selected from zinc phthalocyanine pigments (A2), and the resin-type dispersant contains a block copolymer,
A green colored composition characterized in that the block copolymer contains a block copolymer (B1) containing at least one kind of structural unit selected from the group consisting of the following structural units (I) and (II). relating to things.
(I) A structural unit represented by the following general formula (1) and at least one selected from the group consisting of compounds represented by the following general formula (2) and general formula (3) form a salt. Constituent unit.
(II) A structural unit obtained by converting a structural unit represented by the following general formula (1) into a quaternary salt with a compound represented by general formula (4).

General formula (1)
(However, in general formula (1), R ¹ and R ² are each independently a hydrogen atom or a methyl group, A is an alkylene group having 1 to 8 carbon atoms, -[CH(R ^a )-CH(R ^b )-O]x-CH(R ^a )-CH(R ^b )- or [(CH ₂ )y-O]z-(CH ₂ )y-, R ³ and R ⁴ are , each independently represents a hydrogen atom or a hydrocarbon group that may contain a heteroatom, and R ³ and R ⁴ may be combined with each other to form a ring structure. R ^a and R ^b each independently represent is a hydrogen atom or a methyl group, x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18.)

(However, in general formula (2), R ⁵ and R ⁶ each independently have a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, or a substituent. represents a phenyl group or benzyl group, or -O-R ¹¹ , which may have a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group ^, or a substituent. It represents a phenyl group, a benzyl group, or a (meth)acryloyl group via an alkylene group having 1 to 4 carbon atoms.However, at least one of R ⁵ and R ⁶ contains a carbon atom.
In the general formula (3), R ⁷ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have a substituent, or -O-R ¹¹ , R ¹¹ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have a substituent, or an alkylene having 1 to 4 carbon atoms. Represents a (meth)acryloyl group via a group.
In the general formula (4), R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an acidic group or an ester group thereof, a straight chain or branched chain having 1 to 20 carbon atoms which may have a substituent. or a cyclic alkyl group, a vinyl group which may have a substituent, a phenyl group or a benzyl group which may have a substituent, or -O-R ¹² , where R ¹² is a group which may have a substituent A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group which may have a substituent, a phenyl group or benzyl group which may have a substituent, or a C1 to 4 alkyl group. represents a (meth)acryloyl group via an alkylene group, and X represents a chlorine atom, a bromine atom, or an iodine atom. )

Furthermore, the present invention relates to the green colored composition described above, which further contains a yellow pigment (A3).

The present invention also relates to a photosensitive green colored composition containing the above colored composition, a polymerizable compound (D), and a photopolymerization initiator (E).

The present invention also relates to a color filter including filter segments formed using the photosensitive green colored composition.

The present invention also relates to a liquid crystal display device including the color filter described above.

According to the present invention, a green coloring composition having a viscosity suitable for coating and excellent viscosity stability, a photosensitive green coloring having a fast development speed, excellent viscosity stability, little foreign matter, and excellent solvent resistance. It is possible to provide a composition, a color filter including a filter segment formed using the photosensitive green colored composition, and a color liquid crystal display device.

FIG. 1 is a schematic cross-sectional view of a liquid crystal display device.

Each component of the green coloring composition of the present invention will be explained below.
In addition, in this application, when expressed as "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide", special explanation will be given. "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide and/or methacrylamide", respectively, unless otherwise specified. shall be expressed.
Moreover, "C.I." mentioned in this specification means color index (C.I.).

The phthalocyanine pigment (A) contains at least one pigment selected from the group consisting of an aluminum phthalocyanine pigment (A1) and a halogenated zinc phthalocyanine pigment (A2).

<Phthalocyanine pigment (A)>
The phthalocyanine pigment (A) contains at least one pigment selected from the group consisting of an aluminum phthalocyanine pigment (A1) and a halogenated zinc phthalocyanine pigment (A2). The green colored composition may contain other organic pigments, inorganic pigments, dyes, etc. in order to obtain good optical properties. It is preferable that the green colored composition of the present invention uses together a yellow pigment (A3), which will be described later.

<Aluminum phthalocyanine pigment (A1)>
The aluminum phthalocyanine pigment (A1) is a phthalocyanine pigment having an aluminum atom in the central metal. As the aluminum phthalocyanine pigment (A1), for example, the pigment described in JP-A-2017-111398 is preferable.

<Halogenated zinc phthalocyanine pigment (A2)>
The halogenated zinc phthalocyanine pigment (A2) is a phthalocyanine pigment having a zinc atom as a central metal and a halogen atom as a substituent. For example, the halogenated zinc phthalocyanine pigment (A2) preferably has an average number of 10 to 14 halogen atoms in the molecule, and the halogen atoms have an average number of bromine atoms of 8 to 12 and an average number of chlorine atoms of 2 to 5. Preferred are halogenated zinc phthalocyanines. In order to obtain a high degree of color reproduction, the number of halogen atoms in the molecule is preferably 11 to 13 on average, and the halogen atoms preferably have an average of 8 to 11 bromine atoms, and more preferably an average of 2 to 3 chlorine atoms. . Note that the halogenated zinc phthalocyanine pigment is a pigment composition having a halogen distribution, and the average composition is determined by fluorescent X-ray analysis.

(Yellow pigment (A3))
Yellow pigments include, for example, 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, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233 and the like. Among these, C. I. Pigment Yellow 138,231,233, a pigment described in JP-A-2012-226110 is preferred.

(Other organic pigments)
The red pigment is, for example, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81: 3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296 and the like.

Blue pigments include, for example, 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.

The purple pigment is, for example, 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, etc.

Green pigments include, for example, C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55 and the like.

Inorganic pigments include, for example, titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine blue, deep blue, chromium oxide green, cobalt green, and amber. , synthetic iron black, etc.

<Dye>
As the dye, any of acid dyes, direct dyes, basic dyes, salt dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. can be used. Further, it may be in the form of a lake pigment obtained by forming a lake of these derivatives or dyes.

Furthermore, in the case of acid dyes having acidic groups such as sulfonic acid or carboxylic acid, or in the form of direct dyes, inorganic salts of acid dyes, acid dyes and quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, Or salt-forming compounds with nitrogen-containing compounds such as primary amine compounds, or salt-forming compounds using resin components having these functional groups, or sulfonamidation and use as sulfonic acid amide compounds. This is preferable because it provides a colored composition with excellent fastness.
Further, a salt-forming compound of an acidic dye and a compound having an onium base is also preferable because it has excellent fastness, and more preferably, the compound having an onium base is a resin having a cationic group in the side chain.

In the case of a basic dye, it can be used by forming a salt using an organic acid, perchloric acid, or a metal salt thereof. Among these, salt-forming compounds of basic dyes are preferred because of their excellent resistance and compatibility with pigments, and basic dyes and counter components that act as counter ions, such as organic sulfonic acids, organic sulfuric acids, and fluorine-containing phosphorus, are preferred. It is possible to use a salt-forming compound obtained by forming a salt with an anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or an acid dye. This is more preferable.

Further, when the dye skeleton has a polymerizable unsaturated group, the dye can have excellent resistance, which is preferable.

The chemical structure of dyes includes, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, etc.). dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes Dyes, polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone Examples include dye structures derived from dyes selected from dyes such as dyes based on dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and metal complex dyes thereof.

Among these pigment structures, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium It is preferable to have a pigment structure derived from a dye selected from dyes such as quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes, such as xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes. A dye structure derived from a dye selected from dyes is more preferable. For specific pigment compounds that can form pigment structures, see the "New Edition Dye Handbook" (edited by the Organic Synthetic Chemistry Society; Maruzen, 1970), the "Color Index" (The Society of Dyers and Colourists), and the "Pigment Handbook" (Okawara et al. Kodansha, 1986).

<Refining of pigments>
It is preferable to use the pigment used in the coloring composition of the present invention in a finely divided form, and the method for making it fine is not particularly limited. As exemplified in , it is possible to perform a salt milling process using a kneader method, which is a type of wet grinding, to make the material fine. The average primary particle diameter of the pigment determined by TEM (transmission electron microscope) is preferably in the range of 10 to 80 nm. When it is smaller than 10 nm, it becomes difficult to disperse in an organic solvent, and when it is larger than 80 nm, it may not be possible to obtain a sufficient contrast ratio. For these reasons, the more preferable average primary particle diameter is in the range of 15 to 70 nm.

Salt milling is a process in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is milled using a batch or continuous process such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, sand mill, or planetary mixer. This is a process in which the mixture is mechanically kneaded using a kneader while being heated, and then water-soluble inorganic salts and water-soluble organic solvents are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling. By optimizing the conditions for salt milling pigments, it is possible to obtain pigments with very fine primary particle diameters, narrow distribution widths, and sharp particle size distributions.

As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate, etc. can be used, but it is preferable to use sodium chloride (common salt) from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2,000 parts by mass, most preferably 300 to 1,000 parts by mass, per 100 parts by mass of the pigment, from the viewpoint of both processing efficiency and production efficiency.

The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent is likely to evaporate, a high boiling point solvent with a boiling point of 120° C. or higher is preferred from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, most preferably 50 to 500 parts by weight, per 100 parts by weight of the pigment.

When salt milling the pigment, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, etc. can be used. The resin used is preferably solid at room temperature and insoluble in water, and more preferably partially soluble in the above organic solvent. The amount of resin used is preferably in the range of 5 to 200 parts by weight per 100 parts by weight of the pigment.

<Resin type dispersant (B)>
The resin type dispersant (B) of the present invention contains a block copolymer,
The block copolymer is characterized in that it contains a block copolymer (B1) containing at least one kind of structural unit selected from the group consisting of the following structural units (I) and (II).
(I) A structural unit represented by the following general formula (1) and at least one selected from the group consisting of compounds represented by the following general formula (2) and general formula (3) form a salt. Constituent unit.
(II) A structural unit obtained by converting a structural unit represented by the following general formula (1) into a quaternary salt with a compound represented by general formula (4).

General formula (1)
(However, in general formula (1), R ¹ and R ² are each independently a hydrogen atom or a methyl group, A is an alkylene group having 1 to 8 carbon atoms, -[CH(R ^a )-CH(R ^b )-O]x-CH(R ^a )-CH(R ^b )- or [(CH ₂ )y-O]z-(CH ₂ )y-, R ³ and R ⁴ are , each independently represents a hydrogen atom or a hydrocarbon group that may contain a heteroatom, and R ³ and R ⁴ may be combined with each other to form a ring structure. R ^a and R ^b each independently represent is a hydrogen atom or a methyl group, x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18.)

(However, in general formula (2), R ⁵ and R ⁶ each independently have a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, or a substituent. represents a phenyl group or benzyl group, or -O-R ¹¹ , which may have a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group ^, or a substituent. It represents a phenyl group, a benzyl group, or a (meth)acryloyl group via an alkylene group having 1 to 4 carbon atoms.However, at least one of R ⁵ and R ⁶ contains a carbon atom.
In the general formula (3), R ⁷ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have a substituent, or -O-R ¹¹ , R ¹¹ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have a substituent, or an alkylene having 1 to 4 carbon atoms. Represents a (meth)acryloyl group via a group.
In the general formula (4), R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an acidic group or an ester group thereof, a straight chain or branched chain having 1 to 20 carbon atoms which may have a substituent. or a cyclic alkyl group, a vinyl group which may have a substituent, a phenyl group or a benzyl group which may have a substituent, or -O-R ¹² , where R ¹² is a group which may have a substituent A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group which may have a substituent, a phenyl group or benzyl group which may have a substituent, or a C1 to 4 alkyl group. represents a (meth)acryloyl group via an alkylene group, and X represents a chlorine atom, a bromine atom, or an iodine atom. )

<Block polymer (B1)>
The block polymer (B1) is usually obtained by salt formation or quaternary salting of a block copolymer containing the structural unit represented by the general formula (1), and is represented by the general formula (1). The block copolymer containing the structural unit generally includes a block containing the structural unit represented by the general formula (1) and a block having solvent affinity. The block copolymer having such a structure functions as a coloring material dispersant, with a block adsorbing the coloring material and a block having solvent affinity sharing the functions.

<Block containing the structural unit represented by general formula (1): Colorant adsorption functional block>
The structural unit represented by general formula (1) has basicity and functions as an adsorption site for the coloring material. Furthermore, in the present invention, at least a part of the terminal nitrogen moiety possessed by the structural unit represented by the general formula (1) and one or more members selected from the group consisting of the general formulas (2) to (4) By forming a salt with the compound or converting into a quaternary salt, the site functions as a stronger adsorption site for the coloring material. The structural unit represented by the general formula (1) is highly basic since it particularly contains an amide bond, and is presumed to have a further enhanced ability to adsorb the coloring material.

Examples of monomers for forming the structural unit represented by the above general formula (1) include dialkylaminoalkyl (meth)acrylamides such as dimethylaminoethyl (meth)acrylamide and dimethylaminopropyl (meth)acrylamide; Examples include, but are not limited to, (meth)acrylamide containing a group-substituted amino group. From the viewpoint of compatibility with other components, alkyl group-substituted amino group-containing methacrylamides such as dialkylaminoalkyl methacrylamides are preferred.
The structural unit represented by general formula (1) may consist of one type, or may contain two or more types of structural units.

It is preferable that three or more of the structural units represented by the general formula (1) are included in the block having a coloring material adsorption function that includes the structural units represented by the general formula (1). Among these, from the viewpoint of improving dispersibility and dispersion stability, it is preferable to contain 3 to 100 pieces, more preferably 3 to 50 pieces, and even more preferably 3 to 30 pieces.

In the block copolymer having the structural unit represented by the general formula (1), the content of the structural unit represented by the general formula (1) is preferably 5% by mass to 90% by mass, and 10% by mass to 80% by mass. Mass % is more preferred.

Furthermore, within the scope of achieving the object of the present invention, it may have a structural unit other than the structural unit represented by general formula (1), and it may be copolymerized with the structural unit represented by general formula (1). Any possible structural unit can be contained. For example, structural units having a basic group other than the structural unit represented by general formula (1) such as alkyl group-substituted amino group-containing (meth)acrylates and 1-vinylimidazole, and structural units described below can be used. , specifically, for example, a structural unit represented by the general formula (5) described below.

<Block with solvent affinity>
The block having solvent affinity is a block that does not contain the structural unit represented by the general formula (1) and functions as a solvent affinity site. For example, from among monomers having unsaturated double bonds that are copolymerizable with the monomer inducing the structural unit represented by general formula (1), appropriate selection is made depending on the solvent so as to have solvent affinity. It is preferably used, and examples thereof include a structural unit represented by the following general formula (5).

General formula (5)
(In general formula (5), A' is a direct bond or a divalent linking group, R ¹³ is a hydrogen atom or a methyl group, R ¹⁴ is a hydrocarbon group, -[CH(R ¹⁵ )-CH(R ¹⁶ )-O]x-R ¹⁷ or -[(CH ₂ )y-O]z-R ^17. R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or a methyl group. R ¹⁷ is a hydrogen atom, a hydrocarbon group, -CHO, -CH ₂ CHO, or a monovalent group represented by -CH ₂ COOR ¹⁸ , and R ¹⁸ is a hydrogen atom or a group having 1 to 5 carbon atoms. It is an alkyl group.
The above hydrocarbon group may have a substituent.
x is an integer from 1 to 18, y is an integer from 1 to 5, and z is an integer from 1 to 18. )

In general formula (5), A' is a direct bond or a divalent linking group. A direct bond means that A' does not have an atom, that is, C (carbon atom) in general formula (5) and R ¹⁴ are bonded without using another atom.
Examples of the divalent linking group for A' include an alkylene group having 1 to 10 carbon atoms, an arylene group, a -CONH- group, a -COO- group, an ether group having 1 to 10 carbon atoms (-R'- OR"-: R' and R" each independently represent an alkylene group) and combinations thereof.
Among these, from the viewpoint of dispersibility, A' in general formula (5) is preferably a divalent linking group containing a direct bond, a -CONH- group, or a -COO- group.

In general formula (5), R ¹⁴ is a hydrocarbon group, -[CH(R ¹⁵ )-CH(R ¹⁶ )-O]x-R ¹⁷ or -[(CH ₂ )y-O]z-R ¹⁷ shows.
The hydrocarbon group for R ¹⁴ is preferably an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group.
The alkyl group having 1 to 18 carbon atoms may be linear, branched, or cyclic, and includes, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, Examples include -ethylhexyl group, 2-ethoxyethyl group, cyclopentyl group, cyclohexyl group, bornyl group, isobornyl group, dicyclopentanyl group, dicyclopentenyl group, adamantyl group, and lower alkyl group-substituted adamantyl group.
The above alkenyl group having 2 to 18 carbon atoms may be linear, branched, or cyclic. Examples of such alkenyl groups include vinyl, allyl, and propenyl groups. Although there is no limitation on the position of the double bond in the alkenyl group, from the viewpoint of the reactivity of the obtained polymer, it is preferable that the double bond is located at the terminal of the alkenyl group.
Examples of substituents for aliphatic hydrocarbons such as alkyl groups and alkenyl groups include nitro groups and halogen atoms.

Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, and may further have a substituent. The number of carbon atoms in the aryl group is preferably 6 to 24, more preferably 6 to 12.
Further, examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, and may further have a substituent. The number of carbon atoms in the aralkyl group is preferably 7 to 20, more preferably 7 to 14.
Examples of substituents on aromatic rings such as aryl groups and aralkyl groups include linear and branched alkyl groups having 1 to 4 carbon atoms, as well as alkenyl groups, nitro groups, and halogen atoms.
Note that the above preferred number of carbon atoms does not include the number of carbon atoms of substituents.

In R ¹⁴ above, x is an integer of 1 to 18, preferably an integer of 1 to 4, more preferably an integer of 1 to 2, and y is an integer of 1 to 5, preferably an integer of 1 to 4, more preferably is 2 or 3. z is an integer of 1 to 18, preferably an integer of 1 to 4, more preferably an integer of 1 to 2.

The hydrocarbon group for R ¹⁷ above can be the same as that shown for R ¹⁴ above. R ¹⁸ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and may be linear, branched, or cyclic.

The above ^R14 is preferably selected so as to have excellent compatibility with the solvent described below. Specifically, for example, the above-mentioned solvent is generally used as a solvent for colored resin compositions for color filters. When using glycol ether acetate, ether, or ester solvents, methyl, ethyl, isobutyl, n-butyl, 2-ethylhexyl, benzyl, and the like are preferred.

Furthermore, R ¹⁴ may be substituted with a substituent such as an alkoxy group, a hydroxyl group, an epoxy group, an isocyanate group, etc., within a range that does not impede the dispersion performance of the block copolymer. After synthesis of the polymer, the above substituent may be added by reacting with a compound having the above substituent.

Although the number of structural units constituting this block is not particularly limited, it is preferably 10 to 300 units in order for the solvent-philic part and the color-parent part to work effectively and improve the dispersibility of the coloring material. The number is preferably 10 to 100, more preferably 10 to 70.

<Compounds represented by the following general formulas (2) to (4)>
Examples of the compound represented by the general formula (2) include monobutyl phosphoric acid, dibutyl phosphoric acid, methyl phosphoric acid, dibenzyl phosphoric acid, diphenyl phosphoric acid, phenylphosphinic acid, phenylphosphonic acid, dimethacryloyloxyethyl acid phosphate, etc. .

Examples of the compound represented by the general formula (3) include benzenesulfonic acid, vinylsulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, monomethyl sulfate, monoethyl sulfate, mono-n-propyl sulfate, and the like. Note that a hydrate such as p-toluenesulfonic acid monohydrate may also be used.

Examples of the compound represented by the general formula (4) include methyl chloride, methyl bromide, ethyl chloride, ethyl bromide, methyl iodide, ethyl iodide, n-butyl chloride, hexyl chloride, octyl chloride, dodecyl chloride, Tetradecyl chloride, hexadecyl chloride, phenethyl chloride, benzyl chloride, benzyl bromide, benzyl iodide, chlorobenzene, α-chlorophenylacetic acid, α-bromophenylacetic acid, α-iodophenylacetic acid, 4-chloromethylbenzoic acid, 4-bromomethyl Examples include benzoic acid, 4-iodophenylbenzoic acid, chloroacetic acid, bromoacetic acid, iodoacetic acid, methyl α-bromophenyl acetate, 3-(bromomethyl)phenylboronic acid, and the like.

Among the compounds represented by the general formulas (2) to (4), phenylphosphinic acid, phenylphosphonic acid, dimethacryloyloxyethyl acid phosphate, dibutyl phosphoric acid, benzyl chloride, benzyl One or more selected from the group consisting of bromide, vinylsulfonic acid, and p-toluenesulfonic acid monohydrate are preferred, and among them, phenylphosphinic acid, phenylphosphonic acid, benzylbromide, vinylsulfonic acid, and p-toluene It is preferable to use one or more selected from the group consisting of sulfonic acid monohydrate.

The method for preparing the block copolymer (B1) includes adding one or more compounds selected from the group consisting of the general formulas (2) to (4) to a solvent in which the block copolymer is dissolved or dispersed. Examples include a method of adding, stirring, and further heating if necessary.

In addition, salt formation or quaternization between the structural unit represented by the general formula (1) and the compounds represented by the general formulas (2) to (4) can be carried out, for example, through a plurality of steps. It is also possible to form salts with multiple types of compounds represented by (2) to (4), or to quaternize them. For example, the remaining unquaternized portion after quaternization in (4) may be used. Salt formation may be performed by (2) or (3).
<Other resin-type dispersants>
Known resin-type dispersants can be used in the colored composition of the present invention. The resin-type dispersant has a colorant affinity site that has the property of adsorbing to the added colorant and a site that is compatible with the colorant carrier, and has a colorant affinity site that has the property of adsorbing to the added colorant and a site that is compatible with the colorant carrier. Any substance may be used as long as it has the function of stabilizing it, and specifically, urethane dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amines, etc. salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, poly(lower alkyleneimine) and free carboxyl groups. Oil-based dispersants such as amides and their salts formed by reaction with polyesters having Water-soluble resins such as acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone, water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide/propylene oxide adducts, phosphate esters, etc. are used, and these These can be used alone or in combination of two or more.
Examples of polymeric dispersants having basic functional groups include nitrogen atom-containing graft copolymers and nitrogen atom-containing polymers having functional groups such as tertiary amino groups, quaternary ammonium bases, and nitrogen-containing heterocycles in their side chains. Examples include acrylic block copolymers and urethane polymer dispersants.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167 manufactured by BYK Chemie Japan. , 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti - SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 1 manufactured by Japan Lubrizol, such as Terra-U, 203, 204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS or Bykumen. 6000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 5 3095, 55000, 56000, 76500 etc. 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, 1101, 120, 150, 1501, 1502, 1503, etc. manufactured by Ajinomoto Fine Techno Co., Ltd. Examples include Ajisper PA111, PB711, PB821, PB822, PB824, and the like.

The resin-type dispersant (B) is preferably used in an amount of about 3 to 200% by mass based on the phthalocyanine pigment (A), and more preferably about 5 to 100% by mass from the viewpoint of dispersion stability.

<Dye derivative (b0)>
A pigment derivative (b0) is added to the colored composition used in the present invention, if necessary.
As the dye derivative used in the present invention, known dye derivatives having an acidic group, basic group, neutral group, etc. in the organic dye residue can be used. For example, compounds with acidic substituents such as sulfo groups, carboxyl groups, and phosphoric acid groups, and their amine salts; compounds with basic substituents such as sulfonamide groups and terminal tertiary amino groups; phenyl groups and phthalimide. Examples include compounds having a neutral substituent such as an alkyl group. Since the resin type dispersant used in combination has an acidic group, a dye derivative having a basic group is preferable.
Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, and benzene pigments. Examples include indole pigments such as isoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo. It will be done.

Specifically, the diketopyrrolopyrrole dye derivatives include JP2001-220520A, WO2009/081930 pamphlet, WO2011/052617 pamphlet, WO2012/102399 pamphlet, JP2017-156397A, phthalocyanine. Examples of pigment derivatives include JP-A No. 2007-226161, WO 2016/163351 pamphlet, JP-A 2017-165820, and Japanese Patent No. 5753266; examples of anthraquinone-based pigment derivatives include JP-A No. 63-264674; JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009/025325 pamphlet, and as quinacridone dye derivatives, JP-A-1972- 54128, JP 03-9961, JP 2000-273383, dioxazine dye derivatives, JP 2011-162662, thiazine indigo dye derivatives, JP 2007-314785. Publications, triazine dye derivatives include JP-A-61-246261, JP-A-11-199796, JP-A 2003-165922, JP-A 2003-168208, JP-A 2004-217842, JP2007-314681A, benzisoindole dye derivatives in JP2009-57478A, quinophthalone dye derivatives in JP2003-167112A, JP2006-291194A, JP2006-291194A, 2008-31281, JP 2012-226110, naphthol dye derivatives, JP 2012-208329, JP 2014-5439, azo dye derivatives, JP 2001-172520 Publication, JP 2012-172092, Acidic substituent, JP 2004-307854, Basic substituent, JP 2002-201377, JP 2003-171594, JP 2005 Examples include known dye derivatives described in JP-A-181383, JP-A-2005-213404, and the like. In addition, in these documents, dye derivatives are sometimes described as derivatives, pigment derivatives, dispersants, pigment dispersants, or simply compounds, but the above-mentioned organic dye residues contain acidic groups, basic groups, neutral groups, etc. A compound having a substituent such as a functional group has the same meaning as a dye derivative.

<Binder resin (C)>
The colored composition of the present invention contains a binder resin (C). As the binder resin (C), a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength range of 400 to 700 nm is used. Binder resins are categorized by their main curing method, including thermoplastic resins, thermosetting resins, and active energy ray-curable resins containing ethylenically unsaturated double bonds.Active energy ray-curable resins are thermoplastic resins. The resin may also have a thermosetting function, and from the viewpoint of developability, an alkali-soluble resin is preferable. Further, it may contain a thermoplastic resin that is not curable with active energy rays, and it is also preferable that this resin is alkali-soluble. These can be used alone or in combination of two or more.

The content of the binder resin in the coloring composition of the present invention is preferably 20 to 400 parts by weight, more preferably 50 to 250 parts by weight, based on the total weight of the coloring material (100 parts by weight). It is preferably used in an amount of 20 parts by mass or more because it has good film forming properties and various resistances, and it is preferably used in an amount of 400 parts by mass or less because it has a high coloring material concentration and can express good color characteristics. .

<Thermoplastic resin>
Examples of thermoplastic resins that can be used as the binder resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, Polyvinyl acetate, polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, cellulose, polyethylene (HDPE, LDPE), polybutadiene, polyimide resin, etc. can be mentioned.
The thermoplastic resin is preferably alkali-soluble, and examples thereof include resins having acidic groups such as carboxyl groups and sulfone groups. Specifically, the resin includes an acrylic resin having an acidic group, an α-olefin/(anhydrous) maleic acid copolymer, a styrene/styrene sulfonic acid copolymer, an ethylene/(meth)acrylic acid copolymer, or an isobutylene/(meth)acrylic acid copolymer. Examples include (anhydrous) maleic acid copolymers. Among them, at least one resin selected from acrylic resins having acidic groups and styrene/styrene sulfonic acid copolymers, especially alkali-soluble resins having acidic groups and/or hydroxyl groups, has good developability, heat resistance, and transparency. Since it is expensive, it is preferably used.

<Alkali-soluble resin>
The colored composition of the present invention preferably contains an alkali-soluble resin from the viewpoint of developability, heat resistance, and transparency. It is used to impart development solubility in the alkaline development step during the production of color filters, and has acid groups and/or hydroxyl groups. Moreover, in order to further improve photosensitivity, it is more preferable to use a resin having an ethylenically unsaturated double bond.

<Alkali-soluble resin having ethylenically unsaturated double bonds>
It is preferable that the alkali-soluble resin contained in the coloring composition of the present invention has an ethylenically unsaturated double bond. In particular, by using a resin into which ethylenically unsaturated double bonds are introduced by methods (i) and (ii) shown below, the resin can be three-dimensionally crosslinked when exposed to active energy rays to form a coating film. This increases the crosslinking density and improves chemical resistance.

[Method (i)]
As method (i), for example, the side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other monomers is used. , the carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond is subjected to an addition reaction, and the generated hydroxyl group is further reacted with a polybasic acid anhydride to form an ethylenically unsaturated double bond and a carboxyl group. There is a way to introduce it.

Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, and 3,4-epoxybutyl (meth)acrylate. , and 3,4-epoxycyclohexyl (meth)acrylate, which may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth)acrylate is preferred.

Examples of unsaturated monobasic acids include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl, alkoxyl, halogen, nitro, and cyano substituted products of (meth)acrylic acid, etc. Examples include monocarboxylic acids, and these may be used alone or in combination of two or more.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and these may be used alone or in combination of two or more. I don't mind. If necessary, such as increasing the number of carboxyl groups, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to remove the remaining anhydride. It is also possible to hydrolyze the group. Furthermore, when tetrahydrophthalic anhydride or maleic anhydride, which has ethylenically unsaturated double bonds, is used as the polybasic acid anhydride, the number of ethylenically unsaturated double bonds can be further increased.

As a method similar to method (i), for example, the side chain of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and one or more other monomers There is a method of adding an ethylenically unsaturated monomer having an epoxy group to a part of the carboxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]
Method (ii) involves using an ethylenically unsaturated monomer having a hydroxyl group and copolymerizing it with another unsaturated monobasic acid monomer having a carboxyl group or other monomers. There is a method in which the side chain hydroxyl groups of the obtained copolymer are reacted with an isocyanate group of an ethylenically unsaturated monomer having an isocyanate group.

Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate,
- or hydroxyalkyl methacrylates such as 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate, which may be used alone or in combination of two or more types. may be used in combination. In addition, polyether mono(meth)acrylate obtained by addition polymerizing ethylene oxide, propylene oxide, and/or butylene oxide, etc. to the above-mentioned hydroxyalkyl (meth)acrylate, polyγ-valerolactone, polyε-caprolactone, and/or Polyester mono(meth)acrylate to which poly-12-hydroxystearic acid or the like is added can also be used. From the viewpoint of suppressing coating film foreign matter, 2-hydroxyethyl methacrylate or glycerol mono(meth)acrylate is preferable, and from the viewpoint of sensitivity, it is preferable to use one having 2 to 6 hydroxyl groups. Among them, glycerol mono(meth)acrylate is more preferable.

Examples of the ethylenically unsaturated monomer having an isocyanate group include 2-(meth)acryloyl ethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis[methacryloyloxy]ethyl isocyanate. However, without being limited to these, two or more types can also be used in combination.

The monomers constituting the alkali-soluble resin include the following. For example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-Ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate (meth)acrylates such as acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, or ethoxypolyethylene glycol (meth)acrylate;
Alternatively, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine, etc. Acrylamides, styrenes such as styrene or α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, fatty acid vinyls such as vinyl acetate, or vinyl propionate. etc.

Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide Coumarin, 4,4'-bismaleimidiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylene dimaleimide, N,N'-1,4- Phenylene dimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimide N-substituted maleimides such as hexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine, EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl Acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, PO-modified (meth)acrylate of nonylphenol, etc. can be mentioned.

Moreover, a carboxyl group-containing ethylenically unsaturated monomer can also be used. Examples of the carboxyl group-containing ethylenically unsaturated monomer include acrylic acid, methacrylic acid, ε-caprolactone-added acrylic acid, ε-caprolactone-added methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid.

Moreover, a hydroxyl group-containing ethylenically unsaturated monomer can also be used. Examples of the hydroxyl group-containing ethylenically unsaturated monomer include 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3- or 4-hydroxybutyl (meth)acrylate, or cyclohexane. Examples include hydroxyalkyl (meth)acrylates such as dimethanol mono(meth)acrylate. In addition, polyether mono(meth)acrylate obtained by addition polymerizing ethylene oxide, propylene oxide, and/or butylene oxide, etc. to the above hydroxyalkyl (meth)acrylate, (poly)γ-valerolactone, (poly)ε-caprolactone and/or (poly)ester mono(meth)acrylates to which (poly)12-hydroxystearic acid and the like are added.

Moreover, an ethylenically unsaturated monomer containing a phosphoric acid ester group can also be used. Examples of the phosphoric acid ester group-containing ethylenically unsaturated monomer include monomers that can be obtained by reacting the hydroxyl group of the hydroxyl group-containing ethylenically unsaturated monomer with a phosphoric acid esterifying agent such as phosphorus pentoxide or polyphosphoric acid. can be mentioned.

<Alkali-soluble resin without ethylenically unsaturated double bonds>
The coloring composition of the present invention may contain an alkali-soluble resin having no ethylenically unsaturated double bonds in order to adjust the degree of hardening of the coating film. By synthesizing using at least one carboxyl group-containing ethylenically unsaturated monomer and one or more of the other ethylenically unsaturated monomers mentioned above and not adding an ethylenically unsaturated bond to the side chain, ethylene An alkali-soluble resin having no sexually unsaturated double bonds can be obtained.

The weight average molecular weight (Mw) of the alkali-soluble resin in the present invention is 2,000 or more and 40,000 or less, preferably 3,000 or more and 300,00 or less, and 4,000 or more, in order to impart alkaline development solubility. More preferably, it is 20,000 or less. Moreover, it is preferable that the value of Mw/Mn is 10 or less. If the weight average molecular weight (Mw) is less than 2,000, the adhesion to the substrate will decrease, making it difficult for the exposed pattern to remain. If it exceeds 40,000, the solubility in alkaline development will decrease, a residue will be generated, and the linearity of the pattern will deteriorate.
The acid value of the alkali-soluble resin in the present invention is 50 or more and 200 or less (KOHmg/g) in order to impart alkaline development solubility, preferably 70 or more and 180 or less, more preferably 90 or more and 170 or less. It is. If the acid value is less than 50, the solubility in alkaline development will decrease, a residue will be generated, and the linearity of the pattern will deteriorate. When it exceeds 200, the adhesion to the substrate decreases, making it difficult for the exposed pattern to remain.

<Thermosetting compound (CE)>
In the present invention, a thermosetting compound (CE) can be further included in combination with the binder resin. When producing a color filter using the coloring composition for a color filter of the present invention, by including a thermosetting compound, it reacts during baking of the filter segment and increases the crosslinking density of the coating film, thereby improving the heat resistance of the filter segment. The effect of this is that pigment aggregation during filter segment firing is suppressed and the contrast ratio is improved.

The thermosetting compound may be a low molecular weight compound or a high molecular weight compound such as a resin.
Examples of thermosetting compounds include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds, but the present invention is not limited thereto. It is not something that will be done. Epoxy compounds and oxetane compounds are preferably used in the coloring composition for color filters of the present invention.

(Epoxy compound (CE-1))
The epoxy compound may be a low molecular weight compound or a high molecular weight compound such as a resin.
Examples of such epoxy compounds include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxy Benzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Condensates, polymers of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), phenol Polycondensates of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzenedimethanol, α, α, α', α'-benzenedimethanol) , biphenyl dimethanol, α, α, α', α'-biphenyl dimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.) polycondensates of bisphenols and various aldehydes, glycidyl ether-based epoxy resins made by glycidylating alcohols, etc., alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine-based epoxy resins , glycidyl ester-based epoxy resins, etc., but are not limited to these as long as they are commonly used epoxy compounds. These may be used alone or in combination of two or more.

Commercially available products include, for example, Epicote 807, Epicote 815, Epicote 825, Epicote 827, Epicote 828, Epicote 190P, Epicote 191P (the above are trade names; manufactured by Yuka Shell Epoxy Co., Ltd.), Epicote 1004, Epicote 1256 (the above). are product names; manufactured by Japan Epoxy Resin Co., Ltd.), TECHMORE VG3101L (product name; manufactured by Mitsui Chemicals, Inc.), EPPN-501H, 502H (product name; manufactured by Nippon Kayaku Co., Ltd.), JER 1032H60 (product name) ; made by Japan Epoxy Resin Co., Ltd.), JER 157S65, 157S70 (product name; made by Japan Epoxy Resin Co., Ltd.), EPPN-201 (product name; made by Nippon Kayaku Co., Ltd.), JER152, JER154 (the above are products) Name; manufactured by Japan Epoxy Resin Co., Ltd.), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (product names; manufactured by Nippon Kayaku Co., Ltd.), Celoxide 2021, EHPE-3150 (product names listed above are manufactured by Nippon Kayaku Co., Ltd.) name: manufactured by Daicel Chemical Industries, Ltd.), Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721, (and above) (manufactured by Nagase ChemteX Co., Ltd.), TEPIC-L, TEPIC-H, TEPIC-S (manufactured by Nissan Chemical Industries, Ltd.), and the like.
Examples include, but are not limited to, the following.

The blending amount of the epoxy compound is preferably 0.5 to 300 parts by weight, more preferably 1.0 to 50 parts by weight, per 100 parts by weight of the coloring material. If it is less than 0.5 parts by mass, the effect of improving contrast ratio and heat resistance will be small, and if it is more than 300 parts by mass, problems may occur when forming filter segments by photolithography.

(Oxetane compound (CE-2))
It is preferable to add an oxetane compound to the colored composition of the present invention. As the oxetane compound, any known compound having an oxetane group can be used without particular limitation. Examples of the oxetane compound include those in which the oxetane group is monofunctional, those in which the oxetane group is difunctional, and those in which the oxetane group is difunctional or more.

Examples of monofunctional oxetane groups include (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl- 3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, 3-ethyl-3-{[3-( Examples include triethoxysilyl)propoxy]methyl}oxetane.
Specific examples include OXE-10 and OXE-30 manufactured by Osaka Organic Chemical Industry Co., Ltd., and OXT-101 and OXT-212 manufactured by Toagosei Co., Ltd.

Examples of difunctional oxetane groups include 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl] Benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl Ether-3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3- oxetanyl)-5-oxanonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene Glycose bis(3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl)ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis( 3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) Ether, EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3) -oxetanylmethyl) ether and the like.
Specific examples include OXBP, OXTP manufactured by Ube Industries, Ltd., and OXT-121 and OXT-221 manufactured by Toagosei Co., Ltd.

As for those whose oxetane group is difunctional or more,
Pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol penta Kis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone modified dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone modified dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, Pentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis (3-ethyl-3-oxetanylmethyl) ether, resins containing oxetane groups (for example, oxetane-modified phenol described in Japanese Patent No. 3783462) Examples include polymers obtained by radical polymerization of (meth)acrylic monomers such as novolak resin, etc.) and the above-mentioned OXE-30. Such polymers can be obtained using known polymerization methods.

The content of the oxetane compound used in the colored composition of the present invention is usually 0.5 to 50% by weight, preferably 1 to 40% by weight based on 100% by weight of the solid content of the colored composition. It is preferable that the content of the oxetane compound is within the above range because an excellent coating film with good water stain resistance and high chemical resistance can be obtained.

(melamine compound)
The melamine compound in the present invention refers to a compound having a melamine ring structure. The melamine compound may be a low molecular weight compound or a high molecular weight compound such as a resin. Preferred in the present invention are melamine compounds of the methylol type and ether type, in which the average number of methylol groups and/or ether groups per melamine ring is 5.0 or more. If the average number of methylol groups and/or ether groups per melamine ring is less than 5.0, there will be fewer reaction points and the crosslinked structure during curing will not be sufficiently dense, resulting in reduced contrast ratio reduction during heat treatment and NMP resistance. The effect of improvement may be reduced.

Commercially available products include, for example, Nikarak MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS -001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, MX-410 (manufactured by Sanwa Chemical Co., Ltd.), Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, 370 (manufactured by Nippon Cytec Industries, Ltd.), but is not limited to these.

Among them, Nicarac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW in which the average number of methylol groups and/or ether groups per melamine ring is 5.0 or more. -22, MS-21, MS-11, MW-24X, MX-45 (manufactured by Sanwa Chemical Co., Ltd.) Cymel 232, 235, 236, 238, 300, 301, 303, 350 (manufactured by Nihon Cytec Industries Co., Ltd.) etc. , is preferable in that a dense crosslinked structure can be obtained.

(hardening agent)
Further, the colored composition of the present invention may contain a curing agent (curing accelerator), etc., as necessary, in order to assist in curing the thermosetting compound. Effective curing agents include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, etc., but are not particularly limited to these, and can react with thermosetting compounds. Any curing agent may be used. Examples of the curing agent 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 (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (e.g., imidazole, 2-Methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl- 4-methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), S-triazine derivatives (e.g., 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.). I can do it. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by mass based on 100 parts by mass of the thermosetting compound.

<Polymerizable compound (D)>
The photosensitive colored composition of the present invention includes a colored composition, a polymerizable compound (D), and a photopolymerization initiator (E). The polymerizable compound (D) includes monomers or oligomers that can be cured by ultraviolet rays, heat, etc. to produce transparent resins.

Examples of monomers and oligomers that can be cured by ultraviolet rays or heat to produce transparent resins 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, polypropylene glycol di(meth)acrylate ) acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO modified tri(meth)acrylate, trimethylolpropane EO modified tri(meth)acrylate Acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6 -Hexanediol diglycidyl ether 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 ) Acrylate, tricyclodecanyl (meth)acrylate, (meth)acrylic ester of methylolated melamine, epoxy (meth)acrylate, various acrylic esters and methacrylic esters such as urethane acrylate, (meth)acrylic acid, styrene, Examples include, but are not necessarily limited to, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, acrylonitrile, etc. isn't it.

These commercially available products include KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, and GPO- manufactured by Nippon Kayaku Co., Ltd. 303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, and Aronix M-303, M manufactured by Toagosei Co., Ltd. -305, M-306, M-309, M-310, M-321, M-325, M-350, M-360, M-313, M-315, M-400, M-402, M-403 , M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, Viscoat #310HP, #335HP, #700, #295 manufactured by Osaka Organic Co., Ltd. , #330, #360, #GPT, #400, #405, NK Ester A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., etc. can be suitably used.

(Polymerizable compound having acid group)
The polymerizable compound in the present invention may contain a polymerizable compound having an acid group. Examples of acid groups include sulfonic acid groups, carboxyl groups, and phosphoric acid groups.

Examples of the polymerizable compound having an acid group include esterification products of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohol and (meth)acrylic acid and dicarboxylic acids; polyhydric carboxylic acids and monohydroxyalkyl Examples include esterification products with (meth)acrylates. Specific examples include monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. and monoesters containing free carboxyl groups with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4 -tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, and benzene-1,3,5-tricarboxylic acid, and 2-hydroxyethyl acrylate, 2- Examples include free carboxyl group-containing oligoesters with monohydroxy monoacrylates or monohydroxy monomethacrylates such as hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate, but the effects of the present invention are limited to these. It is not something that will be done.

As these commercially available products, Viscoat #2500P manufactured by Osaka Organic Co., Ltd. and Aronix M-5300, M-5400, M-5700, M-510, M-520 manufactured by Toagosei Co., Ltd., etc. can be suitably used. .

(Polymerizable compound with urethane bond)
The polymerizable compound in the present invention may contain a polymerizable compound containing at least one ethylenically unsaturated bond and at least one urethane bond. For example, polyfunctional urethane acrylate obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and polyfunctional urethane acrylate obtained by reacting an alcohol with a polyfunctional isocyanate and further reacting a (meth)acrylate having a hydroxyl group. Examples include urethane acrylate.

Examples of (meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate. meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide modified penta(meth)acrylate, dipentaerythritol propylene oxide modified penta(meth)acrylate, dipentaerythritol caprolactone modified penta(meth)acrylate, glycerol acrylate Examples include methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and carboxy(meth)acrylate, and a hydroxyl group-containing polyol polyacrylate.

Further, examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

These commercially available products include AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA-167 manufactured by Kyoeisha Chemical Co., Ltd., and DAUA-167 manufactured by Shin-Nakamura Chemical Industry Co., Ltd. UA-160TM, manufactured by Osaka Organic Chemical Industry Co., Ltd., UV-4108F, UV-4117F, etc. can be suitably used.

The above polymerizable compounds can be used alone or in a mixture of two or more in any ratio as necessary.

The blending amount of the polymerizable compound is preferably 1 to 50 parts by mass, based on the total solid content of the photosensitive coloring composition (100 parts by mass), and 2 to 40 parts by mass from the viewpoint of photocurability and developability. It is more preferable that it is part.

<Photopolymerization initiator (E)>
The photosensitive coloring composition of the present invention contains a photopolymerization initiator (E). By including the photopolymerization initiator (E), the composition can be cured by ultraviolet irradiation and filter segments can be formed by photolithography. It is preferable to add a photopolymerization initiator (E) and prepare the composition in the form of a solvent-developable or alkali-developable photosensitive coloring composition.

As the photopolymerization initiator (E), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one , 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino) phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone Acetophenone compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylic benzophenone compounds such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chlorothioxanthone, 2- Thioxanthone compounds such as methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl )-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine , 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(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 triazine compounds such as 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-( O-benzoyloxime)], or oxime ester compounds such as ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) ; Phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, etc. Examples include quinone compounds; borate compounds; carbazole compounds; imidazole compounds; and titanocene compounds.
These photopolymerization initiators can be used alone or in a mixture of two or more in any ratio as necessary.

Commercially available acetophenone compounds include "Omnirad 907" (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one) and "Omnirad 369E” (2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone), “Omnirad 379EG” (2-(dimethylamino)-2-[ (4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone), phosphine-based compounds are all manufactured by IGM Resins, and "Omnirad 819" (bis(2,4, 6-trimethylbenzoyl)-phenylphosphine oxide), "Omnirad TPO" (diphenyl-2,4,6-trimethylbenzoylphosphine oxide), and the like.

In the present invention, among these, it is preferable to contain an oxime ester compound.

(oxime ester compound)
When an oxime ester compound absorbs ultraviolet light, the N—O bond of the oxime is cleaved to generate iminyl radicals and alkyloxy radicals. Since these radicals generate highly active radicals by further decomposition, a pattern can be formed with a small amount of exposure. If the colorant concentration of the photosensitive coloring composition is high, the ultraviolet transmittance of the coating film may be low and the degree of curing of the coating film may be low, but oxime ester compounds are preferably used because they have high quantum efficiency. Ru.

Commercially available products of these oxime ester compounds include 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime)] (IRGACURE OXE-01) and ethanone from BASF. ,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) (IRGACURE OXE 02), N-1919 (manufactured by ADEKA), TRONLY TR-PBG-304, TRONLY TR-PBG-305, TRONLY TR-PBG-309 (all manufactured by Changzhou Strong New Materials Co., Ltd.), etc. are commercially available. In addition, in addition to the above, oxime It is also possible to use ester photopolymerization initiators.

The content of the photopolymerization initiator is preferably 2 to 50 parts by weight, and more preferably 2 to 30 parts by weight from the viewpoint of photocurability and developability, based on 100 parts by weight of the colorant. If it is less than 2 parts by mass, the adhesion of the formed pattern to the base material will deteriorate, and if it exceeds 50 parts by mass, problems may occur in developability or a decrease in brightness after heat treatment at 230° C. may occur.

<Sensitizer (H)>
Furthermore, the photosensitive 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, and anthraquinone derivatives. , polymethine dyes such as xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives , azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, Phthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α-acyloxy esters, acyl oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t- Examples include butylperoxycarbonyl)benzophenone and 4,4'-bis(diethylamino)benzophenone.

Among the above-mentioned sensitizers, thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives are mentioned as sensitizers that can particularly suitably sensitize. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis (dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole and the like are used.

These sensitizers can be used alone or in combination of two or more in any ratio as required.
Commercially available products include "KAYACURE DETX-S" (2,4-diethylthioxanthone, manufactured by Nippon Kayaku Co., Ltd.) and "CHEMARK DEABP"(4,4'-bis(diethylamino)benzophenone, manufactured by Chemark Chemical Co., Ltd.).

More specifically, there are "Pigment Handbook" (edited by Makoto Okawara et al., 1986, Kodansha), "Chemistry of Functional Pigments" (edited by Makoto Okawara et al., 1981, CMC), "Dye Handbook" (edited by Shin Okawara et al., 1981, CMC), and " Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (CMC, 1986). In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region may also be included.

The content when using the sensitizer is preferably 3 to 60 parts by mass based on 100 parts by mass of the photopolymerization initiator contained in the coloring composition, and from the viewpoint of photocurability and developability, the content is preferably 5 to 60 parts by mass. More preferably, the amount is 50 parts by mass.

<Thiol chain transfer agent (I)>
The photosensitive coloring composition of the present invention preferably contains a thiol chain transfer agent as a chain transfer agent. By using thiol together with a photopolymerization initiator, thiyl radicals that act as chain transfer agents and are less susceptible to polymerization inhibition by oxygen are generated in the radical polymerization process after light irradiation, so the resulting colored composition has high sensitivity. .

Further, polyfunctional aliphatic thiols having two or more SH groups bonded to aliphatic groups such as methylene and ethylene groups are preferred. More preferred is a polyfunctional aliphatic thiol having four or more SH groups. By increasing the number of functional groups, the polymerization initiation function is improved, and it is possible to cure from the surface of the pattern to the vicinity of the base material.

Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropionate. trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid Tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s- Examples include triazines, and preferred examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

These thiol-based chain transfer agents can be used alone or in combination of two or more.

Further, the content of the thiol-based chain transfer agent is preferably 1.0 to 10% by mass, more preferably 2.0 to 8.0% by mass based on the total solid content of the coloring composition. In this range, the effect of the chain transfer agent becomes large, and sensitivity, taper shape, wrinkles, film shrinkage rate, etc. become good.

<Polymerization inhibitor (J)>
The photosensitive coloring composition of the present invention may contain a polymerization inhibitor in order to prevent exposure to light due to diffraction of the mask during exposure. By adding a polymerization inhibitor, it is possible to obtain the effect of preventing curing from proceeding outside the desired pattern due to chain polymerization caused by exposure to light.

Examples of polymerization inhibitors include catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, and 2-propylcatechol. , 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-t-butylcatechol, 3-t-butylcatechol, 4-t- Alkylcatechol compounds such as butylcatechol, 3,5-di-t-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, Alkylresorcinol compounds such as 2-n-butylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, 4-t-butylresorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, 2, Alkylhydroquinone compounds such as 5-di-t-butylhydroquinone, phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, and phosphines such as trioctylphosphine oxide and triphenylphosphine oxide. Examples include oxide compounds, phosphite compounds such as triphenyl phosphite and trisnonylphenyl phosphite, pyrogallol, and phloroglucin. The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass based on 100 parts by mass of the coloring composition excluding the solvent. In this range, the effect of the polymerization inhibitor becomes large, and the linearity of the taper, the wrinkles of the coating film, the pattern resolution, etc. become good.

<Ultraviolet absorber (K)>
The photosensitive coloring composition of the invention may also contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorption function, and includes benzotriazole organic compounds, triazine organic compounds, benzophenone organic compounds, salicylic acid ester organic compounds, cyanoacrylate organic compounds, and salicylate organic compounds. Examples include organic compounds.

The content of the ultraviolet absorber is preferably 5 to 70% by weight based on the total of 100% by weight of the photopolymerization initiator and the ultraviolet absorber. If the content of the ultraviolet absorber is less than the above, the effect of the ultraviolet absorber will be small and resolution cannot be ensured, and if it is more than the above, the sensitivity will be lower, resulting in pixel peeling and hole diameter larger than the designed value. Problems may occur, such as when the

At this time, when the photosensitive coloring composition contains a sensitizer, the content of the sensitizer is included in the content of the photopolymerization initiator.

Further, the total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass based on 100% by mass of the solid content of the photosensitive coloring composition. If the total content of the photopolymerization initiator and ultraviolet absorber is less than the above, the adhesion will be weakened and pixel peeling will occur, and if it is more than the above, the sensitivity may be too high and the resolution may deteriorate.

At this time, when the photosensitive coloring composition contains a sensitizer, the content of the sensitizer is included in the content of the photopolymerization initiator.

Examples of benzotriazole organic compounds include 2-(5methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3, 5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'- Hydroxy-5'-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1 -dimethylethyl)-4-hydroxy, mixture of C7-9 side chain and linear alkyl esters, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl) Phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3 -(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300 reaction product, 2-(2H-benzotriazol-2-yl)-4-(1 , 1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] , 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl-4-methylphenol, 2-(3 , 5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3- t-Butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl-3-[3-t-butyl-4-hydroxy-5-(5- Chloro-2H-benzotriazol-2-yl)phenyl]propionate is mentioned. Other oligomer type and polymer type compounds having a benzotriazole structure can also be used.

More specifically, TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, 1130 manufactured by BASF Corporation, ADEKA STAB LA-29, LA-31RG, LA manufactured by ADEKA Corporation. -32, LA-36, KEMISORB71, 73, 74, 79, 279 manufactured by Chemipro Kasei Co., Ltd., and RUVA-93 manufactured by Otsuka Chemical Co., Ltd., and the like.

Examples of triazine-based organic compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4, 6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, 2-(2,4-dihydroxy Reaction product of phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester, 2,4-bis(2-hydroxy-4 -butoxyphenyl"-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-( hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6- Examples include tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine. Other oligomer type and polymer type compounds having a triazine structure can also be used.

More specifically, KEMISORB 102 manufactured by ChemiPro Kasei, TINUVIN 400, 405, 460, 477, 479, 1577ED manufactured by BASF, ADEKA STAB LA-46, LA-F70, CYASORB UV-1164 manufactured by Sun Chemical, etc. Can be mentioned.

Examples of benzophenone organic compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3 water temperature, 2-hydroxy-4-n- Octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone , 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like. Other oligomer type and polymer type compounds having a benzophenone structure can also be used.

More specifically, KEMISORB 10, 11, 11S, 12, 111 made by Chemipro Kasei Co., Ltd., SEESORB 101, 107 made by Shipro Kasei Co., Ltd., ADEKA STAB 1413 made by ADEKA Co., Ltd., UV-12 made by Sun Chemical Co., Ltd., etc. Can be mentioned.

Examples of salicylic acid ester organic compounds include phenyl salicylate, p-octylphenyl salicylate, and t-butylphenyl salicylate. Other oligomer type and polymer type compounds having a salicylic acid ester structure can also be used.

<Antioxidant (L)>
The photosensitive coloring composition of the present invention can contain an antioxidant. Antioxidants reduce the transmittance of the coating film in order to prevent the photopolymerization initiators and thermosetting compounds contained in the photosensitive coloring composition from oxidizing and yellowing due to the thermal process during heat curing and ITO annealing. It can be made higher. In particular, when the concentration of the coloring agent in the coloring composition is high, the amount of crosslinking component in the coating film decreases, so measures such as using a highly sensitive crosslinking component and increasing the amount of photopolymerization initiator are taken, resulting in stronger yellowing during the heat process. can be seen. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation during the heating process and obtain a high transmittance of the coating film.

The "antioxidant" in the present invention may be any compound that has a radical scavenging function or a peroxide decomposition function. Specifically, antioxidants include hindered phenol-based, hindered amine-based, phosphorus-based, and hydroxylamine-based compounds, and known antioxidants can be used. Further, the antioxidant used in the present invention preferably does not contain a halogen atom.

Among these antioxidants, preferred are hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants, and sulfur antioxidants from the viewpoint of achieving both the transmittance and sensitivity of the coating film. Examples include agents.

Examples of hindered phenolic antioxidants include 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H, 3H,5H)-trione, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 4,4'-butylidene-bis-(2-t -butyl-5-methylphenol), stearyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis [3-(3,5-di-t-butyl-4- hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8, 10-tetraoxaspiro[5.5]undecane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3, 5-Tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2'- Methylenebis(6-t-butyl-4-ethylphenol), 2,2'-thiodiethylbis-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis( 3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), i-octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,6-bis( dodecylthiomethyl)-o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4,6-bis(octylthiomethyl)-o-cresol, bis[3 -(3-methyl-4-hydroxy-5-t-butylphenyl)propionic acid] ethylenebisoxybisethylene, 1,6-hexanediolbis[3-(3,5-di-t-butyl-4-hydroxy) phenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2,2'-thio-bis -(6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis-( 4,6-dimethyl-phenol), 2,2'-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)- Examples include phenol. Other oligomer type and polymer type compounds having a hindered phenol structure can also be used.

More specifically, ADEKA STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330 manufactured by ADEKA Corporation, KEMINOX101, 179, 76 manufactured by Chemipro Corporation, 9425, BASF Corporation IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565, Sun Chemical Corporation Syanox CY-1790, CY-2777, etc. can be mentioned.

Examples of hindered amine antioxidants include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6- Tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(2,2,6,6- Tetramethyl-4-piperidyl) sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, a polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, Poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl) imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and 3,5 ,5-trimethylhexanoic acid ester, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino }-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)- 4-piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane, bis(1,2,2,6,6-pentamethyl-4-pyperidinyl)[[3,5-bis(1,1 dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate methyl 1,2,2,6,6-pentamethyl-4-pyriperidyl sebacate, poly[[6-morpholino-s-triazine-2,4- diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 2,2 , 6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid ester, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexa Examples include methylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, etc. It will be done. Other oligomer type and polymer type compounds having a hindered amine structure can also be used.

More specifically, ADEKA STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87 manufactured by ADEKA Co., Ltd. , LA-402F, LA-502XP, KAMISTAB29, 62, 77, 94, manufactured by ChemiPro Kasei Co., Ltd., Tinuvin249, TINUVIN111FDL, 123, 144, 292, 5100, manufactured by BASF Corporation, Cyasorb UV-3346, UV- manufactured by Sun Chemical Co., Ltd. 3529, UV-3853, etc.

Examples of phosphorus antioxidants include di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite, and 2,2'-methylenebis(4,6- di-t-butylphenyl) 2-ethylhexyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, tris(nonylphenyl) phosphite, tetra(C12-C15 alkyl)-4,4'- Isopropylidene diphenyl diphosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenylisodecyl phosphite, tris(isodecyl) phosphite, triphenyl phosphite, tetrakis(2,4-di-t-butylphenyl)-4 ,4-biphenyldiphosphonite, tris(tridecyl)phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi(tridecyl)phosphite, diphenylisooctylphosphite, diphenyltridecylphosphite, 4,4' - Isopropylidene diphenol alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl) phosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di( nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-Methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodium bis(4-t-butylphenyl) phosphite , Sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, Ethyl bis(2,4-phosphite) di-t-butyl-6-methylphenyl) and the like. Other oligomer type and polymer type compounds having a phosphite structure can also be used.

More specifically, ADEKA STAB PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP manufactured by ADEKA Corporation, IRGAFOS168 manufactured by BASF Corporation, HostanoxP- manufactured by Clariant Chemicals Corporation. Examples include EPQ.

Sulfur-based antioxidants include 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], 3,3'-thio Ditridecyl bispropionate, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol , 2,4-bis[(laurylthio)methyl]-o-cresol, and the like. Other oligomer type and polymer type compounds having a thioether structure can also be used.

More specifically, examples include ADEKA STAB AO-412S and AO-503 manufactured by ADEKA Co., Ltd., and KEMINOXPLS manufactured by ChemiPro Kasei Co., Ltd.

These antioxidants can be used alone or in combination of two or more in any ratio as required.

Further, the content of the antioxidant is preferably 0.5 to 5.0% by mass based on 100% by mass of the solid content of the coloring composition because transmittance, spectral characteristics, and sensitivity are good.

<Leveling agent (M)>
It is preferable to add a leveling agent to the photosensitive colored composition of the present invention for the purpose of improving the coating properties of the composition on a transparent substrate and the drying properties of a colored film. As the leveling agent, various surfactants such as silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants can be used.

Examples of silicone surfactants include linear polymers consisting of siloxane bonds and modified siloxane polymers with organic groups introduced into side chains or terminals.

More specifically, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345/346, 347, 348, 349, 370, 377, 378 , 3455, UV3510, 3570, FZ-7002, 2110, 2122, 2123, 2191, 5609 manufactured by Dow Corning Toray Co., Ltd., X-22-4952, X-22-4272, X-22- manufactured by Shin-Etsu Chemical Co., Ltd. 6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341, etc.

Examples of the fluorosurfactant include a surfactant or a leveling agent having a fluorocarbon chain.

More specifically, Surflon S-242, S-243, S-420, S-611, S-651, S-386 manufactured by AGC Seimi Chemical Co., Ltd., and Megafac F-253, F-477 manufactured by DIC Corporation. , F-551, F-552, F-555, F-558, F-560, F-570, F-575, F-576, R-40-LM, R-41, RS-72-K, DS -21, Sumitomo 3M Co., Ltd. FC-4430, FC-4432, Mitsubishi Materials Electronic Chemicals Co., Ltd. EF-PP31N09, EF-PP33G1, EF-PP32C1, Neos Co., Ltd. Ftergent 602A, etc.

Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristele ether, and polyoxyethylene octyldodecyl. Ether, polyoxyalkylene alkyl ether, polyoxyphenylene distyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl Ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitan tetraoleate , glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanol Examples include amides, alkylimidazolines, and the like.

More specifically, Kao Corporation Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430 , 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, LS-110, LS-114, MS-110, A-60, A-90 , B-66, PP-290, Latemur PD-420, PD-430, PD-430S, PD450, Rheodor SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP -O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW- IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH- 60 (K), Amit 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA Pluronic L-23, 31, 44, 61, 62, 64 manufactured by ADEKA Co., Ltd. , 71, 72, 101, 121, TR-701, 702, 704, 913R, (meth)acrylic acid-based (co)polymer Polyflow No. manufactured by Kyoeisha Chemical Co., Ltd. 75, No. 90, No. 95 etc. are mentioned.

Examples of the cationic surfactant include alkyl amine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and ethylene oxide adducts thereof.

More specifically, examples include Acetamin 24, Cortamin 24P, 60W, and 86P Conc manufactured by Kao Corporation.

Examples of anionic surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalene sulfonate, sodium alkyldiphenyl ether disulfonate, and monoethanolamine lauryl sulfate. , triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate.

More specifically, examples include Ftergent 100 and 150 manufactured by Neos Corporation, ADEKA Hope YES-25, ADEKA COL TS-230E, PS-440E, and EC-8600 manufactured by ADEKA Corporation.

Examples of the amphoteric surfactant include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyldimethylaminoacetic acid betaine, and alkyl amine oxides such as lauryl dimethylamine oxide.

More specific examples include Amhitol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, and 20N manufactured by Kao Corporation.

When the photosensitive coloring composition of the present invention contains a surfactant, the amount of the surfactant added is preferably 0.001 to 2.0% by mass based on the total solid content of the composition of the present invention. More preferably, it is 0.005 to 1.0% by mass. Within this range, the coating properties of the coloring composition, pattern adhesion, and transmittance will be well balanced.
The photosensitive coloring composition of the present invention may contain only one type of surfactant, or may contain two or more types of surfactant. When two or more types are included, it is preferable that the total amount falls within the above range.

<Storage stabilizer (N)>
The colored composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Storage stabilizers include, for example, quaternary ammonium chloride such as benzyl trimethyl chloride and diethyl hydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, and organic phosphines such as t-butylpyrocatechol, tetraethylphosphine, and tetraphenyl. , phosphites and the like. The storage stabilizer can be used in an amount of 0.1 to 10% by weight based on the total amount of colorant (100% by weight).

<Adhesion improver (O)>
The photosensitive coloring composition of the present invention may contain an adhesion improver such as a silane coupling agent in order to improve adhesion to the substrate. By improving the adhesion by the adhesion improver, the reproducibility of fine lines becomes better and the resolution improves.

Examples of adhesion improvers include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropylmethyldimethoxysilane. (Meth)acrylic silanes such as methacryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -Epoxysilanes such as glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxy Silane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl- butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, aminosilanes such as hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxy Silane, mercapto compounds such as 3-mercaptopropyltrimethoxysilane, styryl compounds such as p-styryltrimethoxysilane, ureido compounds such as 3-ureidopropyltriethoxysilane, and sulfides such as bis(triethoxysilylpropyl)tetrasulfide. , and silane coupling agents such as isocyanates such as 3-isocyanatepropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the colorant in the coloring composition. It is more preferable within this range because the effect is large and the balance between adhesion, resolution, and sensitivity is good.

<Method for producing colored composition>
The colored composition included in the present invention includes a pigment in a resin-type dispersant, a binder resin, and/or a solvent, preferably together with a dispersion aid (dye derivative or surfactant), in a kneader, a two-roll mill, It can be produced by finely dispersing it using various dispersion means such as a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor. At this time, two or more pigments may be simultaneously dispersed in the pigment carrier, or they may be separately dispersed in the pigment carrier and mixed.

<Dispersed particle size of pigment>
The average dispersed particle diameter of the pigment in the coloring composition is preferably in the range of 30 to 200 nm. More preferably, it is in the range of 40 to 120 nm. Within this range, the viscosity and dispersion stability are high, and when this coloring composition is used alone or in combination with a photopolymerizable material, it not only has high viscosity and dispersion stability, but also high sensitivity and high development speed. A coloring composition can be obtained, and when a color filter is produced using it, a high quality color filter can be obtained.

The dispersed particle diameter of the pigment was measured using Nikkiso's Microtrack UPA-EX150, which employs a dynamic light scattering method (FFT power spectrum method), with particle permeability set to absorption mode and particle shape non-spherical. One example is to set D50 as the average diameter. It is preferable to use the same solvent used for the dispersion as the diluting solvent for measurement, and to measure the sample treated with ultrasonic waves immediately after sample preparation, because results with less variation can be easily obtained.

<Method for producing photosensitive coloring composition>
When used as a photosensitive coloring composition, it can be prepared as a solvent-developable or alkali-developable coloring composition. A solvent-developable or alkali-developable coloring composition is prepared by mixing the coloring composition, a polymerizable compound and/or a photopolymerization initiator, and, if necessary, a solvent, other dispersion aids, additives, etc. can be adjusted. The photopolymerization initiator may be added at the stage of preparing the colored composition, or may be added to the prepared colored composition later.

<Solvent>
The colored composition of the present invention contains a solvent in order to facilitate the formation of a colored film by coating it on a substrate such as glass to a dry film thickness of 0.2 to 5 μm. The solvent is selected in consideration of good coating properties of the coloring composition, solubility of each component of the coloring composition, and safety.

As the solvent, any solvent commonly used in the field can be used, and it can be used alone or as appropriate depending on the application conditions (speed, drying conditions, etc.), taking into consideration performance such as boiling point, SP value, evaporation rate, and viscosity. used in combination.

Examples of the solvents used include ester solvents (solvents containing -COO- in the molecule but not containing -O-), ether solvents (solvents containing -O- but not -COO- in the molecule) , ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- but not -COO- in the molecule), alcohol solvents (solvents containing -COO- in the molecule), Examples include solvents containing -O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate. , methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone, and the like.

Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether. , propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl Examples include ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-propyl ether, anisole, phenetol, and methylanisole.

Ether ester solvents include methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl Examples include ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol diacetate, and the like.

Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, isophorone. Examples include.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, 1,3-butylene glycol, and glycerin.

Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, mesitylene, and the like.

Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.
These solvents may be used alone or in combination of two or more.

Among the above-mentioned solvents, it is preferable to include an organic solvent having a boiling point of 120° C. or more and 180° C. or less at 1 atm from the viewpoint of coating properties and drying properties. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2- Pentanone, N,N-dimethylformamide, N-methylpyrrolidone and the like are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate and the like are more preferred.

<Removal of coarse particles>
The colored composition of the present invention can be produced by centrifugation, filtration using a sintered filter or a membrane filter, etc. to produce coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more. It is preferable to remove mixed dust. As described above, it is preferable that the colored composition does not substantially contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be explained.
The color filter of the present invention includes a red filter segment, a green filter segment, and a blue filter segment. Further, the color filter may further include a magenta filter segment, a cyan filter segment, and a yellow filter segment.

<Color filter manufacturing method>
Color filters can be manufactured by a printing method or a photolithography method.
Forming filter segments by printing can be patterned by simply repeating printing and drying of a colored composition prepared as a printing ink, so it is a low cost and excellent mass-producible method for producing color filters. Furthermore, advances in printing technology have made it possible to print fine patterns with high dimensional accuracy and smoothness. In order to perform printing, it is preferable to use a composition that prevents the ink from drying or solidifying on the printing plate or blanket. It is also important to control the fluidity of the ink on the printing press, and the viscosity of the ink can also be adjusted using a dispersant or extender pigment.

When forming filter segments by photolithography, the colored composition prepared as a solvent-developed or alkali-developed colored resist material is applied onto a transparent substrate by spray coating, spin coating, slit coating, roll coating, etc. Depending on the method, the coating is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to light (irradiation with radiation) through a mask having a predetermined pattern provided in contact with the film or in a non-contact state. Thereafter, the uncured portion is removed by immersion in a solvent or alkaline developer or sprayed with a developer to form a desired pattern, and the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to promote polymerization of the colored resist material, heating can be applied as necessary. According to the photolithography method, a color filter can be manufactured with higher precision than the above-mentioned printing method.

During development, an aqueous solution of sodium carbonate, sodium hydroxide, etc. is used as an alkaline developer, and organic alkalis such as dimethylbenzylamine, triethanolamine, etc. can also be used. Moreover, an antifoaming agent and a surfactant can also be added to the developer.
In order to increase exposure sensitivity, after coating and drying the above colored resist, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is coated and dried to form a film that prevents polymerization inhibition by oxygen. , exposure can also be performed.

The color filter of the present invention can be manufactured by an electrodeposition method, a transfer method, an inkjet method, etc. in addition to the above-mentioned method, and the colored composition of the present invention can be used in any method. The electrodeposition method is a method of manufacturing color filters by electrodepositing filter segments of each color on the transparent conductive film by electrophoresis of colloidal particles using a transparent conductive film formed on a substrate. . Further, the transfer method is a method in which filter segments are formed in advance on the surface of a removable transfer base sheet, and the filter segments are transferred to a desired substrate.

A black matrix can be formed in advance before forming filter segments of each color on a transparent substrate or a reflective substrate. As the black matrix, chromium, a multilayer film of chromium/chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light shielding agent is dispersed can be used, but the black matrix is not limited to these. Alternatively, a thin film transistor (TFT) may be formed in advance on the transparent substrate or reflective substrate, and then filter segments of each color may be formed. Moreover, an overcoat film, a transparent conductive film, etc. are formed on the color filter of the present invention, if necessary.

The color filter of the present invention is attached to a counter substrate using a sealant, liquid crystal is injected through an injection port provided in the sealing part, the injection port is sealed, and a polarizing film or a retardation film is attached to the substrate as necessary. A color liquid crystal display device is manufactured by pasting it on the outside. This color liquid crystal display device supports twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convensed bend (OCB). ) can be used in a liquid crystal display mode that performs colorization using color filters.

Moreover, the color filter of the present invention can also be used for manufacturing color solid-state image sensors, organic EL display devices, quantum dot display devices, electronic paper, etc. in addition to color liquid crystal display devices.

<Liquid crystal display device>
A liquid crystal display device equipped with a color filter of the present invention will be explained.
The liquid crystal display device of the present invention includes the color filter of the present invention and a light source. Examples of the light source include a cold cathode fluorescent lamp (CCFL) and a white LED, but in the present invention, it is preferable to use a white LED because the red reproduction area is expanded. FIG. 1 is a schematic cross-sectional view of a liquid crystal display device 10 equipped with a color filter of the present invention. The device 10 shown in FIG. 1 includes a pair of transparent substrates 11 and 21 that are spaced apart and facing each other, and a liquid crystal LC is sealed between them.

A TFT (thin film transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13. Furthermore, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

On the other hand, the color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21. The red, green, and blue filter segments that make up the color filter 22 are separated by a black matrix (not shown).

A transparent protective film (not shown) is formed as necessary to cover the color filter 22 , a transparent electrode layer 23 made of ITO, for example, is formed thereon, and an alignment layer 24 is formed to cover the transparent electrode layer 23 . is provided.

Furthermore, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Note that a backlight unit 30 is provided below the polarizing plate 15.

The liquid crystal LC is aligned according to a driving mode such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane switching), VA (Vertical Alignment), OCB (Optically Compensated Birefringence), or the like. A TFT (thin film transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13. Furthermore, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

On the other hand, the color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21. The red, green, and blue filter segments that make up the color filter 22 are separated by a black matrix (not shown).

A transparent protective film (not shown) is formed as necessary to cover the color filter 22 , a transparent electrode layer 23 made of ITO, for example, is formed thereon, and an alignment layer 24 is formed to cover the transparent electrode layer 23 . is provided.

Furthermore, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Note that a backlight unit 30 is provided below the polarizing plate 15.

White LED light sources include those in which a fluorescent filter is formed on the surface of a blue LED, and those in which a blue LED resin package contains a phosphor. λ3), has a wavelength (λ4) at which the emission intensity is maximum within the range of 530 nm to 580 nm, has a wavelength (λ5) at which the emission intensity is maximum within the range from 600 nm to 650 nm, and has a wavelength The ratio (I4/I3) of the emission intensity I3 at wavelength λ3 and the emission intensity I4 at wavelength λ4 is 0.2 or more and 0.4 or less, and the ratio (I5/I3) of the emission intensity I3 at wavelength λ3 and the emission intensity I5 at wavelength λ5 is ) is 0.1 or more and 1.3 or less, or a white LED light source (LED1) that has a wavelength (λ1) with maximum emission intensity in the range of 430nm to 485nm and in the range of 530nm to 580nm. spectral characteristics having a second peak wavelength of emission intensity (λ2) within the range, and a ratio (I2/I1) of emission intensity I1 at wavelength λ1 to emission intensity I2 at wavelength λ2 of 0.2 or more and 0.7 or less. It is preferable to use a white LED light source (LED2).

Specific examples of the LED 1 include NSSW306D-HG-V1 (manufactured by Nichia Chemicals) and NSSW304D-HG-V1 (manufactured by Nichia Chemicals).

Specific examples of the LED 2 include NSSW440 (manufactured by Nichia Chemicals) and NSSW304D (manufactured by Nichia Chemicals).

The present invention will be explained below with reference to Examples. In addition, "parts" and "%" in Examples represent "parts by mass" and "% by mass", respectively.

Prior to Examples, each measurement method will be explained.

The weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH/g), and amine value (mgKOH/g) of the resin are as follows.

(Average molecular weight of resin)
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the binder resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. HLC-8220GPC (manufactured by Tosoh Corporation) was used as the equipment, two separation columns were connected in series, and the packing material for both was "TSK-GEL SUPER HZM-N" connected in two series, and the oven temperature was 40. The measurement was performed at a flow rate of 0.35 ml/min using a THF solution as an eluent.
The sample was dissolved in a solvent consisting of 1 wt % of the above eluent, and 20 microliters of the sample was injected. All molecular weights are polystyrene equivalent values.

(Acid value of resin (mgKOH/g))
Add 80 ml of acetone and 10 ml of water to 0.5 to 1 g of the resin solution, stir to dissolve uniformly, and use an automatic titration device ("COM-555" manufactured by Hiranuma Sangyo) with 0.1 mol/L KOH aqueous solution as the titrant. ) to measure the acid value (mgKOH/g) of the resin solution. Then, the acid value per solid content of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

<Production of finely divided phthalocyanine pigment>
(Finely divided phthalocyanine pigments A1-1 to 5)
Finely divided phthalocyanine pigments (A1-1 to A1-5) having the following formulas 51 to 55 were produced according to Examples of JP-A No. 2017-111398. The structure is shown below.

(Finely divided phthalocyanine pigment A1-1)
Formula (51)

(Finely divided phthalocyanine pigment A1-2)
Formula (52)

(Finely divided phthalocyanine pigment A1-3)
Formula (53)

(Finely divided phthalocyanine pigment A1-4)
Formula (54)

(Finely divided phthalocyanine pigment A1-5)
Formula (55)

(Finely divided phthalocyanine pigment (A2-1))
Phthalocyanine pigment C. I. 100 parts of Pigment Green 58 ("FASTGEN GREEN A110" manufactured by DIC Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70° C. for 6 hours. This kneaded material was poured into 3,000 parts of warm water, heated to 70°C and stirred for 1 hour to form a slurry. After repeated filtration and water washing to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight to finely 97 parts of phthalocyanine pigment (A2-1) were obtained.

(Finely divided phthalocyanine pigment (A1-1/A2-1))
Equal amounts of the finely divided phthalocyanine pigment (A1-1) and the finely divided phthalocyanine pigment (A2-1) were mixed to obtain a finely divided phthalocyanine pigment (A1-1/A2-1).

(Finely divided phthalocyanine pigment (A2-2))
A 300 mL flask was charged with 91 parts of sulfuryl chloride, 109 parts of aluminum chloride, 15 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 74 parts of bromine. The temperature was raised to 130° C. over 40 hours, taken out in water, and filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of pulverized sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged into a 1 L double-arm kneader and kneaded at 100° C. for 6 hours. After kneading, the mixture was poured into 2 kg of water at 80° C., stirred for 1 hour, filtered, washed with hot water, dried, and crushed to obtain a finely divided phthalocyanine pigment (A2-2). The resulting finely divided phthalocyanine pigment (A2-2) was found to have an average number of halogen atoms in one molecule of 13.97, of which the average number of bromine atoms was 11.46, according to fluorescent X-ray analysis using Rigaku ZSX100E. It was a halogenated zinc phthalocyanine pigment having an average number of chlorine atoms of 2.51.

(Finely divided phthalocyanine pigment (A2-3))
A 300 mL flask was charged with 91 parts of sulfuryl chloride, 109 parts of aluminum chloride, 15 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 59 parts of bromine. The temperature was raised to 130° C. over 40 hours, taken out in water, and filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of pulverized sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged into a 1 L double-arm kneader and kneaded at 100° C. for 6 hours. After kneading, the mixture was poured into 2 kg of water at 80° C., stirred for 1 hour, filtered, washed with hot water, dried, and crushed to obtain a finely divided phthalocyanine pigment (A2-3). The obtained finely divided phthalocyanine pigment (A2-3) was found to have an average number of 12.71 halogen atoms in one molecule, including an average of 10.22 bromine atoms and an average number of chlorine atoms, according to X-ray fluorescence analysis. was a halogenated zinc phthalocyanine pigment with an average of 2.49 particles.

(Finely divided phthalocyanine pigment (A2-4))
A 300 mL flask was charged with 91 parts of sulfuryl chloride, 109 parts of aluminum chloride, 15 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 44 parts of bromine. The temperature was raised to 130° C. over 40 hours, taken out in water, and filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of pulverized sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged into a 1 L double-arm kneader and kneaded at 100° C. for 6 hours. After kneading, the mixture was poured into 2 kg of water at 80° C., stirred for 1 hour, filtered, washed with hot water, dried, and crushed to obtain a finely divided phthalocyanine pigment (A2-4). The resulting finely divided phthalocyanine pigment (A2-4) was found to have an average of 11.98 halogen atoms in one molecule, including an average of 9.00 bromine atoms and an average of 9.00 chlorine atoms in one molecule. was a halogenated zinc phthalocyanine pigment with an average of 2.98 pieces.

(Finely divided phthalocyanine pigment (A2-5))
A 300 mL flask was charged with 109 parts of sulfuryl chloride, 131 parts of aluminum chloride, 18 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 52 parts of bromine. The temperature was raised to 130° C. over 40 hours, taken out in water, and filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of pulverized sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged into a 1 L double-arm kneader and kneaded at 100° C. for 6 hours. After kneading, the mixture was poured into 2 kg of water at 80° C., stirred for 1 hour, filtered, washed with hot water, dried, and crushed to obtain a finely divided phthalocyanine pigment (A2-5). The resulting finely divided phthalocyanine pigment (A2-5) was found to have an average number of 12.69 halogen atoms in one molecule, including an average of 8.54 bromine atoms and an average number of chlorine atoms, according to X-ray fluorescence analysis. was a halogenated zinc phthalocyanine pigment with an average of 4.16 pieces.

(Finely divided phthalocyanine pigment (A2-6))
A 300 mL flask was charged with 91 parts of sulfuryl chloride, 72 parts of aluminum chloride, 15 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 29 parts of bromine. The temperature was raised to 130° C. over 40 hours, taken out in water, and filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of pulverized sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged into a 1 L double-arm kneader and kneaded at 100° C. for 6 hours. After kneading, the mixture was poured into 2 kg of water at 80° C., stirred for 1 hour, filtered, washed with hot water, dried, and crushed to obtain a finely divided phthalocyanine pigment (A2-6). The resulting finely divided phthalocyanine pigment (A2-6) was found to have an average number of halogen atoms in one molecule of 8.88, including an average of 6.90 bromine atoms and an average number of chlorine atoms, according to X-ray fluorescence analysis. was a halogenated zinc phthalocyanine pigment with an average of 1.98 pieces.

<Production of finely divided yellow pigment>
(Finely divided yellow pigment (A3-1 to 3))
Finely divided phthalocyanine pigments (A3-1 to A3-3) of quinophthalone pigments having the following formulas (56) to (58) were prepared according to Examples of JP-A No. 2012-226110. The structure is shown below.

(Finely refined yellow pigment A3-1)
Formula (56)

(Finely refined yellow pigment A3-2)
Formula (57)

(Finely refined yellow pigment A3-3)
Formula (58)

(Finely refined yellow pigment (A3-4))
C. I. 100 parts of Pigment Yellow 138 (PY138) ("Paliotol Yellow K0960-HD" manufactured by BASF), 700 parts of sodium chloride, and 180 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and heated at 80°C for 6 hours. Kneaded. This mixture was poured into 2,000 parts of warm water, stirred for 1 hour while heating to 80°C to form a slurry, filtered and washed repeatedly to remove salt and solvent, dried overnight at 80°C, and made into a slurry of 95 parts of fine powder. A colored yellow pigment (A3-4) was obtained.

(Finely refined yellow pigment (A3-5))
Isoindoline yellow pigment C. I. 100 parts of pigment yellow 139 ("Irgafore Yellow 2R-CF" manufactured by BASF), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader and kneaded at 60° C. for 10 hours. Next, this mixture was poured into 3 liters of warm water, heated to about 80°C and stirred with a high-speed mixer for about 1 hour to form a slurry, and after repeated filtration and water washing to remove sodium chloride and solvent, It was dried at ℃ for one day and night to obtain a finely divided yellow pigment (A3-5).

(Finely refined yellow pigment (A3-6))
100 parts of a metal complex yellow pigment (C.I. pigment yellow 150, "Yellow Pigment E4GN" manufactured by Lanxess Corporation), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.). The mixture was kneaded at 60°C for 10 hours. Next, this mixture was poured into 3 liters of warm water, heated to about 80°C and stirred with a high-speed mixer for about 1 hour to form a slurry, and after repeated filtration and water washing to remove sodium chloride and solvent, It was dried at ℃ for one day and night to obtain a finely divided yellow pigment (A3-6). The average primary particle diameter was 36.6 nm.

(Finely refined yellow pigment (A3-7))
Yellow pigment C. I. Pigment Yellow 185 ("Paliotol Yellow D1155" manufactured by BASF): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were placed in a stainless steel 1-gallon kneader and kneaded at 120° C. for 8 hours. Next, this kneaded material was poured into 5 liters of warm water, heated to 70°C and stirred for 1 hour to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80°C overnight. , a finely divided yellow pigment (A3-7) was obtained.

Pcは、フタロシアニン骨格を表す。 <Dye derivative (b0)>
The dye derivatives as described below were used.
Pigment derivative (b0-1)

Pc represents a phthalocyanine skeleton.

Pigment derivative (b0-2)

The meanings of the abbreviations shown below are as follows.
HEMA: 2-hydroxyethyl methacrylate EHMA: 2-ethylhexyl methacrylate BMA: n-butyl methacrylate BzMA: Benzyl methacrylate MMA: Methyl methacrylate DMAPMA: Dimethylaminopropyl methacrylamide DMAEMA: Dimethylaminoethyl methacrylamide PGMAc: Propylene glycol Monomethyl ether acetate

<Production of resin type dispersant (B) solution>
(Production of compound (B-1: resin type dispersant) solution containing the unit represented by general formula (1))
In a 500 mL round-bottomed 4-neck separable flask equipped with a condenser, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 250 parts by mass of tetrahydrofuran (THF) and 5.81 parts of dimethylketenemethyltrimethylsilyl acetal as an initiator were added. Parts by mass were added via the addition funnel, and the mixture was sufficiently purged with nitrogen. 0.5 parts by mass of a 1 mol/L acetonitrile solution of tetrabutylammonium m-chlorobenzoate as a catalyst is injected using a syringe, and 19.7 parts by mass of HEMA and 7.5 parts by mass of EHMA, which are block monomers having solvent affinity, are injected using a syringe. , 12.9 parts by mass of BMA, 10.7 parts by mass of BzMA, and 30.9 parts by mass of MMA were added dropwise over 60 minutes using an addition funnel. The temperature was kept below 40°C by cooling the reaction flask with an ice bath. After 1 hour, 18.3 parts by mass of DMAPMA, which is a monomer for coloring material adsorption function block, was added dropwise over 20 minutes. After reacting for 1 hour, 1 part by mass of methanol was added to stop the reaction. The obtained block copolymer THF solution is reprecipitated in hexane, purified by filtration and vacuum drying, and has solvent affinity with the coloring material adsorption functional block containing the structural unit represented by general formula (1). A compound (B-1) containing the block was obtained.

(Manufacture of resin type dispersant (B1-1-1) solution)
In a 100 mL round bottom flask, 10.0 parts by mass of compound (B-1) was dissolved in 40.6 parts by mass of PGMAc, and phenylphosphinic acid (manufactured by Tokyo Kasei Co., Ltd.), which is a compound represented by the above general formula (2), was dissolved in 40.6 parts by mass of PGMAc. .75 parts by mass (0.50 mol of phenylphosphinic acid per 1.0 mol of DMAPMA unit of compound (B-1)) was added, stirred at a reaction temperature of 30°C for 20 hours, and PGMAc was added to a solid content of 20% by mass. A resin-type dispersant (B1-1-1) solution was obtained by adding and adjusting.

(Production of resin type dispersant (B1-1-2) solution)
Resin-type dispersion was carried out in the same manner as the resin-type dispersant (B1-1-1) solution, except that phenylphosphinic acid was added to 1.0 mol of DMAPMA unit of compound (B-1) so that the amount was 1.0 mol. A solution of agent (B1-1-2) was obtained.

(Manufacture of resin type dispersant (B1-1-3) solution)
In a 100 mL round bottom flask, 10.0 parts by mass of compound (B-1) was dissolved in 40.6 parts by mass of methanol, and 0.66 parts by mass of benzyl chloride, which is a compound represented by the above general formula (4), was dissolved in 40.6 parts by mass of methanol. Add 0.50 mol of benzyl chloride to 1.0 mol of DMAPMA unit of compound (B-1), stir at a reaction temperature of 60 ° C. for 20 hours, adjust the solid content by adding PGMAc to 20% by mass, A resin type dispersant (B1-1-3) solution was obtained.

(Manufacture of resin type dispersant (B1-1-4) solution)
The resulting resin-type dispersant (B1-1-3) solution was reprecipitated in hexane, and purified by filtration and vacuum drying. Next, 10.0 parts by mass of the purified product was dissolved in 40.6 parts by mass of PGMAc in a 100 mL round bottom flask, and 0.0 parts by mass of phenylphosphinic acid (manufactured by Tokyo Kasei), which is a compound represented by the general formula (2), was dissolved. Add 75 parts by mass (0.50 mol of phenylphosphinic acid to the remaining 0.5 mol of DMAPMA unit in the resin-type dispersant (B1-1-3)) and stir at a reaction temperature of 30°C for 20 hours to reduce the solid content. Adjustment was made by adding PGMAc to 20% by mass to obtain a resin type dispersant (B1-1-4) solution.

(Production of compound (B-2: resin type dispersant) solution containing the unit represented by general formula (1))
In a 500 mL round-bottomed 4-neck separable flask equipped with a condenser, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 250 parts by mass of tetrahydrofuran (THF) and 5.81 parts by weight of dimethylketenemethyltrimethylsilyl acetal as an initiator were added. Parts by mass were added via the addition funnel, and the mixture was sufficiently purged with nitrogen. 0.5 parts by mass of a 1 mol/L acetonitrile solution of tetrabutylammonium m-chlorobenzoate as a catalyst is injected using a syringe, and 19.7 parts by mass of HEMA and 7.5 parts by mass of EHMA, which are block monomers having solvent affinity, are injected using a syringe. , 12.9 parts by mass of BMA, 10.7 parts by mass of BzMA, and 32.5 parts by mass of MMA were added dropwise over 60 minutes using an addition funnel. The temperature was kept below 40°C by cooling the reaction flask with an ice bath. After 1 hour, 16.7 parts by mass of DMAEMA, which is a monomer for coloring material adsorption function block, was added dropwise over 20 minutes. After reacting for 1 hour, 1 part by mass of methanol was added to stop the reaction. The obtained block copolymer THF solution is reprecipitated in hexane, purified by filtration and vacuum drying, and has solvent affinity with the colorant adsorption functional block containing the structural unit represented by general formula (1). A compound (B-2) containing the block was obtained.

(Manufacture of resin type dispersant (B1-2-1) solution)
In a 100 mL round bottom flask, 10.0 parts by mass of compound (B-2) was dissolved in 40.6 parts by mass of PGMAc, and phenylphosphinic acid (manufactured by Tokyo Kasei Co., Ltd.), which is a compound represented by the above general formula (2), was dissolved in 40.6 parts by mass of PGMAc. .75 parts by mass (0.50 mol of phenylphosphinic acid per 1.0 mol of DMAEMA unit of compound (B-2)) was added, stirred at a reaction temperature of 30°C for 20 hours, and PGMAc was added to a solid content of 20% by mass. By adding and adjusting, a resin-type dispersant (B1-2-1) solution was obtained.

(Manufacture of resin type dispersant (B1-2-2) solution)
Resin-type dispersion was carried out in the same manner as the resin-type dispersant (B1-2-1) solution, except that phenylphosphinic acid was added to 1.0 mol of DMAEMA unit of compound (B-2) so that the amount was 1.0 mol. A solution of agent (B1-2-2) was obtained.

(Manufacture of resin type dispersant (B1-2-3) solution)
In a 100 mL round bottom flask, 10.0 parts by mass of compound (B-2) was dissolved in 40.6 parts by mass of methanol, and 0.66 parts by mass of benzyl chloride ( 0.50 mol of benzyl chloride was added to 1.0 mol of DMAEMA unit of compound (B-2), stirred at a reaction temperature of 60°C for 20 hours, and adjusted by adding PGMAc to a solid content of 20% by mass, A resin type dispersant (B1-2-3) solution was obtained.

(Manufacture of resin type dispersant (B1-2-4) solution)
The resulting resin-type dispersant (B1-2-3) solution was reprecipitated in hexane, and purified by filtration and vacuum drying. Next, 10.0 parts by mass of the purified product was dissolved in 40.6 parts by mass of PGMAc in a 100 mL round-bottomed flask, and 0.0 parts by mass of phenylphosphinic acid (manufactured by Tokyo Kasei), which is a compound represented by the general formula (2), was dissolved. Add 75 parts by mass (0.50 mol of phenylphosphinic acid to 0.5 mol of DMAEMA unit remaining in the resin-type dispersant (B1-2-3)), stir at a reaction temperature of 30°C for 20 hours, and reduce the solid content. Adjustment was made by adding PGMAc to 20% by mass to obtain a resin type dispersant (B1-2-4) solution.

(Manufacture of compound (B-3: resin type dispersant) solution containing the unit represented by general formula (1))
In a 500 mL round-bottomed 4-neck separable flask equipped with a condenser, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 250 parts by mass of tetrahydrofuran (THF) and 5.81 parts of dimethylketenemethyltrimethylsilyl acetal as an initiator were added. Parts by mass were added via the addition funnel, and the mixture was sufficiently purged with nitrogen. 0.5 parts by mass of a 1 mol/L acetonitrile solution of tetrabutylammonium m-chlorobenzoate as a catalyst was injected using a syringe, and 10.0 parts by mass of HEMA and 9.9 parts by mass of BzMA were added as block monomers having solvent affinity. , 30.0 parts by mass of MMA were added dropwise over 60 minutes using an addition funnel. The temperature was kept below 40°C by cooling the reaction flask with an ice bath. After 1 hour, 50.1 parts by mass of DMAEMA, which is a monomer for coloring material adsorption function block, was added dropwise over 60 minutes. After reacting for 2 hours, 1 part by mass of methanol was added to stop the reaction. The obtained block copolymer THF solution is reprecipitated in hexane, purified by filtration and vacuum drying, and has solvent affinity with the coloring material adsorption functional block containing the structural unit represented by general formula (1). A compound (B-3) containing the block was obtained.

(Manufacture of resin type dispersant (B1-3-1) solution)
In a 100 mL round bottom flask, 10.0 parts by mass of compound (B-3) was dissolved in 40.6 parts by mass of PGMAc, and phenylphosphinic acid (manufactured by Tokyo Kasei) 2, which is a compound represented by the general formula (2) above, was dissolved. .25 parts by mass (0.50 mol of phenylphosphinic acid per 1.0 mol of DMAEMA unit of compound (B-3)) was added, stirred at a reaction temperature of 30°C for 20 hours, and PGMAc was added to a solid content of 20% by mass. A resin-type dispersant (B1-3-1) solution was obtained by adding and adjusting.

(Manufacture of resin type dispersant (B1-3-2) solution)
Resin-type dispersion was carried out in the same manner as the resin-type dispersant (B1-3-1) solution, except that phenylphosphinic acid was added to 1.0 mol of DMAEMA unit of compound (B-3) so that the amount was 1.0 mol. A solution of agent (B1-3-2) was obtained.

(Manufacture of resin type dispersant (B1-3-3) solution)
In a 100 mL round bottom flask, 10.0 parts by mass of compound (B-3) was dissolved in 40.6 parts by mass of methanol, and 1.98 parts by mass of benzyl chloride, which is a compound represented by the above general formula (4), was dissolved in 40.6 parts by mass of methanol. 0.50 mol of benzyl chloride was added to 1.0 mol of DMAEMA unit of compound (B-3), stirred at a reaction temperature of 60°C for 40 hours, and adjusted by adding PGMAc to a solid content of 20% by mass, A resin type dispersant (B1-3-3) solution was obtained.

(Manufacture of resin type dispersant (B1-3-4) solution)
The resulting resin-type dispersant (B1-3-3) solution was reprecipitated in hexane, and purified by filtration and vacuum drying. Next, 10.0 parts by mass of the purified product was dissolved in 40.6 parts by mass of PGMAc in a 100 mL round bottom flask, and phenylphosphinic acid (manufactured by Tokyo Kasei) 2. Add 25 parts by mass (0.50 mol of phenylphosphinic acid to 0.5 mol of DMAEMA unit remaining in the resin type dispersant (B1-4-3)) and stir at a reaction temperature of 30°C for 40 hours to reduce the solid content. Adjustment was made by adding PGMAc to 20% by mass to obtain a resin type dispersant (B1-3-4) solution.

<Production example of binder resin (C)>
(Preparation of binder resin (C-1) liquid)
196 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device in a separable 4-necked flask, the temperature was raised to 80°C, the inside of the reaction vessel was replaced with nitrogen, and then added dropwise. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.) 1 part of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition was completed, the reaction was continued for an additional 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content, and PGMAc was added to the previously synthesized resin solution so that the nonvolatile content was 20%. A binder resin (C-1) solution was prepared. The weight average molecular weight (Mw) was 26,000.

(Preparation of binder resin (C-2) liquid)
207 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device in a separable 4-necked flask, the temperature was raised to 80°C, the inside of the reaction vessel was replaced with nitrogen, and then added dropwise. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2'-azobis A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After the dropwise addition was completed, the reaction was continued for an additional 3 hours to obtain a copolymer resin solution. Next, the entire amount of the obtained copolymer solution was stirred while stopping nitrogen gas and injecting dry air for 1 hour. After cooling to room temperature, 2-methacryloyloxyethyl isocyanate (Karens A mixture of 6.5 parts of MOI), 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was added dropwise at 70° C. over 3 hours. After the dropwise addition was completed, the reaction was continued for an additional hour to obtain an acrylic resin solution. After cooling to room temperature, approximately 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content. Cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20%. A binder resin (C-2) was prepared. The weight average molecular weight (Mw) was 18,000.

(Preparation of binder resin (C-3) liquid)
370 parts of cyclohexanone was charged into a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device, the temperature was raised to 80°C, and the inside of the flask was replaced with nitrogen. 18 parts of milphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2.0 parts of 2,2'-azobisisobutyronitrile. part of the mixture was added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 100°C for 3 hours, and then a solution of 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100°C for 1 hour. Next, the inside of the container was replaced with air, and 9.3 parts of acrylic acid (100% of glycidyl groups), 0.5 parts of trisdimethylaminophenol, and 0.1 part of hydroquinone were added to the container, and heated at 120°C. The reaction was continued for 6 hours, and the reaction was terminated when the acid value of the solid content reached 0.5, to obtain a solution of acrylic resin. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 parts of triethylamine were added and reacted at 120° C. for 3.5 hours to obtain a solution of acrylic resin.
After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the nonvolatile content. PGMAc was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. A binder resin (C-3) solution was prepared. The weight average molecular weight (Mw) was 19,000.

(Preparation of binder resin (C-4) liquid)
A separable flask equipped with a cooling tube was prepared as a reaction tank, and on the other hand, as a monomer dropping tank, 40 parts of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 40 parts of methacrylic acid, and methacrylic acid were prepared. Prepare a well-stirred mixture of 120 parts of methyl, 4 parts of t-butylperoxy-2-ethylhexanoate ("Perbutyl O" manufactured by NOF Corporation), and 40 parts of PGMAc, and use it as a chain transfer agent dropping tank to add n-dodecane. A mixture of 8 parts of thiol and 32 parts of PGMAc was prepared by stirring thoroughly.
After charging 395 parts of PGMAc into a reaction tank and replacing the atmosphere with nitrogen, the reaction tank was heated in an oil bath while stirring to raise the temperature of the reaction tank to 90°C. After the temperature of the reaction tank stabilized at 90°C, dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. Each dropwise addition took 135 minutes while maintaining the temperature at 90°C. Sixty minutes after the dropwise addition was completed, the temperature of the reaction tank was raised to 110°C. After maintaining the temperature at 110°C for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of a mixed gas of oxygen/nitrogen = 5/95 (volume ratio) was started. Next, 70 parts of glycidyl methacrylate, 0.4 parts of 2,2'-methylenebis(4-methyl-6-t-butylphenol), and 0.8 parts of triethylamine were placed in a reaction tank, and the mixture was allowed to react at 110°C for 12 hours. Ta. After that, 150 parts of PGMAc was added and cooled to room temperature, and approximately 2 g of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the nonvolatile content, and the nonvolatile content was 20% by mass in the resin solution synthesized earlier. PGMAc was added to obtain a binder resin (C-4) solution. The weight average molecular weight of the resin was 18,000, and the acid value per solid content was 2 mgKOH/g.

(Preparation of binder resin (CM) liquid)
Binder resin (C-2) to (C-4) liquids were mixed in equal amounts to form a binder resin (CM) liquid.

<Method for producing colored composition (single color)>
[Example 1]
(Preparation of colored composition (R-1))
The following mixture was stirred and mixed until it was homogeneous, and then dispersed for 3 hours using an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan) using zirconia beads with a diameter of 0.5 mm. The mixture was filtered through a 0 μm filter to produce a colored composition (R-1) containing 24.3% by mass of non-volatile components.
Pigment (A1-1): 20 parts Resin type dispersant (B1-1-4: 20% non-volatile content liquid): 5 parts Binder resin (C-1: 20% non-volatile content liquid): 20 parts Solvent (P): 55 copies

[Examples 2 to 34, Comparative Example 1, Production Examples 1 to 8]
(Preparation of colored compositions (R-2 to 43))
Colored compositions (R-2 to R-43) were produced in the same manner as in Example 1, except that the material types and masses were changed as listed in Table 1.

<Production method of colored composition (coloring material mixture)>
[Example 101]
(Preparation of colored composition (X-1))
The following raw materials were mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a colored composition (X-1).
Coloring composition (R-1: 25% nonvolatile content liquid): 40 parts Coloring composition (R-36: 25% nonvolatile content liquid): 16 parts Binder resin (C-1: 20% nonvolatile content liquid): 30 parts Solvent (P): 14 parts

[Examples 102 to 141, Comparative Example 101]
(Preparation of colored compositions (X-2 to 42))
Colored compositions (X-2 to 42) were prepared in the same manner as in Example 101, except that the material type and mass were changed as listed in Table 2.

<Evaluation of colored composition>
The obtained colored compositions (R-1 to 35, X-1 to 42) were tested for viscosity and storage stability in the following manner. The test results are shown in Table 3.
The meaning of the evaluation rank is as follows.
◎: Extremely good 〇: Good △: Possible for practical use ×: Not suitable for practical use

(Measurement of viscosity characteristics)
The viscosity at a rotation speed of 20 rpm was measured using an E-type viscometer ("ELD-type viscometer" manufactured by Toki Sangyo Co., Ltd.). The evaluation ranks are as follows.
○: Viscosity 4.0 or more and less than 20.0
×: Viscosity 20 or more
(Storage stability)
The storage stability of the colored compositions obtained in Examples and Comparative Examples was evaluated by the following method.
The initial viscosity on the next day after preparing the colored composition and the viscosity over time accelerated at 40°C for one week were measured at 25°C using an E-type viscometer ("ELD-type viscometer" manufactured by Toki Sangyo Co., Ltd.). The measurement was performed at a rotation speed of 50 rpm. From the values of the initial viscosity and the viscosity over time, the rate of change in viscosity over time was calculated using the following formula, and the storage stability was evaluated in two stages.
[Viscosity change rate over time] = | ([Initial viscosity] - [Viscosity over time]) / [Initial viscosity] | × 100
○: Change rate less than 5% ×: Change rate 5% or more

(Foreign substance evaluation)
Foreign matter evaluation was performed by coating a colored composition on a transparent substrate so that the dry coating film was about 2.0 μm, and heat-treating it in an oven at 230°C for 1 hour. The number was measured. For evaluation, surface observation was performed using a metallurgical microscope "BX60" (manufactured by Olympus Systems). The magnification was set to 500 times, and the number of foreign substances observable in five arbitrary fields of view was measured using transmission. The evaluation criteria are as follows.
◎: Number of foreign objects is less than 5
〇: Number of foreign substances is 5 or more and less than 20
△: Number of foreign substances is 21 or more and less than 100
×: Number of foreign objects is 100 or more

<Method for producing photosensitive coloring composition>
[Example 201]
(Photosensitive coloring composition (Y-1))
The following raw materials were mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a photosensitive coloring composition (Y-1).
Coloring composition (R-1: 20% non-volatile content): 50.0 parts Binder resin (CM: 20% non-volatile content): 15.0 parts Thermosetting compound (CE-1): 1.0 parts Heat Curable compound (CE-2): 1.0 part Polymerizable compound (D): 3.0 parts Photoinitiator (E): 1.8 parts Sensitizer (H): 0.2 parts Thiol chain Transfer agent (I): 0.4 part Polymerization inhibitor (J): 0.1 part Ultraviolet absorber (K): 0.1 part Antioxidant (L): 0.1 part Leveling agent (M: nonvolatile content) 3%): 1.0 part Storage stabilizer (N): 0.1 part Silane coupling agent (O): 0.2 part Solvent (P): 26.0 part

[Examples 202 to 275, Comparative Examples 201 to 202]
(Preparation of photosensitive coloring composition (Y-2 to 77))
Photosensitive coloring compositions (Y-2 to 77) were prepared in the same manner as in Example 201, except that the type of coloring composition in Example 201 was changed as shown in Table 4. In addition, each raw material is as follows.

<Thermosetting compound (CE)>
・Epoxy compound (CE-1)
(CE-1-1) 1,2- of 2,2'-bis(hydroxymethyl)-1-butanol
Epoxy-4-(2-oxiranyl)cyclohexane adduct
[EHPE-3150 (manufactured by Daicel)],
(CE-1-2) Glycidyl etherified epoxy compound of sorbitol
[Denacol EX611 (manufactured by Nagase ChemteX Corporation)],
(CE-1-3) Triglycidyl isocyanurate (CE-1-1) to (CE-1-3) were mixed in equal amounts to prepare an epoxy compound (CE-1).
・Oxetane compound (CE-2):
3-Ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane
[Aron oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)]

<Polymerizable compound (D)>
(D-1) Trimethylolpropane triacrylate
[Aronix M309 (manufactured by Toagosei Co., Ltd.)]
(D-2) Dipentaerythritol penta and hexaacrylate (E-2)
[Aronix M402 (manufactured by Toagosei Co., Ltd.)]
(D-3) Polybasic acidic acrylic oligomer
[Aronix M520 (manufactured by Toagosei Co., Ltd.)]
(D-4) Caprolactone-modified dipentaerythritol hexaacrylate
[KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.)]

(D-5) Polyfunctional urethane acrylate as shown below Pentaerythritol triacrylate (432 g, hexamethylene diisocyanate 84 g) was charged into a 5-necked reaction vessel with a content of 1 liter, and reacted at 60°C for 8 hours to form a (meth)acryloyl group. A product containing a polyfunctional urethane acrylate (D-5) having It was confirmed by IR analysis that no isocyanate groups were present in the reaction product.

(D-6) Bifunctional bisphenol A type (meth)acrylate
[ABE-300 (manufactured by Shin Nakamura Chemical Co., Ltd.)]
(D-7) Ethoxylated isocyanuric acid triacrylate
[A-9300 (manufactured by Shin Nakamura Chemical Co., Ltd.)]
The above (D-1) to (D-7) were mixed in the same amount to obtain a polymerizable compound (D).

<Photopolymerization initiator (E)>
(E-1) 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one
[Irgacure 907 (manufactured by BASF Japan)]
(E-2) 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone
[Irgacure 379 (manufactured by BASF Japan)]
(E-3) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide
[Lucirin TPO (manufactured by Ciba Japan)]
(E-4) 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole
[Biimidazole (manufactured by Kurogane Kasei Co., Ltd.)]
(E-5) p-dimethylaminoacetophenone
[DMA (manufactured by Daiki Fine Co., Ltd.)]
(E-6) Ethan-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(O-acetyloxime)
[Irgacure OXE02 (manufactured by BASF Japan)]
(E-7) 1-[4-(2-hydroxyethoxy)-phenyl] -2-hydroxy-2-methyl-1-propan-1-one
[Irgacure 2959 (manufactured by BASF Japan)]
(E-8) Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide
[Irgacure 819 (manufactured by BASF Japan)]
The above (E-1) to (E-8) were mixed in the same amount to prepare a photopolymerization initiator (E).

<Sensitizer (H)>
(H-1) 2,4-diethylthioxanthone
[Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.)]
(H-2) 4,4'-bis(diethylamino)benzophenone
[CHEMARK DEABP (manufactured by Chemark Chemical)]
As described above, (H-1) and (H-2) were mixed in the same amount to prepare a sensitizer (H).

<Thiol chain transfer agent (I)>
(I-1) Trimethylolethane tris (3-mercaptobutyrate)
[TEMB (manufactured by Showa Denko)]
(I-2) Trimethylolpropane tris (3-mercaptobutyrate)
[TPMB (manufactured by Showa Denko)]
(I-3) Pentaerythritol tetrakis (3-mercaptopropionate)
[PEMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
(I-4) Trimethylolpropane tris (3-mercaptopropionate)
[TMMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
(I-5) Tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate
[TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.)]
The above (I-1) to (I-5) were mixed in the same amount to prepare a thiol chain transfer agent (I).

<Polymerization inhibitor (J)>
(J-1) 3-Methylcatechol (J-2) Methylhydroquinone (J-3) t-Butylhydroquinone Above, (J-1) to (J-3) are mixed in equal amounts, and a polymerization inhibitor is added. (J).

<Ultraviolet absorber (K)>
(K-1) 2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine
[TINUVIN400 (manufactured by BASF Japan)]
(K-2) 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol
[TINUVIN900 (manufactured by BASF Japan)]
The above (K-1) to (K-2) were mixed in the same amount to prepare an ultraviolet absorber (K).

<Antioxidant (L)>
(L-1) Pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (L-2) Dioctadecyl 3,3'-thiodipropanoate (L-3) Tris[2 , 4-di-(t)-butylphenyl]phosphine (L-4) bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (L-5) p-octylphenyl salicylate or more, (L -1) to (L-5) were mixed in the same amount to prepare an antioxidant (L).

<Leveling agent (M)>
BYK-330 manufactured by BYK Chemie Co., Ltd. 1 copy,
1 copy of "Mega Fac F-551" manufactured by DIC Corporation,
A mixed solution in which 1 part of "Emulgen 103" manufactured by Kao Corporation was dissolved in 97 parts of PGMAc.

<Storage stabilizer (N)>
(N-1) 2,6-bis(1,1-dimethylethyl)-4-methylphenol (“BHT” manufactured by Honshu Chemical Industry Co., Ltd.)
(N-2) Triphenylphosphine (“TPP” manufactured by Hokuko Chemical Industry Co., Ltd.)
The above (N-1) to (N-2) were mixed in the same amount to prepare a storage stabilizer (N).

<Adhesion improver (O)>
(O-1) 3-glycidoxypropyltriethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(O-2) 3-methacryloxypropyltriethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(O-3)N-2-(aminoethyl)-3-aminopropyltrimethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(O-4) 3-Mercaptopropyltrimethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
As described above, (O-1) to (O-4) were mixed in the same amount to prepare a silane coupling agent (O).

<Solvent (P)>
(P-1) PGMAc 30 parts (P-2) Cyclohexanone 30 parts (P-3) Ethyl 3-ethoxypropionate 10 parts (P-4) Propylene glycol monomethyl ether 10 parts (P-5) Cyclohexanol acetate 10 parts (P-6) Dipropylene glycol methyl ether acetate 10 parts Above, (P-1) to (P-6) were mixed in the above mass parts, respectively, to prepare a solvent (P).

<Evaluation of photosensitive coloring composition>
Each test was conducted in the following manner. The results of the test are shown in Table 5.
The meaning of the evaluation rank is as follows.
◎: Very good 〇: Good △: Possible for practical use ×: Not suitable for practical use

(Development speed evaluation)
The photosensitive coloring composition was spin-coated onto a 10 mm x 10 mm glass substrate with a thickness of 0.7 mm using a spin coater so that the dry film thickness was 1.0 μm, and dried at 70° C. for 20 minutes. 2 ml of a 2% by mass aqueous potassium hydroxide solution was added dropwise to the above coating film, and the time until the coating thickness disappeared was measured to evaluate the development speed of the photosensitive coloring composition. The evaluation ranks are as follows.
○: Less than 10 seconds △: 10 seconds or more, less than 15 seconds ×: 15 seconds or more (measurement of viscosity characteristics)
The viscosity at a rotation speed of 20 rpm was measured using an E-type viscometer ("ELD-type viscometer" manufactured by Toki Sangyo Co., Ltd.). The evaluation ranks are as follows.
〇: Viscosity 2.0 or more and less than 10.0
×: Viscosity 10.0 or more
(Storage stability)
The storage stability of the photosensitive coloring compositions obtained in Examples and Comparative Examples was evaluated by the following method.
The initial viscosity on the next day after preparing the photosensitive coloring composition and the aging viscosity after aging at 40°C for one week were measured using an E-type viscometer ("ELD-type viscometer" manufactured by Toki Sangyo Co., Ltd.). The measurement was carried out at a temperature of 50 rpm. From the values of the initial viscosity and the viscosity over time, the rate of change in viscosity over time was calculated using the following formula, and the storage stability was evaluated in two stages.
[Viscosity change rate over time] = | ([Initial viscosity] - [Viscosity over time]) / [Initial viscosity] | × 100
◎: Rate of change is less than 5% ○: Rate of change is 5% or more and less than 10% ×: Rate of change is 10% or more

(Foreign substance evaluation)
Foreign matter evaluation was performed by coating a photosensitive coloring composition on a transparent substrate so that the dried coating film was approximately 2.0 μm, and heat-treating it in an oven at 230°C for 1 hour. The number of foreign objects was counted. For evaluation, surface observation was performed using a metallurgical microscope "BX60" (manufactured by Olympus Systems). The magnification was set to 500 times, and the number of foreign substances observable in five arbitrary fields of view was measured using transmission. The evaluation criteria are as follows.

◎: Number of foreign objects is less than 5
〇: Number of foreign substances is 5 or more and less than 20
△: Number of foreign objects is 21 or more but less than 100 ×: Number of foreign objects is 100 or more

(Solvent resistance evaluation)
A photosensitive coloring composition was coated on a transparent substrate so that the dry coating thickness was about 2.0 μm, and heat treatment was performed at 230°C for 1 hour in an oven.The coated substrate obtained was then immersed in an N-methylpyrrolidone solution for 30 minutes. After immersion, it was washed with ion-exchanged water, air-dried, and the pattern in the 100 μm photomask portion was observed and evaluated using an optical microscope. The evaluation ranks are as follows.
〇: Good with no change in appearance or color
△: Wrinkles etc. occur in some parts, but the color is good with no change
×: Peeling and discoloration occur

10 Liquid crystal display device 11 Transparent substrate 12 TFT array 13 Transparent electrode layer 14 Alignment layer 15 Polarizing plate 21 Transparent substrate 22 Color filter 23 Transparent electrode layer 24 Alignment layer 25 Polarizing plate 30 Backlight unit 31 White LED light source LC Liquid crystal

Claims (4)

A green colored composition comprising a phthalocyanine pigment (A), a yellow pigment (A3), a resin-type dispersant (B), and a binder resin (C), wherein the phthalocyanine pigment is an aluminum phthalocyanine pigment (A1). including ;
The yellow pigment (A3) contains at least one selected from the group consisting of the following (A3-1) to (A3-7),
and the resin-type dispersant includes a block copolymer,
A green colored composition characterized in that the block copolymer contains a block copolymer (B1) containing at least one kind of structural unit selected from the group consisting of the following structural units (I) and (II). thing.
(I) A structural unit represented by the following general formula (1) and at least one selected from the group consisting of compounds represented by the following general formula (2) and general formula (3) form a salt. Constituent unit.
(II) A structural unit obtained by converting a structural unit represented by the following general formula (1) into a quaternary salt with a compound represented by general formula (4).

General formula (1)

(However, in general formula (1), R ¹ and R ² are each independently a hydrogen atom or a methyl group, A is an alkylene group having 1 to 8 carbon atoms, -[CH(R ^a )-CH(R ^b )-O]x-CH(R ^a )-CH(R ^b )- or [(CH ₂ )y-O]z-(CH ₂ )y-, R ³ and R ⁴ are , each independently represents a hydrogen atom or a hydrocarbon group that may contain a heteroatom, and R ³ and R ⁴ may be combined with each other to form a ring structure. R ^a and R ^b each independently represent is a hydrogen atom or a methyl group, x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18.)

(However, in general formula (2), R ⁵ and R ⁶ each independently have a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, or a substituent. represents a phenyl group or benzyl group, or -O-R ¹¹ , which may have a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group ^, or a substituent. It represents a phenyl group, a benzyl group, or a (meth)acryloyl group via an alkylene group having 1 to 4 carbon atoms.However, at least one of R ⁵ and R ⁶ contains a carbon atom.
In the general formula (3), R ⁷ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have a substituent, or -O-R ¹¹ , R ¹¹ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have a substituent, or an alkylene having 1 to 4 carbon atoms. Represents a (meth)acryloyl group via a group.
In the general formula (4), R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an acidic group or an ester group thereof, a straight chain or branched chain having 1 to 20 carbon atoms which may have a substituent. or a cyclic alkyl group, a vinyl group which may have a substituent, a phenyl group or a benzyl group which may have a substituent, or -O-R ¹² , where R ¹² is a group which may have a substituent A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group which may have a substituent, a phenyl group or benzyl group which may have a substituent, or a C1 to 4 alkyl group. represents a (meth)acryloyl group via an alkylene group, and X represents a chlorine atom, a bromine atom, or an iodine atom. )

(A3-1): Compound represented by the following structural formula
(A3-2): Compound represented by the following structural formula
(A3-3): Compound represented by the following structural formula

(A3-4):C. I. pigment yellow 138
(A3-5):C. I. pigment yellow 139
(A3-6):C. I. pigment yellow 150
(A3-7):C. I. Pigment Yellow 185
A photosensitive green colored composition comprising the colored composition according to claim 1 , a polymerizable compound (D), and a photopolymerization initiator (E). A color filter formed using a base material and the photosensitive green colored composition according to claim 2 . A liquid crystal display device comprising the color filter according to claim 3 .