JP2020016821A - Color filter coloring composition and color filter - Google Patents

Abstract

To provide a color filter coloring composition that can be used to form a film having little wrinkles on a surface thereof after being photo-cured, and a color filter.SOLUTION: A color filter coloring composition comprises a colorant (A), binder resin (B), a photopolymerizable compound (C), photopolymerization initiator (D), sensitizer (E), and organic solvent, the sensitizer (E) being an anthracene compound. Preferably, a mass ratio (D/E) of the photopolymerization initiator (D) to the sensitizer (E) falls within tha range of 10/90 to 90/10.SELECTED DRAWING: Figure 1

Description

The present invention relates to a coloring composition for a color filter that can be used for forming a color filter of a liquid crystal display device or the like.

  Color filters used in liquid crystal display devices and the like have been required to have conflicting performances of increasing the resolution of the color filters and increasing the aperture ratio in order to promote higher image quality and lower power consumption of the color liquid crystal display devices. Patent Document 1 discloses that a coloring layer is formed directly or via a passivation film such as a silicon nitride film on a driving substrate on which TFTs are arranged in a high aperture ratio structure, and this substrate and a liquid crystal are driven. A COA (Color Filter on Array) system in which a transparent electrode is bonded to a substrate formed by vapor deposition or sputtering. In a normal color filter, the width of a light-shielding portion cannot be reduced to a certain value or more to prevent crosstalk between a gate electrode and a transparent electrode. On the other hand, in a COA method, a thick film is placed on a driving substrate on which TFTs are arranged. By forming a colored layer on the film, insulation can be secured and the width of the light shielding portion can be reduced. For this reason, it has been considered that the COA method can greatly increase the aperture ratio and easily obtain high image quality and low power consumption of the color liquid crystal display device.

  Therefore, in Patent Document 2, a photopolymerizable monomer having six polymerizable unsaturated groups and an alkyleneoxy group in one molecule, and four polymerizable unsaturated groups and an alkyleneoxy group in one molecule. A colored composition for a color filter, comprising a photopolymerizable monomer and a photopolymerizable monomer having no alkyleneoxy group and having 5 to 6 polymerizable unsaturated groups in one molecule is disclosed. I have.

JP-A-2004-094263 JP 2014-142582A

  However, in the COA method, the insulating property is inferior due to its structure, so that it is necessary to increase the thickness of the coating as compared with a general filter segment. Therefore, when using a conventional coloring composition for a color filter, the color filter had a difference in photocurability between the coating surface and a deep portion near the substrate, which led to a difference in heat curing shrinkage in post cure, and the color filter In addition, there is a problem that image quality is deteriorated due to wrinkles. In addition, there was a problem that it took a long time for development when the coating film was thick.

  An object of the present invention is to provide a coloring composition for a color filter capable of forming a coating film having a high developing speed and having less wrinkles on the surface after post-curing, and a color filter.

A colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerizable initiator (D), a sensitizer (E), and an organic solvent,
A coloring composition for a color filter, wherein the sensitizer (E) is an anthracene compound.

According to the present invention described above, it is possible to provide a coloring composition for a color filter and a color filter capable of forming a film with less wrinkles on the surface after photocuring.

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

First, terms in this specification are defined.
In the present application, there is no particular description when it is described as “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, or “(meth) acrylamide”. As long as they represent "acryloyl and / or methacryloyl", "acryl and / or methacryl", "acrylic and / or methacrylic", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide", respectively. And
In addition, “CI” described in this specification means a color index (CI).

<Colorant (A)>
The coloring composition for a color filter of the present specification (hereinafter, referred to as a coloring composition) can be arbitrarily selected from known pigments and dyes as the coloring agent (A). As the pigment, there are organic pigments and inorganic pigments, and organic pigments are preferable. Pigments and dyes can be used alone or in combination of two or more.

The content of the coloring agent (A) is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more based on 100% by mass of the nonvolatile content of the coloring composition. Further, the upper limit of the content is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less. Use of an appropriate amount of the coloring agent (A) further improves the color reproducibility of the coating.
When a dye is used as the colorant (A), the content of the dye is preferably from 1 to 800 parts by mass, more preferably from 5 to 400 parts by mass, per 100 parts by mass of the pigment. When an appropriate amount of the dye is used, the brightness and the contrast ratio are further improved.

(Organic pigment)
Organic pigments, for example, diketopyrrolopyrrole pigments, azo, disazo, or azo pigments such as polyazo, aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthantrone, indanthrone, pyranthrone, or biolanthrone and the like Examples include anthraquinone pigments, quinacridone pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, sulene pigments, and metal complex pigments.

(Red pigment)
Red pigments include, for example, C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 149, 166, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 221, 242, 246, 254, 255, 264, 268, 269, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, diketopyrrolopyrrole pigments described in JP-T-2011-523433, or JP-A No. And the like. Among these, C.I. I. Pigment Red 177, 242, 254, 269 is preferably used.

(Green pigment)
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, 58, JP-A 2008- Examples include zinc phthalocyanine pigments described in 19383, JP-A-2007-320986, JP-A-2004-70342, and aluminum phthalocyanine pigments described in Japanese Patent No. 4893859. Among these, C.I. I. Pigment Green 7, 36, 58, and aluminum phthalocyanine pigments are preferred. Particularly, aluminum phthalocyanine pigments are most preferably used in terms of high contrast ratio and high brightness.

<Aluminum phthalocyanine pigment>
As the aluminum phthalocyanine pigment, a compound represented by the following general formula (1) is preferable.

General formula (1)

[In the formula (1), X _{1 to} X ₄ each independently represent an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or a cycloalkyl optionally having a substituent. Group, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or Represents an arylthio group which may have a substituent.
Y _{1 to} Y ₄ each independently represent a halogen atom, a nitro group, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent.
Z represents —OP (＝ O) R ₁ R ₂ , —OC (＝ O) R ₃ , —OS (＝ O) ₂ R ₄ or a hydroxyl group. R ₁ and R ₂ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent or Represents an aryloxy group which may have a group. R ₃ represents a hydrogen atom, an alkyl group optionally having a substituent, a cycloalkyl group optionally having a substituent, an aryl group optionally having a substituent, or a hetero group optionally having a substituent. Represents a ring group. R ₄ represents a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent.
a ₁ , a ₂ , a ₃ , a ₄ , b ₁ , b ₂ , b ₃ and b ₄ each independently represent an integer of 0 to 4, and a ₁ + b ₁ , a ₂ + b ₂ , a ₃ + b ₃ , a ₄ + b ₄ each represents an integer of 0 to 4, and may be the same or different. ]

The “alkyl group” of the alkyl group which may have a substituent in X _{1 to} X ₄ is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, Examples thereof include a linear or branched alkyl group such as an n-hexyl group, an n-octyl group, a stearyl group, and a 2-ethylhexyl group. Similarly, the “alkyl group having a substituent” includes a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2,2,3,3-tetrafluoropropyl Group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, , 4-dichlorobenzyl group and the like.

  The “aryl group” of the aryl group which may have a substituent includes a phenyl group, a naphthyl group, an anthryl group and the like. Similarly, the “aryl group having a substituent” includes a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, a 2,4-dichlorophenyl group, a pentafluorophenyl group, a 2-amino Phenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group, 2-aminoanthra And a quinonyl group.

  The “cycloalkyl group” of the optionally substituted cycloalkyl group includes a cyclopentyl group, a cyclohexyl group, an adamantyl group, and the like. Similarly, the “cycloalkyl group having a substituent” includes a 2,5-dimethylcyclopentyl group, a 4-tert-butylcyclohexyl group, and the like.

  Examples of the “heterocyclic group” of the optionally substituted heterocyclic group include a pyridyl group, a pyrazyl group, a piperidino group, a pyranyl group, a morpholino group, and an acridinyl group. Similarly, the “heterocyclic group having a substituent” includes a 3-methylpyridyl group, an N-methylpiperidyl group, an N-methylpyrrolyl group, and the like.

  “Alkoxyl group” of the alkoxyl group which may have a substituent is a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a neopentyloxy group, Examples thereof include a linear or branched alkoxyl group such as 3-dimethyl-3-pentyloxy, n-hexyloxy group, n-octyloxy group, stearyloxy group, and 2-ethylhexyloxy group. Similarly, the “alkoxyl group having a substituent” includes a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, and a 2,2-ditrifluoro group. Examples include a methylpropoxy group, a 2-ethoxyethoxy group, a 2-butoxyethoxy group, a 2-nitropropoxy group, and a benzyloxy group.

  Examples of the “aryloxy group” of the optionally substituted aryloxy group include a phenoxy group, a naphthoxy group, an anthryloxy group, and the like. Similarly, the “aryloxy group having a substituent” includes a p-methylphenoxy group, a p-nitrophenoxy group, a p-methoxyphenoxy group, a 2,4-dichlorophenoxy group, a pentafluorophenoxy group, a 2-methyl-4-chloro group Phenoxy groups and the like.

  The `` alkylthio group '' of the alkylthio group which may have a substituent includes a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, an octylthio group, a decylthio group, a dodecylthio group, an octadecylthio group, and the like. Can be Similarly, the “alkylthio group having a substituent” includes a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, a phenylcarbonylaminoethylthio group, and the like.

  The “arylthio group” of the arylthio group which may have a substituent includes a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-anthrylthio group, and the like. Similarly, the “arylthio group having a substituent” includes a chlorophenylthio group, a trifluoromethylphenylthio group, a cyanophenylthio group, a nitrophenylthio group, a 2-aminophenylthio group, a 2-hydroxyphenylthio group, and the like.

When X _{1 to} X ₄ have a substituent, the substituents may be the same or different; for example, a halogen group such as fluorine, chlorine and bromine; a functional group such as an amino group, a hydroxyl group and a nitro group; an alkyl group , An aryl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, an alkylthio group, an arylthio group, and the like. Further, these substituents may be plural. The alkyl group, an aryl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, an alkylthio group and arylthio group are as described in X ₁ to X ₄ above.

Y _{1 to} Y _{4 each} represent a halogen atom, a nitro group, a phthalimidomethyl group (C ₆ H ₄ (CO) ₂ N—CH ₂ —) which may have a substituent, or a sulfamoyl group (H ₂ NSO ₂ —). No. Further, a phthalimidomethyl group having a substituent represents a structure in which a hydrogen atom in the phthalimidomethyl group is substituted by a substituent. The sulfamoyl group having a substituent represents a structure in which a hydrogen atom in the sulfamoyl group is substituted by a substituent. Desirable Y _{1 to} Y ₄ are a halogen atom and a sulfamoyl group. In the present specification, an aluminum phthalocyanine pigment in which b _{1 to} b ₄ is 0 (that is, there is no Y _{1 to} Y ₄ ) can be preferably used. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. An optionally substituted phthalimidomethyl group, and "substituent" good Surufamoiruru group which may have a substituent are the same as described in X ₁ to X _4.

In the aluminum phthalocyanine pigment, among the compounds represented by the general formula (1), a ₁ , a ₂ , a _3, and a ₄ are 0 for a substituent to a phthalocyanine ring, and Y _{1 to} Y ₄ are halogen atoms. Compounds represented by the following general formula (2) are preferred.

General formula (2)

[In the general formula (2), Y represents a halogen atom, b represents an average value of the number of substituents of the halogen atom, and represents a value of 0 to 16.
Z represents —OP (＝ O) R ₁ R ₂ , —OC (＝ O) R ₃ , —OS (＝ O) ₂ R ₄ or a hydroxyl group. R ₁ and R ₂ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent or Represents an aryloxy group which may have a group. R ₃ represents a hydrogen atom, an alkyl group optionally having a substituent, a cycloalkyl group optionally having a substituent, an aryl group optionally having a substituent, or a hetero group optionally having a substituent. Represents a ring group. R ₄ represents a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent. ]

  In the general formula (2), the “halogen atom” includes fluorine, bromine, chlorine and iodine, and bromine and chlorine are preferred.

  Aluminum color phthalocyanine pigments in which b is 0 and are not substituted with halogen at all are preferred in applications where color density is strongly required among color filters, because they are excellent in terms of color density. On the other hand, in applications where the demand for color density is not strong, b is preferably 8 to 15 from the viewpoint of hue and fastness.

In the aluminum phthalocyanine pigment represented by the general formula (1), Z represents -OP (= O) R ₁ R ₂ , -OC (= O) R ₃ or OS (= O, from the viewpoint of fastness and color characteristics. ) ₂ R ₄ , and more preferably -OP (= O) R ₁ R ₂ . Further, at least one of R _1, R _2, but is preferably an aryloxy group which may have a well aryl group or a substituent having a substituent, R ₁ and R ₂ are either Is more preferably an aryl group or an aryloxy group, and further preferably, both R ₁ and R ₂ are a phenyl group or a phenoxy group. Further, R ₃ and R ₄ are preferably an aryl group which may have a substituent or a heterocyclic group which may have a substituent.

The alkyl group for R _{1 to} R ₄ is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, an n-octyl group, a stearyl group, A linear or branched alkyl group such as a 2-ethylhexyl group is exemplified. Among these, an alkyl group having 1 to 6 carbon atoms is preferable. Examples of the substituent of the alkyl group having a substituent include a halogen atom such as chlorine, fluorine and bromine, an alkoxyl group such as a methoxy group, an aryl group such as a phenyl group and a tolyl group, and a nitro group. Further, there may be a plurality of substituents. Examples of the alkyl group having a substituent include a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2-ethoxyethyl group, a 2-butoxyethyl group, 2-nitropropyl, benzyl, 4-methylbenzyl, 4-tert-butylbenzyl, 4-methoxybenzyl, 4-nitrobenzyl, 2,4-dichlorobenzyl and the like. No.

The aryl group in R _{1 to} R ₄ includes a monocyclic aromatic hydrocarbon group such as a phenyl group and a p-tolyl group; and a condensed aromatic hydrocarbon group such as a naphthyl group and an anthryl group. Among these, a monocyclic aromatic hydrocarbon group is preferable, and an aryl group having 6 to 12 carbon atoms is more preferable. Examples of the substituent of the aryl group having a substituent include a halogen atom such as chlorine, fluorine, and bromine, an alkoxyl group, an amino group, and a nitro group. Further, there may be a plurality of substituents. Examples of the aryl group having a substituent include a p-bromophenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, a 2,4-dichlorophenyl group, a pentafluorophenyl group, a 2-dimethylaminophenyl group, and a 2-methyl -4-chlorophenyl group, 4-methoxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group and the like.

The alkoxyl group in R ₁ and R ₂ is a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a neopentyloxy group, a 2,3-dimethyl-3-pentyl A straight-chain or branched alkoxyl group such as an oxy group, an n-hexyloxy group, an n-octyloxy group, a stearyloxy group and a 2-ethylhexyloxy group is exemplified. Among these, an alkoxyl group having 1 to 6 carbon atoms is preferable. Examples of the substituent of the alkoxyl group having a substituent include a halogen atom such as chlorine, fluorine and bromine, an aryl group such as an alkoxyl group, a phenyl group and a tolyl group, and a nitro group. Further, there may be a plurality of substituents. Examples of the alkoxyl group having a substituent include a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, and a 2,2-ditrifluoromethyl Examples include a propoxy group, a 2-ethoxyethoxy group, a 2-butoxyethoxy group, a 2-nitropropoxy group, and a benzyloxy group.

The aryloxy group in R ₁ and R ₂ is derived from a condensed aromatic hydrocarbon group such as an aryloxy group consisting of a monocyclic aromatic hydrocarbon group such as a phenoxy group and a p-methylphenoxy group, a naphthaloxy group and an anthryloxy group. Aryloxy group. Among these, an aryloxy group composed of a monocyclic aromatic hydrocarbon group is preferable, and an aryloxy group having 6 to 12 carbon atoms is more preferable. Examples of the substituent of the aryloxy group having a substituent include a halogen atom such as chlorine, fluorine, and bromine, an alkyl group, an alkoxyl group, an amino group, and a nitro group. Further, there may be a plurality of substituents. Examples of the aryloxy group having a substituent include a p-nitrophenoxy group, a p-methoxyphenoxy group, a 2,4-dichlorophenoxy group, a pentafluorophenoxy group, and a 2-methyl-4-chlorophenoxy group.

The cycloalkyl group for R ₃ is a monocyclic aliphatic hydrocarbon group such as a cyclopentyl group, a cyclohexyl group, a 2,5-dimethylcyclopentyl group, a 4-tert-butylcyclohexyl group, or a condensed aliphatic group such as a bornyl group or an adamantyl group. Group hydrocarbon groups. Among them, a cycloalkyl group having 5 to 12 carbon atoms is preferable. Examples of the substituent of the cycloalkyl group having a substituent include a halogen atom such as chlorine, fluorine, and bromine, an alkyl group, an alkoxyl group, a hydroxyl group, an amino group, and a nitro group. Further, there may be a plurality of substituents. Examples of the cycloalkyl group having a substituent include a 2,5-dichlorocyclopentyl group and a 4-hydroxycyclohexyl group.

Examples of the heterocyclic group represented by R ₃ and R ₄ include an aliphatic heterocyclic group such as a pyridyl group, a pyrazyl group, a piperidino group, a pyranyl group, a morpholino group, and an acridinyl group, and an aromatic heterocyclic group. Among these, a heterocyclic group having 4 to 12 carbon atoms is preferable, and a heterocyclic group having 5 to 13 ring members is more preferable. Examples of the substituent of the heterocyclic group having a substituent include a halogen atom such as chlorine, fluorine, and bromine, an alkyl group, an alkoxyl group, a hydroxyl group, an amino group, and a nitro group. Further, there may be a plurality of substituents. Examples of the heterocyclic group having a substituent include a 3-methylpyridyl group, an N-methylpiperidyl group, and an N-methylpyrrolyl group.

  Typical examples of Z in the general formula (1) include the following structures (* represents a bonding position of a substituent to an Al atom in the general formula (1)). Is not limited to these. Further, cyclized isomers of the exemplified compounds are also included in the preferred examples of the present invention.

  The compound represented by the general formula (2) can be synthesized by, for example, a production method described in JP-A-2017-194637.

[Method for producing aluminum phthalocyanine pigment]
An example of a method for producing the compound represented by the general formula (2) will be described.
The compound represented by the general formula (2) is obtained by synthesizing a compound represented by the following general formula (3) by a known method, and then W ₁ P (＝ O) R ₁ R ₂ and W ₂ C (＝ O) R _3. Alternatively, it can be produced by reacting with an acidic compound represented by W ₃ S (＝ O) ₂ R ₄ . W ₁ , W ₂ and W ₃ each independently represent a halogen atom or a hydroxyl group. R _{1, R 2,} R 3, _{R 4} and halogen atom have the same meanings as _{R 1,} a halogen atom R _2, R 3, _{R 4} and _Y 1 to Y ₄ in the general formula (1).

General formula (3)

[In the general formula (3), X _{1 to} X ₄ each independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, and a cyclo which may have a substituent. An alkyl group, a heterocyclic group optionally having a substituent, an alkoxyl group optionally having a substituent, an aryloxy group optionally having a substituent, an alkylthio group optionally having a substituent, or And an arylthio group which may have a substituent.
Y _{1 to} Y ₄ each independently represent a halogen atom, a nitro group, a phthalimidomethyl group optionally having a substituent, or a sulfamoyl group optionally having a substituent.
Z ₁ represents a hydroxyl group or a halogen atom, a ₁ , a ₂ , a ₃ , a ₄ , b ₁ , b ₂ , b ₃ and b ₄ each independently represent an integer of 0 to 4, and a ₁ + b ₁ , A ₂ + b ₂ , a ₃ + b ₃ , and a ₄ + b ₄ each represent an integer of 0 to 4, and may be the same or different. ]

(Yellow pigment)
As the yellow pigment, an organic pigment or an inorganic pigment can be appropriately selected and used. As the yellow pigment, a pigment having high coloring properties and high heat resistance, particularly a pigment having high heat decomposition resistance, is preferable, and an organic pigment is preferable.

  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, 181 182,185,187,188,193,194,198,199,213,214,218,219,220,221 include yellow pigments quinophthalone pigments described in Japanese Patent No. 4,993,026 discloses. Among these, C.I. from the viewpoint of the contrast ratio and brightness of the filter segment. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180185 and at least one selected from the group consisting of quinophthalone pigments described in Japanese Patent No. 4993026. I. Pigment Yellow 138, 139, 150, 185 or the quinophthalone pigment described in Japanese Patent No. 4993026 is more preferable.

(Blue pigment)
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, 22, 60, 64, JP-A-2004-333817, Aluminum phthalocyanine pigments described in Japanese Patent No. 4893859 and the like can be mentioned. Further, C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 and the like can be used in combination. Among these, C.I. from the viewpoints of brightness and contrast ratio. I. Pigment Blue 15: 1 and 15: 6 are preferred.

<Dye>
Examples of the dye include an acid dye, a direct dye, a basic dye, a salt-forming dye, an oil-soluble dye, a disperse dye, a reactive dye, a mordant dye, a vat dye, and a sulfur dye. Further, as the dye, a derivative thereof or a lake pigment obtained by rake of the dye can also be used.

The acid dye preferably has an acid group such as sulfonic acid and carboxylic acid. The direct dye may form a salt-forming compound of an inorganic salt of an acid dye or an acid dye with a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound. preferable. Further, a salt-forming compound for forming a salt between the resin component having these functional groups and the acid dye is also preferable. Further, the salt forming compound is sulfonamide-modified to be modified into a sulfonamide compound, so that a colored composition having excellent fastness can be easily obtained.
Further, a salt-forming compound of an acid dye and a compound having an onium base is also preferable because of excellent heat resistance. Note that the compound having an onium base is preferably a resin having a cationic group.

  Although the basic dye can be used as it is, a salt forming compound which forms a salt with an organic acid or perchloric acid or a metal salt thereof is preferable. A salt forming compound of a basic dye is preferable because of its excellent resistance (light resistance, solvent resistance) and affinity with a pigment. The cation component serving as a counter ion in the salt-forming compound of a basic dye includes organic sulfonic acid, organic sulfuric acid, a fluorine-containing phosphorus anion compound, a fluorine-containing boron anion compound, a cyano-group-containing nitrogen anion compound, and a halogenated carbon. An anion compound having a conjugate base of an organic acid having a hydrogen group and a salt forming compound obtained by forming a salt with an acid dye are preferable. In addition, the resistance of the salt-forming compound is further improved when a polymerizable unsaturated group is contained in the molecule.

  Dyes include, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthraquinone dyes) Pyridone dyes), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinone imine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes, polymethine dyes Dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes Indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, and rhodamine dyes, and the like of these metal complex dyes. Among these, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium, from the viewpoint of color characteristics such as hue, difficulty in color separation, and color unevenness, Dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferable, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are more preferable. Specific compounds of the dyes are described in “New Edition Dye Handbook” (edited by The Society of Synthetic Organic Chemistry, Maruzen, 1970), “Color Index” (The Society of Dysers and colors), “Dye Handbook” (edited by Okawara et al .; Kodansha, 1986).

<Refinement of pigment>
In the present specification, the colorant (A) is preferably finely divided in advance and then mixed with another material. Examples of the miniaturization method include wet grinding, dry grinding, and dissolution precipitation. In the present specification, a salt milling treatment by a kneader method, which is a kind of wet grinding, is preferable.
The average primary particle diameter is determined from about 20 particles based on an enlarged image of a pigment by a TEM (transmission electron microscope). The average primary particle diameter is preferably from 5 to 90 nm. When the average primary particle diameter is appropriate, the dispersibility is further improved, and the contrast ratio is further improved. The average primary particle diameter is more preferably from 10 to 70 nm. When the particle has a short axis length and a horizontal axis length, the horizontal axis length is defined as a particle diameter.

  Salt milling treatment is a batch or continuous method using a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent, such as a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, and a planetary mixer. This is a process of mechanically kneading while heating using a kneader, and then removing the water-soluble inorganic salt and the water-soluble organic solvent by washing with water. The water-soluble inorganic salt functions as a crushing aid, and the pigment is crushed by utilizing the hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle diameter, a narrow distribution range, and a sharp particle size distribution.

  Examples of the water-soluble inorganic salt include: Examples thereof include sodium chloride, barium chloride, potassium chloride, and sodium sulfate. Of these, inexpensive sodium chloride (salt) is preferable. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by mass, more preferably 300 to 1000% by mass, based on 100% by mass of the pigment, in terms of both processing efficiency and production efficiency.

  The water-soluble organic solvent can wet the pigment and the water-soluble inorganic salt. The water-soluble organic solvent may be any as long as it is soluble (mixed) in water and does not substantially dissolve the inorganic salt used. In the present specification, a high boiling solvent having a boiling point of 120 ° C. or higher is preferred from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. Examples of the water-soluble organic solvent include 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. No. The amount of the water-soluble organic solvent to be used is preferably 5 to 1000 parts by mass, more preferably 50 to 500% by mass, based on 100 parts by mass of the pigment.

  A resin can be added to the salt milling treatment as needed. Examples of the type of resin include a natural resin, a modified natural resin, a synthetic resin, and a synthetic resin modified with a natural resin. The resin is preferably solid at room temperature (25 ° C.) and insoluble in water. It is also preferable that the resin is partially soluble in an organic solvent. The amount of the resin used is preferably from 5 to 200% by mass based on 100% by mass of the pigment.

<Dye derivative>
The coloring composition can contain a dye derivative. Thereby, the dispersibility of the colorant (A) is further improved. A dye derivative is a compound in which an acidic dye, a basic group, or a neutral group is bonded to an organic dye residue. The dye derivative is, for example, a compound having an acidic substituent such as a sulfo group, a carboxy group or a phosphate group and an amine salt thereof; a compound having a sulfonamide group or a basic substituent such as a tertiary amino group at a terminal; phenyl And a compound having a neutral substituent such as a phthalimidoalkyl group.

Organic dyes, for example, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, Examples include isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, sulene pigments, metal complex pigments, and azo pigments such as azo, disazo and polyazo.
Diketopyrrolopyrrole-based dye derivatives are described in JP-A-2001-220520, WO2009 / 081930, WO2011 / 052617, WO2012 / 102399, JP-A-2017-156397, and phthalocyanine-based dye derivatives are described in JP-A-2007-226161, WO2016 / 163351, JP-A-2017-165820, JP-A-5573266; Anthraquinone-based dye derivatives are disclosed in JP-A-63-264677, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009 / 025325, pamphlet; quinacridone-based dye derivatives are disclosed in JP-A-8-54128, JP-A-03-9961 and JP-A-2000-273383; dioxazine-based dye derivatives are described in JP-A-2011-162662; thiazineindigo-based dye derivatives are described in JP-A-2007-314785. Publications: Triazine dye derivatives are disclosed in JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, JP-A-2007-314681; Benzoisoindole-based dye derivatives are described in JP-A-2009-57478; quinophthalone-based dye derivatives are described in JP-A-2003-167112 and JP-A-2006-291194; JP, JP 2012-226110 A Naphthol-based dye derivatives are disclosed in JP-A-2012-208329 and JP-A-2014-5439; azo-based dye derivatives are described in JP-A-2001-172520 and JP-A-2012-172092; JP-A-2004-307854; basic substituents are described in JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, JP-A-2005-213404, and the like, respectively. And dye derivatives. Note that in these publications, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound, and the like. The compound having a substituent such as a sex group has the same meaning as the dye derivative.

The dye derivatives can be used alone or in combination of two or more.

<Resin type dispersant>
The coloring composition preferably contains a dispersant, and more preferably a resin-type dispersant. Thereby, the dispersibility of the colorant (A) is further improved. The resin-type dispersant preferably has a carboxyl group. The structure of the resin-type dispersant includes a straight-chain structure and a comb-type structure.

<Comb-shaped resin dispersant>
Examples of the comb-type resin-type dispersant having a carboxyl group include the following (J1) and (J2).
[Resin dispersant (J1)]
The resin-type dispersant (J1) can be produced by a known method such as WO2008 / 007776, JP-A-2008-029901, JP-A-2009-155406, and the like. The synthesis method is, for example, a hydroxyl group of a polymer having a hydroxyl group and a resin-type dispersant which is a reaction product of an acid anhydride group of a tetracarboxylic dianhydride, or a hydroxyl group of a compound having a hydroxyl group, A resin-type dispersant which is a polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product of a carboxylic dianhydride with an acid anhydride group.

[Resin dispersant (J2)]
The resin-type dispersant (J2) can be produced by a known method such as WO2008 / 007776, JP-A-2009-155406, JP-A-2010-185934, JP-A-2011-157416, and the like. The synthesis method is, for example, in the presence of a reaction product of a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tetracarboxylic dianhydride, a hydroxyl group, a t-butyl group or an oxetane skeleton, or a heat treatment such as a blocked isocyanate. Obtained by reacting an ethylenically unsaturated monomer having a cross-linking group, a resin-type dispersant having a side chain obtained by polymerizing the other monomer, and a thylene unsaturated monomer having an isocyanate group in the hydroxyl group of the side chain. It is a resin type dispersant.

<Linear resin type dispersant>
The linear resin-type dispersant can be manufactured using all known methods, for example, JP-A-2009-251481, JP-A-2007-23195, JP-A-1996-143651, Can be synthesized using a known method as shown in the following. As an example of a method for producing a linear dispersant, a dispersant having a carboxyl group is produced by adding a tricarboxylic anhydride to a hydroxyl group using a vinyl polymer having one hydroxyl group at one end as a raw material. Can be done.

[Other resin type dispersants]
Other resin-type dispersants other than those described above are preferably dispersants having a colorant affinity site having a property of adsorbing to the colorant and a site compatible with components other than the colorant. Other resin-type dispersants include, for example, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt, Polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly (lower alkylene imine) with a polyester having a free carboxyl group, and salts thereof. Oil-based dispersant, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinyl pyrrolidone, etc. Resin, water-soluble polymer compound, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct, phosphoric acid ester, and the like. Examples of the polymer dispersant having a basic functional group include a nitrogen atom-containing graft copolymer and a nitrogen atom having a functional group containing a tertiary amino group, a quaternary ammonium base, or a nitrogen-containing heterocyclic ring in a side chain. Containing acrylic block copolymers and urethane polymer dispersants.

  Commercially available resin-type dispersants include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166 manufactured by Big Chem Japan. , 167, 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-Terra-U, 203, 204, or BYK-P104, P104S, 220S, LPN6919, or LACTIMON, LACTIMON-WS, or BYKUMEN; 00, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402 manufactured by BASF. , 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 45 0, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., and Ajispa-PA111, PB711, PB821, PB822, PB824, etc., manufactured by Ajinomoto Fine Techno Co., Inc. .

Resin-type dispersants can be used alone or in combination of two or more.

  The amount of the resin-type dispersant to be used is preferably about 5 to 200% by mass, more preferably 10 to 100% by mass, based on 100 parts by mass of the colorant (A). When used in an appropriate amount, a film is easily formed.

<Photopolymerizable compound (C)>
The coloring composition can contain the photopolymerizable compound (C). The photopolymerizable compound (C) includes a monomer or an oligomer which is cured by ultraviolet light or heat to form a transparent resin.

The photopolymerizable compound (C) is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxy. Ethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) Acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, trimethylolpropane PO-modified tri (meth) acrylate, trimethylo Lepropane EO-modified tri (meth) acrylate, isocyanuric acid EO-modified di (meth) acrylate, isocyanuric acid EO-modified tri (meth) acrylate, ditrimethylolpropanetetra (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 Of dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate and methylolated melamine (T) Various acrylates and methacrylates such as acrylates, epoxy (meth) acrylates and urethane acrylates, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

  Commercial products of the photopolymerizable compound (C) include, for example, KAYARAD R-128H, KAYARAD R526, KAYARAD PEG400DA, KAYARAD MAND, KAYARD NPGDA, KAYARAD R-167, KAYARAD HX-220, KAYARAD R- manufactured by Nippon Kayaku Co., Ltd. 551, KAYARAD R712, KAYARAD R-604, KAYARAD R-684, KAYARAD GPO-303, KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPEA-12, KAYARAD DPHA-2D, KAYARAD-D-A-D-A-D-A-D-A-D-A-D-A-D-A-A , KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-1 0: M-303, M-305, M-306, M-309, M-310, M-321, M-325, M-350, M-360, M-313, M-315 manufactured by Toa Gosei Co., Ltd. , M-400, M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A; Biscoat # 310HP, Biscoat # 335HP, Biscoat # 700, Biscoat # 295, Biscoat # 330, Biscoat # 360, Biscoat #GPT, Biscoat # 400, Biscoat # 405; A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., and the like.

(Polymerizable compound having acid group)
The photopolymerizable compound (C) can have an acid group. Examples of the acid group include a sulfonic acid group, a carboxyl group, and a phosphoric acid group.

  The photopolymerizable monomer having an acid group is, for example, an esterified product of a free hydroxyl group-containing poly (meth) acrylate of a polyhydric alcohol and (meth) acrylic acid with a dicarboxylic acid; a polyvalent carboxylic acid; Examples thereof include esterified products with hydroxyalkyl (meth) acrylates. Specific examples include, for example, monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. Carboxyl group-containing monoesters of carboxylic acids with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid and terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,2 Tricarboxylic acids such as 4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid and benzene-1,3,5-tricarboxylic acid And monohydroxy monoacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, or free carboxyl group-containing oligoesters thereof, and the like. Can be

  Commercial products of the photopolymerizable compound (C) having an acid group include, for example, Viscoat # 2500P manufactured by Osaka Organic Co., Ltd., and M-5300, M-5400, M-5700, M-510, and M-510 manufactured by Toagosei Co., Ltd. 520 and the like.

(Polymerizable compound having urethane bond)
The photopolymerizable compound (C) includes a compound containing at least one ethylenically unsaturated bond and at least one urethane bond. The compound is obtained, for example, by reacting a polyfunctional isocyanate with a (meth) acrylate having a hydroxyl group and a polyfunctional isocyanate, or by reacting a polyfunctional isocyanate with an alcohol and further reacting a (meth) acrylate having a hydroxyl group. Examples include the obtained polyfunctional urethane acrylate.

  Examples of the (meth) acrylate 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, 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 methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, containing epoxy group Compound with carboxy (meth) reaction product of acrylate, hydroxyl group-containing polyol polyacrylate, and the like.

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

  The structure of the alcohol is not limited, but the use of a polyhydric alcohol is preferable because the degree of crosslinking of the cured coating film increases and the coating film resistance increases. Examples of the polyhydric alcohol include propylene glycol, ethylene glycol, glycerin, trimethylolpropane, and pentaerythritol.

  Commercial products of the photopolymerizable compound (C) having a urethane bond include, for example, AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, and UF-8001G manufactured by Kyoeisha Chemical Co., Ltd. DAUA-167; UA-160TM manufactured by Shin-Nakamura Chemical Co., Ltd .; UV-4108F, UV-4117F manufactured by Osaka Organic Chemical Industry Co., Ltd., and the like.

  The compounding amount of the photopolymerizable compound (C) is preferably from 5 to 400 parts by mass, more preferably from 10 to 300 parts by mass, based on 100 parts by mass of the coloring agent (A). Thereby, photocurability and developability are further improved. The photopolymerizable compound (C) can be used alone or in combination of two or more.

<Photopolymerizable initiator (D)>
The coloring composition contains a photopolymerizable initiator (D) and a sensitizer (E). The sensitizer (E) contains an anthracene compound. This makes it difficult for the formed film to have a difference in photocurability between the surface of the film and a deep portion near the substrate. In addition, the difference in thermosetting shrinkage is suppressed, and wrinkles are hardly generated on the surface of the film after post-curing.

  The photopolymerizable initiator (D) is, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1 -One, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl ) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone or acetophenones such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one Compounds: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Or benzoin-based compounds such as benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenylsulfide, or 3,3 Benzophenone compounds such as', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4- Thioxanthone-based compounds such as diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 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 2,4- Triazine compounds such as trichloromethyl- (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O- Benzoyl oxime)] or an oxime ester compound such as ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime); bis Phosphine compounds such as (2,4,6-trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone Compounds; borate compounds; carbazole compounds; imidazole compounds; titanocene compounds and the like. Of these, oxime ester compounds are more preferred.

  Commercially available products include, for example, "IRGACURE 907" (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one) and "IRGACURE" manufactured by BASF as acetophenone-based compounds. 369 "(2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone)," IRGACURE 379 "2-benzyl-2-. Dimethylamino-1- (4-morpholinophenyl) -butan-1-one and phosphine-based compounds are, for example, all manufactured by BASF and manufactured by "IRGACURE 819" (bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide). ), "IRGACURE TPO" (2,4,6-trimethylbenzoyldiphenyl) Scan fins oxide) and the like.

  The photopolymerization initiator (D) can be used alone or in combination of two or more.

  The content of the photopolymerization initiator (D) is preferably 5 to 200 parts by mass with respect to 100 parts by mass of the colorant (A), and is 10 to 150 parts by mass from the viewpoint of photocurability and developability. Is more preferable.

<Sensitizer (E)>
The sensitizer (E) contains an anthracene compound. Anthracene compounds are anthracene and its derivatives, for example, 9,10-diethoxyanthracene, 9,10-bis (octanoyloxy) anthracene, 9,10-dibutoxyanthracene, 9,10-diacetyloxyanthracene, 9 , 10-dipropionyloxyanthracene, 1-methyl-9,10-diacetyloxyanthracene, 1-methyl-9,10-dipropionyloxyanthracene, 2,3-dimethyl-9,10-diacetyloxyanthracene, , 3-Dimethyl-9,10-dipropionyloxyanthracene, 9,10-bis (methoxycarbonyloxy) anthracene, 9,10-bis (ethoxycarbonyloxy) anthracene, 1-methyl-9,10-bis (methoxycarbonyl Oxy) Toracene, 1-methyl-9,10-bis (ethoxycarbonyloxy) anthracene, 2,3-dimethyl-9,10-bis (methoxycarbonyloxy) anthracene, 2,3-dimethyl-9,10-bis (ethoxy Carbonyloxy) anthracene, 2-chloroanthracene-9,10-dimethyl ether, 2-chloroanthracene-9,10-diethyl ether and the like. Commercially available anthracene compounds include, for example, "Anthracure UVS-1101" (9,10-diethoxyanthracene, manufactured by Kawasaki Kasei Kogyo Co., Ltd.) and "Anthracure UVS-581" (9,10-bis (octanoyloxy)). Anthracene UV-1331 "(9,10-dibutoxy anthracene, manufactured by Kawasaki Chemical Industries, Ltd.).

  In the present specification, other sensitizers other than the anthracene compound can be used in combination. Other sensitizers include, for example, unsaturated ketones represented by chalcone derivatives, dibenzalacetone, etc .; 1,2-diketone derivatives represented by benzyl, camphorquinone, etc .; benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, thioxanthone Polymethine dyes such as derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, marine derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxanol derivatives; acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives , Azulhenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinopol Irazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxaliloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyrin derivative, annulene derivative, spiropyran derivative, spirooxazine derivative, thiospiropyran Derivative, metal arene complex, organic ruthenium complex, or Michler's ketone derivative, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-bi (Diethylamino) benzophenone and the like. Also, "Dye Handbook" edited by Nobuo Ogawara et al. (1986, Kodansha), "Chemistry of Functional Dyes" edited by Nobuo Ogawara et al. (1981, CMC), "Special Functional Materials" edited by Chusaburo Ikemori et al. (1986, (CMC).

  The sensitizers (E) can be used alone or in combination of two or more.

  The sensitizer (E) is preferably 3 to 200 parts by mass, more preferably 5 to 100 parts by mass, based on 100 parts by mass of the photopolymerizable compound (C). In particular, the anthracene compound is preferably from 5 to 150 parts by mass, more preferably from 10 to 80 parts by mass, per 100 parts by mass of the photopolymerizable compound (C). Thereby, photocurability and developability are further improved.

The mass ratio of the photopolymerizable initiator (D) to the sensitizer (E) is preferably D / E = 10/90 to 90/10, and more preferably 70/30 to 30/70. When used in an appropriate ratio, a difference in photocurability between the surface of the coating film and a deep portion near the substrate is less likely to occur.
<Binder resin (B)>
The binder resin (B) is a so-called transparent resin, and preferably has a transmittance of 80% or more, and more preferably 95% or more, in the entire wavelength region of 400 to 700 nm of the resin. Examples of the binder resin (B) include a thermoplastic resin, a thermosetting resin, and an active energy ray-curable resin having an ethylenically unsaturated double bond (hereinafter, referred to as an active energy ray-curable resin). The active energy ray-curable resin may have thermosetting properties. Further, the active energy ray-curable resin may be an alkali-soluble resin from the viewpoint of developability. Further, the thermoplastic resin preferably has alkali solubility.

  The content of the binder resin (B) is preferably from 20 to 400 parts by mass, more preferably from 50 to 250 parts by mass, per 100 parts by mass of the coloring agent (A). When it is contained in an appropriate amount, the formation of a film becomes easier, and good color characteristics are easily obtained.

<Thermoplastic resin>
Thermoplastic resin, for example, acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, Examples include polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resin.
The thermoplastic resin preferably has alkali solubility. Examples of the alkali-soluble thermoplastic resin include a resin having an acidic group such as a carboxyl group or a sulfone group. The thermoplastic resin is an acrylic resin having an acidic group, an α-olefin / (anhydride) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or an isobutylene / (anhydrous ) Maleic acid copolymer and the like. Among these, acrylic resins and styrene / styrenesulfonic acid copolymers having an acidic group in terms of developability, heat resistance, and transparency are preferable.

<Active energy ray-curable resin>
The active energy ray-curable resin preferably has alkali solubility. The active energy ray-curable resin having alkali solubility is preferably synthesized by the following methods (i), (ii) and (iii). The coating formed by using the active energy ray-curable resin having alkali solubility has higher chemical resistance due to the cross-linking density by three-dimensional cross-linking.

[Method (i)]
Method (i) is, for example, to the side chain epoxy group of the copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other monomers, 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 reacted with a polybasic anhydride to introduce an ethylenically unsaturated double bond and a carboxyl group. How to

  Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, And 3,4-epoxycyclohexyl (meth) acrylate. Among these, glycidyl (meth) acrylate is preferred from the viewpoint of reactivity with the unsaturated monobasic acid in the next step.

  Examples of the unsaturated monobasic acid include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl (meth) acrylic acid, alkoxyl, halogen, nitro, and cyano-substituted products. And the like.

  Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. Further, when increasing the number of carboxyl groups, if necessary, use of a tricarboxylic anhydride such as trimellitic anhydride, use of a tetracarboxylic dianhydride such as pyromellitic dianhydride, the remaining anhydride And the like can be hydrolyzed. When tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the number of ethylenically unsaturated double bonds can be further increased.

  A similar method of the method (i) is, for example, a side chain of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with one or more other monomers. This is a method in which an ethylenically unsaturated monomer having an epoxy group is subjected to an addition reaction to a part of the carboxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]
The method (ii) uses an ethylenically unsaturated monomer having a hydroxyl group and copolymerizes an unsaturated monobasic acid monomer having a carboxyl group with another monomer. This is a method in which an isocyanate group of an ethylenically unsaturated monomer having an isocyanate group is reacted with a side chain hydroxyl group of a polymer. Further, an ethylenically unsaturated monomer having a phosphate group can also be used.

  Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, Examples include hydroxyalkyl methacrylates such as glycerol mono (meth) acrylate and cyclohexanedimethanol mono (meth) acrylate. In addition, polyether mono (meth) acrylate obtained by addition-polymerizing ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, polyγ-valerolactone, polyε-caprolactone, and / or Polyester mono (meth) acrylate to which poly-12-hydroxystearic acid or the like has been added is exemplified. Among these, 2-hydroxyethyl methacrylate or glycerol mono (meth) acrylate is preferred from the viewpoint of suppressing foreign matter in the coating. Also, glycerol mono (meth) acrylate is preferable in terms of photosensitivity.

  Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloylethyl isocyanate, 2- (meth) acryloyloxyethyl isocyanate, and 1,1-bis [methacryloyloxy] ethyl isocyanate. Can be

  Other monomers other than the above include, 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, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acryl (Meth) acrylates such as methacrylate or ethoxypolyethylene glycol (meth) acrylate; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide (Meth) acrylamide such as diacetone (meth) acrylamide or acryloylmorpholine; styrene such as styrene and α-methylstyrene; vinyl ether such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether or isobutyl vinyl ether A fatty acid vinyl such as vinyl acetate or vinyl propionate; and the like.

Or cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide Coumarin, 4,4'-bismaleimidodiphenylmethane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, N, N'-1,3-phenylenedimaleimide, N, N'-1,4- Phenylenedimaleimide, 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-succinimide Imidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N- [4- (2-benzimidazolyl) phenyl N-substituted maleimides such as maleimide and 9-maleimidoacridine; compounds represented by the following general formula (4), specifically EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, Phenol ethylene oxide (EO) modified (meth) acrylate, paracumylphenol EO or propylene oxide (PO) modified (meth) acrylate, Nonylphenol EO modified (meth) Acrylate, PO-modified (meth) acrylate of nonylphenol and the like.

General formula (4)

(In the general formula (4), R ₆ is a hydrogen atom or a methyl group, R ₇ is an alkylene group having 2 or 3 carbon atoms, and R ₈ is a carbon atom which may have a benzene ring. It is an alkyl group of numbers 1 to 20, and n is an integer of 1 to 15.)

  Further, the unsaturated monobasic acid can also be used. Other than the above examples, for example, ε-caprolactone-added acrylic acid, ε-caprolactone-added methacrylic acid and the like can be mentioned.

  Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, Or hydroxyalkyl (meth) acrylates such as cyclohexanedimethanol mono (meth) acrylate. Also, polyether mono (meth) acrylates obtained by addition-polymerizing ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) ester mono (meth) acrylate to which (poly) 12-hydroxystearic acid or the like has been added.

The ethylenically unsaturated monomer having a phosphoric acid group is, for example, a monomer which can be synthesized by reacting a hydroxyl group of an ethylenically unsaturated monomer having a hydroxyl group with a phosphoric acid esterifying agent such as phosphorus pentoxide or polyphosphoric acid. Is mentioned.

[Method (iii)]
In the method (iii), an unsaturated ethylenic double bond can be introduced by copolymerizing a side chain type cyclic ether-containing monomer with one or more other monomers.
The side chain type cyclic ether-containing monomer is, for example, an unsaturated compound containing at least one skeleton selected from the group consisting of a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton, and a lactone skeleton.
The tetrahydrofuran skeleton is, for example, tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, (meth) acrylic acid tetrahydrofuran-3-yl ester;
The furan skeleton is, for example, 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan-2-butyl-3-en-2-one, 1-furan. Furan-2-butyl-3-methoxy-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexen-3-one, 6-furan-2-yl-hex-1-one En-3-one, 2-furan-2-yl-1-methyl-ethyl acrylate, 6- (2-furyl) -6-methyl-1-hepten-3-one;
The tetrahydropyran skeleton is, for example, (tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -oct-1-en-3-one, tetrahydro-2-methacrylate Pyran-2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one and the like;
As the pyran skeleton, 4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyrone, 4- (1,5-dioxa-6-oxo-7-octenyl) -6 -Methyl-2-pyrone;
The lactone skeleton may be, for example, 2-propenoic acid 2-methyl-tetrahydro-2-oxo-3-furanyl ester, 2-propenoic acid 2-methyl-7-oxo-6-oxabicyclo [3.2.1] oct-2. -Yl ester, 2-methyl-2-propenoic acid 2-methyl-hexahydro-2-oxo-3,5-methano-2H-cyclopenta [b] furan-7-yl ester, 2-propenoic acid 2-methyl-tetrahydro-2-oxo -2H-pyran-3-yl ester, 2-propenoic acid (tetrahydro-5-oxo-2-furanyl) methyl ester, 2-propenoic acid hexahydro-2-oxo-2,6-methanofuro [3,2-b] -6-yl ester, 2-methyl-2-propenoic acid 2- (tetrahydro-5-oxo-3-furanyl) ethyl ester, 2-propenoic acid 2- Tyl-decahydro-8-oxo-5,9-methano-2H-furo [3,4-g] -1-benzopyran-2-yl ester, 2-methyl-2-propenoic acid 2-[(hexahydro-2- Oxo-3,5-methano-2H-cyclopenta [b] furan-6-yl) oxy] ethyl ester, 3-oxo-3-[(tetrahydro-2-oxo-3-furanyl) oxy] propyl 2-propenoate And 2-propenoic acid 2-methyl-2-oxy-1-oxaspiro [4.5] dec-8-yl ester. Among these, tetrahydrofurfuryl (meth) acrylate is preferred in terms of pigment dispersibility and availability.

Monomers can be used alone or in combination of two or more.

It is preferable to use an active energy ray-curable resin having alkali solubility as the binder resin (B) for the coloring composition.

  The weight average molecular weight (Mw) of the binder resin (B) is preferably from 2,000 to 40,000, more preferably from 3,000 to 300,00, even more preferably from 4,000 to 20,000. Further, the molecular weight dispersity (Mw / Mn) is preferably 10 or less. When the weight average molecular weight (Mw) is 2,000 or more, the adhesion to the substrate is further improved. On the other hand, when the molecular weight is 40,000 or less, the developability is improved, the residue can be suppressed, and the straightness of the formed pattern is further improved.

The acid value (mgKOH / g) of the alkali-soluble resin is preferably 50 or more and 200 or less, more preferably 70 or more and 180 or less, and even more preferably 90 or more and 170 or less in order to impart alkali development solubility. When the acid value is appropriate, alkali developability is improved, and adhesion to a substrate and pattern formability are further improved.

<Organic solvent>
The coloring composition can contain an organic solvent. Thereby, the dispersion of the coloring agent (A) is assisted, and the viscosity of the coloring composition is easily adjusted.

  Organic solvents include, for example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 4-butanediol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5- Trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutanol Methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene , N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o- Dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono Ethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, Lenglycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, Diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl Diether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol di Acetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol Monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

  The organic solvents can be used alone or in combination of two or more.

  The amount of the organic solvent used is preferably about 500 to 4000 parts by mass with respect to 100 parts by mass of the colorant (A).

<Epoxy compound>
The coloring composition can contain an epoxy compound. This further improves the heat resistance of the coating.
Epoxy compounds include, for example, phenol novolak type epoxy resin, cresol novolak type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, biphenol type An epoxy resin, a bisphenol-A novolak type epoxy resin, a naphthalene skeleton-containing epoxy resin, an alicyclic epoxy resin, a heterocyclic epoxy resin, and the like can be given. Among these, alicyclic epoxy resins are preferred from the viewpoints of improvement of water spots after development, heat resistance and chemical resistance.

  Commercial products of phenol novolak type epoxy resins include, for example, Epicron N-740, Epicron N-770, Epicron N-775 manufactured by DIC, and D.C. E. FIG. N438, RE-306 manufactured by Nippon Kayaku Co., Ltd., jER152, jER154 manufactured by Mitsubishi Chemical Corporation, and the like.

  Commercial products of the cresol novolak type epoxy resin include, for example, Epicron N-660, Epicron N-665, Epicron N-670, Epicron N-673, Epicron N-680, Epicron N-695, Epicron N-665 manufactured by DIC Corporation. EXP, Epicron N-672-EXP, Nippon Kayaku's EOCN-102S, EOCN-103S, EOCN-104S, Union Carbide's UVR-6650, Sumitomo Chemical's ESCN-195, and the like.

  Commercially available products of the trishydroxyphenylmethane type epoxy resin include, for example, Nippon Kayaku's EPPN-503, EPPN-502H, EPPN-501H, Dow Chemical's TACTIX-742, Mitsubishi Chemical's jER E1032H60, and the like. .

  Commercial products of dicyclopentadiene phenol type epoxy resin include, for example, Epicron EXA-7200 manufactured by DIC, TACTIX-556 manufactured by Dow Chemical Company, and the like.

  Commercially available bisphenol-type epoxy resins include, for example, jER828 and jER1001 manufactured by Mitsubishi Chemical Corporation, UVR-6410 manufactured by Union Carbide Co., and D.C. E. FIG. R-331, bisphenol-A type epoxy resin such as YD-8125 manufactured by Nippon Epoxy Corporation, UVR-6490 manufactured by Union Carbide Co., Ltd., bisphenol-F type epoxy resin such as YDF-8170 manufactured by Nippon Epoxy Corporation, etc. Is mentioned.

  Commercially available biphenol type epoxy resins include, for example, biphenol type epoxy resins such as NC-3000 and NC-3000H manufactured by Nippon Kayaku Co., Ltd., and bixylenol type epoxy resins such as jER YX-4000 and jER YL-6121 manufactured by Mitsubishi Chemical Corporation. And the like.

  Commercial products of bisphenol A novolak type epoxy resin include, for example, Epicron N-880 manufactured by DIC, jER E157S75 manufactured by Mitsubishi Chemical Corporation, and the like.

  Commercial products of the naphthalene skeleton-containing epoxy resin include, for example, NC-7000 and NC-7300 manufactured by Nippon Kayaku Co., Ltd., and EXA-4750 manufactured by DIC.

  Commercial products of the alicyclic epoxy resin include, for example, Saixide 2021P, 2081, 2000 manufactured by Daicel, Eporide PB3600, PB4700, GT401, EHPE-3150, Cyclomer M100, and TTA3150 manufactured by Kusumoto Kasei Co., Ltd.

  Commercial products of the heterocyclic epoxy resin include, for example, TEPIC-L, TEPIC-H, and TEPIC-S manufactured by Nissan Chemical Industries, Ltd.

Epoxy compounds can be used alone or in combination of two or more.

  The content of the epoxy compound is preferably from 0.5 to 50% by mass, more preferably from 1 to 40% by mass, based on 100% by mass of the nonvolatile content of the coloring composition. When contained in an appropriate amount, the heat resistance is further improved.

<Oxetane compound>
The coloring composition can contain an oxetane compound. Examples of the oxetane compound include a compound having a monofunctional oxetane group, a compound having a bifunctional oxetane group, and a compound having a trifunctional or more oxetane group. From the viewpoint of heat resistance, a compound having an oxetane group having two or more functional groups is preferable.

Compounds having a monofunctional oxetane group include, for example, (3-ethyloxetane-3-yl) methyl acrylate, (3-ethyloxetane-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- (Triethoxysilyl) propoxy] methyl dioxetane.
Examples of commercially available products include OXE-10 and OXE-30 manufactured by Osaka Organic Chemical Industry Co., Ltd. OXT-101 and 212 manufactured by Toagosei Co., Ltd.

  Compounds having a bifunctional oxetane group include, for example, 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-oxa-nonane, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [( -Ethyl-3-oxetanylmethoxy) methyl] propane, ethyleneglycosebis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethyleneglycolbis (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) 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.

  Examples of commercially available products include OXBP and OXTP manufactured by Ube Industries, Ltd., and OXT-121 and OXT-221 manufactured by Toagosei Co., Ltd.

  Compounds having three or more oxetane groups are, for example, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritoltetrakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa (3-ethyl) -3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa (3- Ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3-E (3-3-oxetanylmethyl) ether, a resin containing an oxetane group (for example, an oxetane-modified phenol novolak resin described in Japanese Patent No. 3784462) or a (meth) acrylic monomer such as OXE-30 described above is subjected to radical polymerization. The obtained polymer is mentioned.

  The content of the oxetane compound is usually preferably from 0.5 to 50% by mass, more preferably from 1 to 40% by mass, based on 100% by mass of the nonvolatile content of the coloring composition. When contained in an appropriate amount, the coating is less likely to be stained by the developer or the washing water, and the chemical resistance is further improved.

<Polyfunctional thiol>
The coloring composition can contain a polyfunctional thiol. The polyfunctional thiol acts as a chain transfer agent during photocuring. When a polyfunctional thiol is used in combination with a photopolymerization initiator, thiyl radicals, which are hardly inhibited by polymerization due to oxygen upon light irradiation, are generated, so that the photosensitivity of the coloring composition is improved.

  The polyfunctional thiol is preferably a polyfunctional aliphatic thiol having two or more thiol groups (SH groups) bonded to an aliphatic group such as a methylene or ethylene group, and more preferably a polyfunctional aliphatic thiol having four or more SH groups. preferable. By increasing the number of SH groups, the photoreactivity of the photopolymerizable compound (C) is improved, and there is little difference in the degree of curing from the surface of the coating to the vicinity of the substrate.

  Polyfunctional thiols include, for example, hexanedithiol, decanedithiol, 1,4-butanediol bisthioglycolate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate , Trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionate (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamido) ) -4,6-dimercapto -s- triazine, and the like, preferably ethylene glycol bisthiopropionate, trimethylolpropane tris thiopropionate, pentaerythritol tetrakis thiopropionate and the like.

Polyfunctional thiols can be used alone or in combination of two or more.

The content of the polyfunctional thiol is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, based on 100% by mass of the nonvolatile content of the coloring composition. When an appropriate amount is used, the chain transfer effect is increased, the light sensitivity is improved, the tapered shape after development is improved, and wrinkling of the coating can be suppressed.

<Ultraviolet absorber>
The coloring composition can contain an ultraviolet absorber. The ultraviolet absorber is an organic compound having an ultraviolet absorbing function, and examples thereof include a benzotriazole organic compound, a triazine organic compound, a benzophenone organic compound, a cyanoacrylate organic compound, and a salicylate organic compound.

  The content of the ultraviolet absorber is preferably from 5 to 70% by mass in the total of 100% by mass of the photopolymerization initiator and the ultraviolet absorber. When an appropriate amount of an ultraviolet absorber is contained, sensitivity and resolution are further improved, and appropriate light sensitivity can be obtained. When a sensitizer is used, the content of the photopolymerization initiator includes the content of the sensitizer.

<Polymerization inhibitor>
The coloring composition may contain a polymerization inhibitor. This prevents exposure due to the diffracted light of the mask at the time of exposure, and can be adjusted so that the photocuring does not progress to outside the desired pattern.

  Examples of the polymerization inhibitor include catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, and 2-propyl. Catechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert Alkyl catechol-based compounds such as -butylcatechol and 3,5-di-tert-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol Alkyl resorcinol compounds such as lucinol, 2-n-butyl resorcinol, 4-n-butyl resorcinol, 2-tert-butyl resorcinol, 4-tert-butyl resorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, Alkylhydroquinone-based compounds such as 2,5-di-tert-butylhydroquinone, phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tribenzylphosphine; trioctylphosphine oxide; triphenylphosphine oxide; Phosphine oxide compounds such as triphenyl phosphite and trisnonyl phenyl phosphite Compounds, pyrogallol, phloroglucinol and the like.

The content of the polymerization inhibitor is preferably from 0.01 to 0.4% by mass based on 100% by mass of the nonvolatile content of the coloring composition. When an appropriate amount is used, an appropriate polymerization inhibiting effect is obtained, and the linearity of the taper, the wrinkling of the coating, the pattern resolution, and the like are further improved.

<Antioxidant>
The coloring composition can contain an antioxidant. The antioxidant prevents the photopolymerization initiator or the thermosetting resin or the like contained in the coloring composition from being oxidized and yellowed by a heat process such as thermosetting, so that the transmittance of the coating film can be increased. .

  In the present specification, the “antioxidant” is a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Examples of the antioxidant include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds. Further, the antioxidant is preferably a compound containing no halogen atom. Among these, a hindered phenol-based antioxidant, a hindered amine-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant are preferable from the viewpoint of achieving both the transmittance and the sensitivity of the coating film.

Hindered phenolic antioxidants include, for example, 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) , 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5- Di-t-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4 -Nonylphenol, 2,2'-isobutylidene-bis- (4,6-dimethyl-phenol), 4,4'-butylidene-bis- (2-t-butyl-5-methylphenol), 2,2'-thio Bis- (6-tert-butyl-4-methylphenol), 2,5-di-tert-amyl-hydroquinone, 2,2′thiodiethylbis- (3,5-di-tert-butyl-4-hydroxyphenyl) ) -Propionate, 1,1,3-tris- (2′-methyl-4′-hydroxy-5′-tert-butylphenyl) -butane, 2,2′-methylene-bis- (6- (1-methyl -Cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydro) Cinnamamide) and the like. Other examples include oligomer-type and polymer-type compounds having a hindered phenol structure.
Commercially available products are, for example, ADEKA's ADK STAB AO-20, AO-30, AO-40, AO50, AO60, AO80, AO320, Chemipro's KEMINOX 101, 179, 76, 9425, BASF's IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565, and Cyanox CY-1790, CY-2777 manufactured by Sun Chemical.

Hindered amine antioxidants include, for example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate , N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl- 4-piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3 , 4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} (2,2,6, 6-tetramethyl-4-piperidi L) imino {hexamethyl} (2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl)} (2 , 2,6,6-tetramethyl-4-piperidyl) imino {hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl) Polycondensation product with -4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N′-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2 2,6,6-pentamethyl-4-piperidyl) amino {-1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, etc. Other oligomers having a hindered amine structure Type and port Limmer type compounds are also included.
Commercial products are, for example, ADEKA ADK STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, LA-502XP, Chemipa Kasei's KAMISTAB 29, 62, 77, 29, 94, BASF's Tinuvin 249, TINUVIN 111FDL, 123, 144, 292, 5100, Sun Chemical's Siasorb UV-3346, UV-3529, UV-3853 and the like.

Examples of the phosphorus-based antioxidant include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi (tridecyl) phosphite, diphenylisooctylphosphite, and diphenylisophosphite. Decyl phosphite, diphenyl tridecyl phosphite, triphenyl phosphite, tris (nonyl phenyl) phosphite, 4,4 'isopropylidene diphenol alkyl phosphite, tris nonyl phenyl phosphite, tris dinonyl phenyl phosphite, tris ( 2,4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearylpentaerythritol diphosphite, 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) butanetriphosphite, 3,5-di-t- Butyl-4-hydroxybenzyl phosphite diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1, 3-bis (diphenoxyphosphonyloxy) -be And bis (2,4-ditert-butyl-6-methylphenyl) phosphite. Other examples include oligomer-type and polymer-type compounds having a phosphite structure.
Commercial products include, for example, ADEKA's ADK STAB PEP-36, PEP-8, HP-10, ADK STAB 2112, 1178, 1500, C, 3013, TPP, BASF's IRGAFOS168, Clariant Chemical's Hostanox P-EPQ, and the like. Can be

Examples of the sulfur-based antioxidant include 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and 2,4-bis [(octylthio) methyl]. -O-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol, 2,2-bis {[3- (dodecylthio) -1-oxopropoxy] methyl} propane-1,3-diylbis [3 -(Dodecylthio) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and the like. Other examples include oligomer type and polymer type compounds having a thioether structure.
Examples of commercially available products include ADK STAB AO-412S and AO-503 manufactured by ADEKA, and KEMINOXPLS manufactured by Chemipa Kasei.

Examples of the benzotriazole-based antioxidant include oligomer-type and polymer-type compounds having a benzotriazole structure.
Commercially available products include, for example, ADEKA ADK STAB LA-29, LA-31RG, LA-32, LA-36, -412S, Chemipro Kasei KEMISORB 71, 73, 74, 79, 279, BASF TINUVIN PS, 99 -2, 384-2, 900, 928, 1130 and the like.

Benzophenone antioxidants include, for example, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy- 4-octadecyloxybenzophenone, 2,2'dihydroxy-4-methoxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy- 4-methoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like. Other examples include oligomer-type and polymer-type compounds having a benzophenone structure.
Commercially available products include, for example, ADK STAB 1413 manufactured by ADEKA, KEMISORB 10, 11, 11S, 12, 111 manufactured by Chemipa Kasei Co., Ltd., UV-12, UV-329 manufactured by Sun Chemical.

Examples of the triazine-based antioxidant include 2,4-bis (allyl) -6- (2-hydroxyphenyl) 1,3,5-triazine and the like. Other examples include oligomer-type and polymer-type compounds having a triazine structure.
Commercially available products include, for example, ADEKA's ADK STAB LA-46 and F70, Chemipro Kasei's KEMISORB 102, BASF's TINUVIN 400, 405, 460, 477, 479, and Sun Chemical's Siasorb UV-1164.

  Examples of the salicylate antioxidant include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate, and the like. Other examples include oligomer-type and polymer-type compounds having a salicylate structure.

Antioxidants can be used alone or in combination of two or more.

  The content of the antioxidant is preferably 0.5 to 5% by mass based on 100% by mass of the nonvolatile content of the coloring composition. Thereby, transmittance, spectral characteristics, and sensitivity are further improved.

<Adhesion improver>
The coloring composition can contain an adhesion improver. The adhesion improver is preferably a silane coupling agent. Since the adhesion to the substrate is improved by the adhesion improver, the reproducibility of fine lines after development is improved, and the resolution is further improved.

  Examples of the adhesion improver include vinyl silane such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, (Meth) acrylsilanes such as methacryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxysilane 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycol Epoxysilanes such as sidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyl Methoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl Aminosilanes such as -butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, hydrochloride of N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxy Silanes, mercaptos such as 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureides such as 3-ureidopropyltriethoxysilane, sulfides such as bis (triethoxysilylpropyl) tetrasulfide; Isoshi Silane coupling agent of isocyanates such as sulphonate propyl triethoxy silane.

The adhesion improvers can be used alone or in combination of two or more.

The adhesion improver is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the coloring agent (A). When used in an appropriate amount, the balance among adhesion, resolution and sensitivity is further improved.

<Leveling agent>
The coloring composition can contain a leveling agent. This further improves coatability. As the leveling agent, for example, various surfactants such as a silicone-based surfactant, a fluorine-based surfactant, a nonionic surfactant, and a cationic (surfactant and an anionic surfactant) can be used.

Examples of the silicone-based surfactant include a linear polymer comprising a siloxane bond and a modified siloxane polymer having an organic group introduced into a side chain or a terminal.
Commercially available products are, for example, BYK-300, BYK-306, BYK-310, BYK-313, BYK-315N, BYK-320, BYK-322, BYK-323, BYK-330, BYK-331, BYK-BYK-300. -333, BYK-342, BYK-345 / 346, BYK-347, BYK-348, BYK-349, BYK-370, BYK-377, BYK-378, BYK-3455, BYK-UV3510, BYK-3570, Toray -Dow Corning FZ-7001, FZ-7002, FZ-2110, FZ-2122, FZ-2123], FZ-2191, FZ-5609, Shin-Etsu Chemical X-22-4952, X-22- 4272, X-22-6266, KF-351A, K354L, KF-355A, F-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, etc. KF-6004 and the like.

Examples of the fluorinated surfactant include a surfactant having a fluorocarbon chain.
Commercially available products are, for example, Surflon S-242, S-243, S-420, S-611, S-651, S-386, manufactured by AGC Seimi Chemical Co., Ltd., Megafac F-253, F-479, F-577, manufactured by DIC. -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 And FC-4430 and FC-4432 manufactured by Sumitomo 3M Limited, EF-PP31N09, EF-PP33G1 and EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals, and 602A manufactured by Neos Corporation.

  Nonionic surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myrster ether, polyoxyethylene octyl Dodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene alkenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene Alkyl ether phosphate, sorbitan monolaurate, sorbitan monopalmitate, Bitane monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan monolaurate, sorbitan eskioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, Polyoxyethylene orbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbite tetraoleate, glycerol monostearate, glycerol monooleate Eate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol Stearate, polyethylene glycol monomethyl oleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl amines, alkyl alkanol amides, alkyl betaine such as alkyl imidazoline and alkyl dimethyl amino acetic acid betaine.

  Commercially available products include, for example, Kao Corporation's Emulgen 103, Emulgen 104P, Emulgen 106, Emulgen 108, Emulgen 109P, Emulgen 120, Emulgen 123P, Emulgen 130K, Emulgen 147, Emulgen 150, Emulgen 210P, Emulgen 220, Emulgen 306P, Emulgen 320P Emulgen 350, Emulgen 404, Emulgen 408, Emulgen 409PV, Emulgen 420, Emulgen 430, Emulgen 705, Emulgen 707, Emulgen 709, Emulgen 1108, Emulgen 1118S-70, Emulgen 1135S-70, Emulgen 1150S-60, Emulgen 2020G-HA , Emulgen 2025G, Emulgen LS-106, Emulgen LS-110, Emulgen LS-114, Emulgen MS-110, Emulgen A-60, Emulgen A-90, Emulgen B-66, Emulgen PP-290, Latemul PD-420, Latemul PD-430, Latemul PD-430S, Latemul PD450, Rheodol SP -L10, Reodol SP-P10, Reodol SP-S10V, Reodol SP-S20, Reodol SP-S30V, Reodol SP-O10V, Reodol SP-O30V, Reodol Super SP-L1, Reodol AS-10V, Reodol AO-10V, Reodol AO-15V, Reodol TW-L120, Reodol TW-L106, Reodol TW-P120, Reodol TW-S120V, Reodol TW-L106V, Reodol TW-S320V, Reodol T -O120V, Reodol TW-O106V, Reodol TW-IS399C, Reodol Super TW-L120, Reodol 430V, Reodol 440V, Reodol 460V, Reodol MS-50, Reodol MS-60, Reodol MO-60, Reodol MS-165V, Emanone 1112, Emanone 3199V, Emanone 3299V, Emanone 3299RV, Emanone 4110, Emanone CH-25, Emanone CH-40, Emanone CH-60 (K), Amyte 102, Amyte 105, Amyte 105A, Amyte 302, Amyte 320, Amyne PK- 02S, Aminor L-02, Homogenol L-95, Adeka Corporation Adecapluronic L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, and Adecapluronic TR-701, 702, 704, 913R.

Examples of the cationic surfactant include alkylamine salts, alkylquaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and ethylene oxide adducts thereof.
Commercially available products include, for example, Acetamine 24, 26, Coatamine 24P, 86P Conc, Kao Corporation, KP341, Shin-Etsu Chemical Co., Ltd., and (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. 95 and the like.

  Anionic surfactants include, for example, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanol lauryl sulfate Examples include amine, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate.

  Examples of the commercially available products include Neogent's Futagent 100 and 150, ADEKA's Adeka Hope YES-25, Adeka Coal TS-230E, PS-440E, EC-8600, and the like.

Surfactants can be used alone or in combination of two or more.

  The content of the surfactant is preferably from 0.001 to 2% by mass, more preferably from 0.005 to 1.0% by mass, based on 100% by mass of the nonvolatile content of the coloring composition. When the coloring composition is contained in an appropriate amount, the balance of the coating properties, pattern adhesion, and transmittance of the coloring composition is further improved.

<Method for producing colored composition>
The coloring composition may be, for example, a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, together with a colorant (A), a dispersant, a binder resin (B), and an organic solvent. Alternatively, it can be produced by finely dispersing using various dispersing means such as an attritor (colorant dispersion). At this time, two or more kinds of coloring agents or the like may be dispersed at the same time, or those in which the coloring agents are separately dispersed may be mixed. When the colorant (A) is a dye or the like and has high solubility, specifically, it has high solubility in the solvent to be used. It does not need to be manufactured.

  Further, the coloring composition can be prepared as a solvent developing type or alkali developing type coloring composition. The solvent-developing or alkali-developable coloring composition comprises the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent and other dispersing aids and additives. And the like can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

<Dispersion aid>
When dispersing the colorant (A), a dispersing aid such as a dye derivative, a dispersant, and a surfactant can be appropriately contained. When a dispersing agent is used, it is easy to suppress re-aggregation of the colorant (A) after dispersion. Therefore, the coloring composition using the dispersing agent further improves brightness, contrast, and storage stability. The pigment derivative and the dispersant are as described above.

<Surfactant>
Surfactants include, for example, sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Anionic surfactants such as sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate ; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include alkyl betaines such as betaine acetate and amphoteric surfactants such as alkyl imidazolines.

  The content of the surfactant is preferably from 0.1 to 55 parts by mass, more preferably from 0.1 to 45 parts by mass, per 100 parts by mass of the coloring agent (A). When contained in an appropriate amount, sufficient dispersibility can be obtained.

<Removal of coarse particles>
The colored composition of the present invention is obtained by, for example, centrifugal separation, filtration using a sintered filter or a membrane filter, or the like, coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more. It is preferable to remove the mixed dust. As described above, it is preferable that the coloring composition does not substantially contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Color filter>
The color filter of the present specification preferably includes a substrate and a filter segment formed from the coloring composition. Preferably, the filter segment comprises a red, green and blue filter segment. Further, the color filter can further include a magenta filter segment, a cyan filter segment, and a yellow filter segment as necessary. The substrate is preferably a transparent substrate or a reflective substrate. The substrate may be referred to as a substrate.

<Production method of color filter>
As a method for producing a color filter, a printing method and a photolithography method are preferable, and a photolithography method is more preferable.

  The photolithography method uses, for example, a photosensitive coloring composition prepared as a solvent-developing or alkali-developing colored resist on a transparent substrate using a coating method such as spray coating, spin coating, slit coating, or roll coating. Then, coating is performed so that the dry film thickness is about 0.2 to 10 μm. The coating is exposed to ultraviolet light through a mask having a predetermined pattern.

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

The development includes, for example, aqueous solutions of sodium carbonate, sodium hydroxide and the like as alkali developing solutions; and organic alkalis such as dimethylbenzylamine, triethanolamine and tetramethylammonium hydroxide. Further, an antifoaming agent or a surfactant can be used as the developer. Examples of the developing method include a shower developing method, a spray developing method, a dip (immersion) developing method, and a paddle (liquid puddle) developing method.

In order to increase the sensitivity to exposure to ultraviolet light, a water-soluble or alkali-soluble resin (for example, polyvinyl alcohol or a water-soluble acrylic resin) can be formed on the resist film formed from the photosensitive coloring composition. This can prevent oxygen that inhibits the ultraviolet curing of the resist film.

  The color filter can be manufactured by an electrodeposition method, a transfer method, an ink-jet method, or the like in addition to the above method. The electrodeposition method is a method of producing a color filter by forming each color filter segment on a transparent conductive film by electrophoresis of colloid particles using a transparent conductive film formed on a substrate. . The transfer method is a method in which a filter segment is previously formed on the surface of a peelable transfer base sheet, and the filter segment is transferred to a desired substrate.

The substrate is preferably a transparent material. Examples of the substrate include glass plates such as soda lime glass, low alkali borosilicate glass, and alkali-free aluminoborosilicate glass; and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate. In addition, it is preferable that a transparent electrode formed of indium oxide, tin oxide, or the like be provided on the surface of the base material for driving the liquid crystal after forming the panel.
When the color filter is used for a solid-state imaging device, the substrate is preferably a silicon wafer.

The thickness of the substrate is about 0.1 to 3 mm.

  Before forming each color filter segment on the substrate, a black matrix can be formed in advance. As the black matrix, for example, a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used. However, the black matrix is not limited thereto. Alternatively, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. On the color filter of the present invention, an overcoat film, a transparent conductive film or the like is formed as necessary.

  The color filter is adhered to the counter substrate using a sealant, the liquid crystal is injected from the injection port provided in the seal section, and then the injection port is sealed.If necessary, a polarizing film or a retardation film is formed on the outside of the substrate. By laminating, a color liquid crystal display device can be manufactured. The color liquid crystal display device includes a twisted nematic (TN), a super twisted nematic (STN), an in-plane switching (IPS), a vertical alignment (VA), an optically-convened bend (OCB). ) Can be used in a liquid crystal display mode for performing colorization using a color filter.

Further, the color filter of the present invention can be used for manufacturing a color solid-state imaging device, an organic EL display device, a quantum dot display device, electronic paper, and the like, in addition to the color liquid crystal display device.
<Liquid crystal display device>
The liquid crystal display device of the present specification includes a color filter. It is preferable that the liquid crystal display further includes a light source. The light source includes a cold cathode fluorescent lamp (CCFL) and a white LED. Among these, a white LED is preferable in the present specification in that the red reproduction region is widened. An example of an embodiment of the liquid crystal display device will be described with reference to FIG. Note that the upper side in FIG. The liquid crystal display device 10 includes a pair of transparent substrates 11 and a transparent substrate 21 that are arranged to face each other. A liquid crystal LC is sealed between these.

  The liquid crystal LC is aligned according to a drive mode such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane switching), VA (Vertical Alignment), OCB (Optically Compensated Birefringence), and the like. Above the transparent substrate 11, a TFT (thin film transistor) array 12 is formed. A transparent electrode layer 13 is formed thereon. An alignment layer 14 is provided above the transparent electrode layer 13. Further, a polarizing plate 15 is formed below the transparent substrate 11. The transparent electrode layer 13 can be formed, for example, by depositing ITO (indium tin oxide).

  A color filter 22 is formed below the transparent substrate 21. The red, green and blue filter segments constituting the color filter 22 are separated by a black matrix (not shown).

  The transparent substrate 21 is provided above the color filter 22. Further, a transparent electrode layer 23 is formed below the color filter 22, and an alignment layer 24 is further provided below the transparent electrode layer 23.

Further, a polarizing plate 25 is provided above the transparent substrate 21. Further, a backlight unit 30 is provided below the polarizing plate 15.
The backlight unit 30 preferably uses a white LED light source 31.

  The white LED light source includes one in which a fluorescent filter is formed on the surface of a blue LED, and one in which a phosphor is contained in a resin package of the blue LED. For example, the emission has a wavelength (λ3) at which the emission intensity is maximum in the wavelength range of 430 nm to 485 nm, has a wavelength (λ4) at which the emission intensity is maximum within the range of 530 nm to 580 nm, and is 600 nm to 650 nm. And the ratio (I4 / I3) of the emission intensity I3 at the wavelength λ3 to the emission intensity I4 at the wavelength λ4 is 0.2 or more and 0.4 or less. Preferably, a white LED light source (LED1) having a spectral characteristic in which the ratio (I5 / I3) of the emission intensity I3 at the wavelength λ3 to the emission intensity I5 at the wavelength λ5 is 0.1 or more and 1.3 or less. Further, the emission has a wavelength (λ1) at which the emission intensity is maximum in the wavelength range of 430 nm to 485 nm, has a second emission intensity peak wavelength (λ2) in the range of 530 nm to 580 nm, and has a wavelength of λ1. Also, a white LED light source (LED2) having a spectral characteristic in which the ratio (I2 / I1) of the light emission intensity I1 at the wavelength λ2 to the light emission intensity I2 at the wavelength λ2 is 0.2 or more and 0.7 or less is preferable.

  When the LED 1 is a commercially available product, for example, NSSW306D-HG-V1 (manufactured by Nichia Corporation), NSSW304D-HG-V1 (manufactured by Nichia Corporation) and the like can be mentioned.

  The LED 2 is a commercially available product, for example, NSSW440 (manufactured by Nichia), NSSW304D (manufactured by Nichia), and the like.

  Hereinafter, the present invention will be described based on Production Examples and Examples, but the present invention is not limited thereto. In Production Examples and Examples, “parts” means “parts by mass” and “%” means “% by mass” unless otherwise specified.

Hereinafter, a method of measuring physical properties will be described.

(Identification of phthalocyanine)
The identification of the phthalocyanine compound was performed by matching the molecular ion peak of the mass spectrum obtained using a time-of-flight mass spectrometer (autoflex III (TOF-MS), manufactured by Bruker Daltonics) with the mass number obtained by calculation, In addition, the measurement was performed by matching the theoretical values with the ratios of carbon, hydrogen, and nitrogen obtained using an elemental analyzer (2400 CHN elemental analyzer, manufactured by Perkin-Elmer).

(Calculation of the average number of halogen atom substitutions)
The average value of the number of substitutions of halogen atoms in the phthalocyanine compound is determined by using a liquid obtained by burning a pigment by an oxygen combustion flask method and absorbing the burned substance in water using an ion chromatograph (ICS-2000 ion chromatography, DIONEX Co., Ltd.). And the amount of halogen was quantified and converted to the average value of the number of substitution of halogen atoms.

(Weight average molecular weight (Mw))
The weight average molecular weight (Mw) of the binder resin was measured by gel permeation chromatography (GPC) equipped with an RI detector. HLC-8220GPC (manufactured by Tosoh Corporation) was used as an apparatus, two separation columns were connected in series, and both fillers were connected using "TSK-GEL SUPER HZM-N" in a double column. The measurement was performed at a flow rate of 0.35 ml / min using tetrahydrofuran (THF) as an eluent. The sample was dissolved in a solvent consisting of 1 wt% of the above eluent, and 20 microliter was injected. All molecular weights are in terms of polystyrene.

(Acid value of resin)
The acid value of the resin is a value obtained by converting the measured acid value (mgKOH / g) into a nonvolatile component in accordance with the potentiometric titration method of JIS K0070.

<Synthesis of resin type dispersant having aromatic carboxyl group>
(Synthesis of Resin Dispersant R-1: An ethylenically unsaturated monomer was polymerized in the presence of a reaction product of a compound having two hydroxyl groups and an acid anhydride group of an aromatic tetracarboxylic anhydride. Polymer)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 6.0 parts of 3-mercapto-1,2-propanediol, 9.5 parts of pyromellitic anhydride, propylene glycol monomethyl ether acetate (PGMAC) 62 parts and 0.2 part of 1,8-diazabicyclo- [5.4.0] -7-undecene were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 100 ° C. and reacted for 7 hours. After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the temperature in the system was cooled to 70 ° C., and 65 parts of methyl methacrylate, 5.0 parts of ethyl acrylate, and t-butyl were added. 53.5 parts of a PGMAC solution in which 15 parts of acrylate, 5.0 parts of methacrylic acid, 10 parts of hydroxyethyl methacrylate, and 0.1 part of 2,2′-azobisisobutyronitrile were added, and reacted for 10 hours. . The reaction was terminated after confirming that the polymerization had proceeded by 95% by measuring the nonvolatile content. Propylene glycol monomethyl ether acetate was added to the previously synthesized dispersant so that the nonvolatile content was 50% by mass, to obtain a resin-type dispersant solution R-1 having an acid value of 70.5 and a weight average molecular weight of 10,000.

(Synthesis of Resin Dispersants R-2 to R-3)
Synthesis was carried out in the same manner as in R-1 except that the raw materials and the charged amounts shown in Table 1 were used, to obtain resin-type dispersants R-2 to R-3.

PGMAC: propylene glycol monomethyl ether acetate DBU: 1,8-diazabicyclo- [5.4.0] -7-undecene MMA: methyl methacrylate EA: ethyl acrylate tBA: t-butyl acrylate MAA: methacrylic acid HEMA: hydroxyethyl methacrylate HPMA : Hydroxypropyl methacrylate AIBN: 2,2'-azobisisobutyronitrile

<Production Example of Binder Resin (B) Solution>
(Preparation of binder resin (B-1) solution)
196 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirrer in a separable four-necked flask, heated to 80 ° C., and the inside of the reaction vessel was replaced with nitrogen. From a tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, and 20.7 parts of paracumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) , A mixture of 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the completion of the dropwise addition, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and propylene glycol monomethyl ether was added to the previously synthesized resin solution so that the nonvolatile content was 20%. Acetate was added to prepare a binder resin (B-1) solution. The weight average molecular weight (Mw) was 26,000.

(Preparation of binder resin (B-2) solution)
207 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirrer in a separable four-necked flask, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen, and then dropped. From a 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 completion of the dropwise addition, the reaction was continued for another 3 hours to obtain a resin solution. Next, nitrogen gas was stopped with respect to the whole amount of the obtained resin solution, and the mixture was stirred while injecting dry air for 1 hour, and then cooled to room temperature. Then, 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko KK) was used. A mixture of 6.5 parts, 0.08 part of dibutyltin laurate and 26 parts of cyclohexanone was added dropwise at 70 ° C. over 3 hours. After the completion of the dropwise addition, the reaction was continued for another hour to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content became 20%. Thus, a binder resin (B-2) solution was prepared. The weight average molecular weight (Mw) was 18,000.

(Preparation of binder resin (B-3) solution)
370 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas inlet pipe, a dropping pipe, and a stirrer, the temperature was raised to 80 ° C., and the flask was purged with nitrogen. 18 parts of millphenol 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 2,2′-azobisisobutyronitrile 2.0 Parts of the mixture were added dropwise over 2 hours. After dropping, the mixture was further reacted at 100 ° C. for 3 hours. Then, a solution prepared by dissolving 1.0 part of azobisisobutyronitrile 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 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone were put into 9.3 parts of acrylic acid (100% of glycidyl group) in the container, and the mixture was heated at 120 ° C. The reaction was continued for 6 hours, and the reaction was terminated when the acid value of the nonvolatile component became 0.5 mgKOH / g, to obtain a solution of an acrylic resin. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 part of triethylamine were successively added and reacted at 120 ° C. for 3.5 hours to obtain an acrylic resin solution.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes, and the non-volatile content was measured. Propylene glycol monomethyl ether was added to the previously synthesized resin solution so that the non-volatile content was 20% by mass. Acetate was added to prepare a binder resin (B-3) solution. The weight average molecular weight (Mw) was 19000.

(Preparation of binder resin (B-4) solution)
A separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas inlet pipe, a dropping pipe, and a stirrer was prepared. On the other hand, dimethyl-2,2 ′-[oxybis (methylene)] bis-2 was used as a monomer dropping tank. -40 parts of propenoate, 40 parts of methacrylic acid, 120 parts of methyl methacrylate, 4 parts of t-butylperoxy-2-ethylhexanoate ("Perbutyl O" manufactured by NOF Corporation) and 40 parts of propylene glycol monomethyl ether acetate are thoroughly stirred. A mixture was prepared, and as a chain transfer agent dropping tank, a mixture in which 8 parts of n-dodecanethiol and 32 parts of propylene glycol monomethyl ether acetate were thoroughly stirred and mixed was prepared.
The reaction vessel was charged with 395 parts of propylene glycol monomethyl ether acetate, and after purging with nitrogen, the mixture was heated in an oil bath with stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction tank was stabilized at 90 ° C., dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping was performed over a period of 135 minutes while maintaining the temperature at 90 ° C. After 60 minutes from the completion of the dropping, the temperature was raised and the temperature of the reaction vessel was set to 110 ° C. After maintaining at 110 ° C. for 3 hours, a gas introducing 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 part of 2,2′-methylenebis (4-methyl-6-t-butylphenol) and 0.8 part of triethylamine were charged into the reaction vessel, and the mixture was reacted at 110 ° C. for 12 hours. . Thereafter, 150 parts of propylene glycol monomethyl ether acetate was added, and the mixture was cooled to room temperature. About 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes, and the nonvolatile content was measured. Propylene glycol monomethyl ether acetate was added so as to be 20% by mass to obtain a binder resin (B-4) solution. The weight average molecular weight of the resin was 18,000, and the acid value per nonvolatile content was 2 mgKOH / g.

<Method for producing raw phthalocyanine compound represented by general formula (3)>
(Production of Raw Material Phthalocyanine Compound (Q-1))
In a reaction vessel, 225 parts of phthalodinitrile and 78 parts of aluminum chloride anhydride were mixed and stirred with 1250 parts of n-amyl alcohol. To this, 266 parts of DBU was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. while stirring was poured into a mixed solvent consisting of 5000 parts of methanol and 10,000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine (Q-1). Elemental analysis was performed on the obtained chloroaluminum phthalocyanine. The calculated value (C) was 66.85%, (H) was 2.80%, and (N) was 19.49%. 7%, (H) 3.0%, and (N) 19.2%, indicating that the compound was the target compound.

(Production of Raw Material Phthalocyanine Compound (Q-2))
To 1200 parts of concentrated sulfuric acid, 100 parts of a phthalocyanine compound (Q-1) were gradually added at room temperature. After stirring at 40 ° C. for 3 hours, the sulfuric acid solution was poured into 24000 parts of cold water at 3 ° C. The blue precipitate was filtered, washed with water, and dried to obtain 92 parts of hydroxyaluminum phthalocyanine (phthalocyanine compound (Q-2)).

(Production of Raw Material Phthalocyanine Compound (Q-3))
To 1500 parts of concentrated sulfuric acid, 100 parts of the phthalocyanine compound (Q-1) were added in an ice bath. Thereafter, 108 parts of trichloroisocyanuric acid was gradually added, and the mixture was stirred at 25 ° C. for 6 hours. Subsequently, this sulfuric acid solution was poured into 9000 parts of cold water at 3 ° C., and the formed precipitate was filtered, washed with water, washed with 1% aqueous sodium hydroxide solution, washed with water in this order, dried, and dried to obtain 165 parts of phthalocyanine. Compound (Q-3) was produced. When the number of chlorine substitutions was calculated, it was 7.8 on average, and a peak corresponding to the same molecular weight was confirmed from the mass spectrum, and it was identified as the target compound.

(Production of Raw Material Phthalocyanine Compound (Q-4))
In the production of the phthalocyanine compound (Q-3), 143 parts of the phthalocyanine compound (Q) was produced in the same manner as in the production of the phthalocyanine compound (Q-3) except that 108 parts of trichloroisocyanuric acid was changed to 186 parts of N-bromosuccinimide. -4). When the number of bromine substitutions was calculated, the average was 6.0, and a peak corresponding to the same molecular weight was confirmed from the mass spectrum, and it was identified as the target compound.

(Production of Raw Material Phthalocyanine Compound (Q-5))
In the same manner as in the production of the phthalocyanine compound (Q-3), except that 108 parts of trichloroisocyanuric acid was changed to 249 parts of 1,3-dibromo-5,5-dimethylhydantoin in the production of the phthalocyanine compound (Q-3). Thus, 187 parts of a phthalocyanine pigment (Q-5) were produced. When the number of bromine substitutions was calculated, the average was 10.3, and a peak corresponding to the same molecular weight was confirmed from the mass spectrum, and it was identified as the target compound.

(Production of Raw Material Phthalocyanine Compound (Q-6))
406 parts of aluminum chloride, 94 parts of sodium chloride and 10 parts of ferric chloride were heated and melted, and 100 parts of the phthalocyanine compound (Q-1) was added at 140 ° C. The temperature was raised to 160 ° C., and 190 parts of chlorine were blown. The above reaction solution was poured into 5000 parts of water, filtered, washed with warm water, washed with 1% aqueous hydrochloric acid, washed with warm water, washed with 1% aqueous sodium hydroxide solution, washed with warm water, and then dried to obtain crude chlorinated product. 175 parts of aluminum phthalocyanine were obtained. The obtained crude salt chlorinated aluminum phthalocyanine was dissolved in 1200 parts of concentrated sulfuric acid and stirred at 50 ° C. for 3 hours. Next, the solution was poured into 7200 parts of water while stirring, heated to 70 ° C., filtered, washed with warm water, washed with 1% aqueous sodium hydroxide solution, washed with warm water, and dried to obtain 165 parts of a phthalocyanine compound (Q-6). ) Manufactured. When the number of chlorine substitutions was calculated, the average was 15.0, and a peak corresponding to the same molecular weight was confirmed from the mass spectrum, and it was identified as the target compound.

A structural list of the obtained raw material phthalocyanine compound is shown.

<Production method of micronized pigment>
(Manufacture of red fine processing pigment (PR-1))
Red pigment C.I. I. Pigment Red 254 (PR254) (“IRGAFOR RED B-CF” manufactured by BASF), 152 parts, a dye derivative of the chemical formula (5) 8 parts, sodium chloride 1600 parts, and diethylene glycol 190 parts were stainless steel 1 gallon kneader (Inoue Seisakusho) And kneaded at 60 ° C. for 10 hours. Next, the mixture was poured into 3 liters of warm water, stirred for about 1 hour with a high-speed mixer while heating to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and the solvent. C. for one day and night to obtain a red refined pigment (PR-1). The average primary particle diameter of the obtained pigment was 35 nm.

General formula (5)

(Manufacture of red fine processing pigment (PR-2))
Red pigment C.I. I. Pigment Red 177 (PR177) (“Chromophthal Red A2B” manufactured by BASF), 500 parts, sodium chloride (3500 parts) and diethylene glycol (250 parts) were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. . Next, the kneaded material is put into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, and filtration and washing are repeated to remove sodium chloride and diethylene glycol, followed by drying at 80 ° C. all day and night. Thus, a red micronized pigment (PR-2) was obtained. The average primary particle diameter of the obtained pigment was 30 nm.

(Production of blue micronized pigment (PB-1))
Blue pigment C.I. I. Pigment Blue 15: 6 (PB15: 6) ("Lionol Blue ES" manufactured by Toyo Color Co., Ltd.), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), and 120 Kneaded at 12 ° C for 12 hours. Next, the kneaded material is put into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, and filtration and washing are repeated to remove sodium chloride and diethylene glycol, followed by drying at 80 ° C. all day and night. Thus, a blue micronized pigment (PB-1) was obtained. The average primary particle diameter of the obtained pigment was 25 nm.

(Production of purple micronized pigment (PV-1))
Dioxazine purple pigment C.I. I. Pigment Violet 23 (PV23) (Clariant "Fast Violet RL") 500 parts, sodium chloride 2500 parts, and polyethylene glycol (Tokyo Kasei Co., Ltd.) 250 parts were charged in a stainless steel 1 gallon kneader (Inoue Seisakusho). Kneading was performed at 120 ° C. for 12 hours. Next, this mixture was poured into about 5 liters of warm water, stirred for about 1 hour with a high-speed mixer while heating to about 70 ° C. to form a slurry, and then filtered and washed with water to remove sodium chloride and diethylene glycol. It was dried at 80 ° C. all day and night to obtain a purple finely treated pigment (PV-1). The average primary particle diameter of the obtained pigment was 30 nm.

(Production of green micronized pigment (PG-1))
Phthalocyanine green pigment C.I. I. Pigment Green 58 (manufactured by DIC Corporation, "FASTOGEN GREEN A110") (200 parts), sodium chloride (1400 parts), and diethylene glycol (360 parts) were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C for 6 hours. Next, the kneaded material was put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C to form a slurry, and filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying at 85 ° C for 24 hours. Thus, a green refined pigment (PG-1) was obtained. The average primary particle diameter of the obtained pigment was 30 nm.

(Production of yellow micronized pigment (PY-1))
Quinophthalone yellow pigment C.I. I. Pigment Yellow 138 (“Paliotol Yellow L0960HD” manufactured by BASF), 200 parts, sodium chloride (1400 parts), and diethylene glycol (360 parts) were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded material was put into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, and filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying at 85 ° C. for 24 hours. Thus, a yellow refined pigment (PY-1) was obtained.

(Manufacture of yellow fine processing pigment (PY-2))
100 parts of the quinophthalone compound (b), 1200 parts of sodium chloride, and 120 parts of diethylene glycol described in JP-A-2012-226110 were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), and kneaded at 60 ° C. for 6 hours. Salt milled. The obtained kneaded material was poured into 3 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, and filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and dried at 80 ° C. for 24 hours. , 98 parts of a yellow refined pigment (PY-2). The average primary particle size was 31 nm.

(Manufacture of yellow refined pigment (PY-3))
C. I. Pigment Yellow 150 (PY150) (manufactured by LANXESS, "E4GN") (100 parts), sodium chloride (700 parts), and diethylene glycol (180 parts) were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C for 6 hours. The 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 at 80 ° C. all day and night, and 95 parts of yellow A refined pigment (PY-3) was obtained. The average primary particle size was 35 nm.

<Production of dye derivative>
(Synthesis of Dye Derivative 2)
According to the synthesis method described in JP-A-2004-307854, a dye derivative (2) was obtained.

Dye derivative (2)

<Production method of aluminum phthalocyanine pigment composition>
[Production Example 1]
(Production of aluminum phthalocyanine pigment composition A-1)
To the reaction vessel, 2,000 parts of N, N-dimethylformamide, 100 parts of the starting phthalocyanine compound (Q-2), and 52 parts of diphenyl phosphate were added. After reacting at 85 ° C. for 3 hours, 31 parts of a resin-type dispersant (R-1) solution was added so that the resin content in the pigment composition was 10%, and the mixture was stirred for 10 minutes. Thereafter, this solution was poured into 8000 parts of water. The reaction product was filtered, washed with 16,000 parts of water, and dried at 60 ° C. under reduced pressure for 24 hours to obtain an aluminum phthalocyanine compound (P-1) and a resin-type dispersant (R-1). 148 parts of a pigment dispersion A-1 having a resin ratio of 10% was obtained at a yield of 94%.

[Production Examples 2 to 7]
(Production of pigment compositions A-2 to A-7)
Except that the aluminum phthalocyanine compound, the acidic compound, and the resin-type dispersant were respectively changed to the conditions described in Table 2, the same operation as that of the pigment composition A-1 was performed to obtain pigment compositions A-2 to A-7, respectively. Was. Table 2 shows the results of the yield, yield, halogen atom X and halogen substituent number n.

A structural list of the obtained phthalocyanine compound is shown.

<Production method of pigment dispersion>
[Production Example 8]
(Preparation of Pigment Dispersion (PD-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. And a red pigment dispersion (P-R1) was prepared.
Red refined pigment (PR-1): 12.0 parts Resin-type dispersant (R-1): 7.2 parts Binder resin (B-1): 22.0 parts Solvent / PGMAC (methoxypropyl acetate): 58.8 parts

[Production Examples 9 to 21]
(Preparation of Pigment Dispersions PD-2 to PD-14)
Pigment dispersions PD-2 to PD-14 were obtained in the same manner as in Production Example 33 except for using the materials and compounding ratios shown in Table 4.

<Coloring composition for color filter (R-1)>
[Example 1]
The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a coloring composition for a color filter (R-1).
-Pigment dispersion (PD-1: 20% liquid) 40.0 parts-Pigment dispersion (PD-2: 20% liquid) 20.0 parts-Binder resin (B-2: 20% liquid) 15.0 parts -3.0 parts of polymerizable compounds (C-1) ("Aronix M-309" trimethylolpropane triacrylate manufactured by Toagosei Co., Ltd.)
0.8 parts of photopolymerization initiator (D-1) (“IRGACURE OXE02” 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone 1 manufactured by BASF) -(O-acetyloxime)])
-0.7 parts of sensitizer (E-1) ("Anthracure UVS-1101" 9,10-diethoxyanthracene manufactured by Kawasaki Kasei Kogyo Co., Ltd.)
・ 0.6 parts of polyfunctional thiol (pentaerythritol tetrakis (3-mercaptopropionate) manufactured by SC Organic Chemicals)
・ 15.9 parts of organic solvent propylene glycol monomethyl ether acetate (PGMAC)
・ 4.0 parts of leveling agent solution (L-1)

[Examples 2 to 24, Comparative Examples 1 to 3]
<Coloring composition for color filter (R-2 to 27)>
Corresponding coloring compositions for color filters (R-2 to 27) were obtained by mixing the pigment dispersion, the binder resin solution, and the solvent in the same manner as in Example 1 as shown in Table 5.

The symbols in the table are as follows.
・ Photopolymerizable compound (C)
(C-1): dipentaerythritol hexaacrylate ("Aronix M-402" manufactured by Toagosei Co., Ltd.)
(C-2): General formula (6): where m = 1, a = 3, b = 3
Caprolactone-modified dipentaerythritol hexaacrylate ("KAYAARDDPCA-30" manufactured by Nippon Kayaku Co., Ltd.)

General formula (6)

(C-3): Succinic anhydride adduct of a mixture of pentaerythritol triacrylate and dipentaerythritol triacrylate ("Aronix M-520" manufactured by Toagosei Co., Ltd .; acid value: 30 mg KOH / g)

(C-4): polyfunctional urethane acrylate (synthesized by the following method)
A 5-liter reaction vessel having a content of 1 liter was charged with 432 g of pentaerythritol triacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and 84 g of hexamethylene diisocyanate, and reacted at 60 ° C. for 8 hours to have a (meth) acryloyl group. A product containing a polyfunctional urethane acrylate (C-4) was obtained. The proportion of the polyfunctional urethane acrylate (C-4) in the product was 70% by mass, and the remainder was occupied by other photopolymerizable monomers. In addition, it was confirmed by IR analysis that there was no isocyanate group in the reaction product.

・ Photopolymerizable initiator (D)
D-1: "Irgacure OXE02" (1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone 1- (O-acetyloxime)] manufactured by BASF
D-2: "Irgacure 907" (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one manufactured by BASF)

・ Sensitizer (E)
E-1: “Anthracure UVS-1101” (9,10-diethoxyanthracene manufactured by Kawasaki Kasei Kogyo Co., Ltd.)
E-2: “Anthracure UVS-581” (9,10-bis (octanoyloxy) anthracene, manufactured by Kawasaki Kasei Kogyo Co., Ltd.)
E-3: "Anthracure UV-1331" (9,10-dibutoxyanthracene, manufactured by Kawasaki Chemical Industry Co., Ltd.)
E-4: “CHEMARK DEABP” (4,4′-bis (diethylamino) benzophenone manufactured by Chemark Chemical Co.)
Epoxy compound A: "TTA3150" manufactured by Kusumoto Kasei Co., Ltd. Poly (2-oxiranyl) -1,2-cyclohexanediol-2-ethyl-2- (hydroxymethyl) -1,3-propanediol ether / thiol chain transfer Agent A: Pentaerythritol tetrakisthiopropionate / leveling agent solution (L-1: mixed solution below)
A mixed solution in which 1 part of BYK-330 manufactured by BYK-Chemie, 1 part of Megafac F-551 manufactured by DIC, and 1 part of Emulgen 103 manufactured by Kao Corporation are dissolved in 97 parts of propylene glycol monomethyl ether acetate (PGMAC). .

<Evaluation of coloring composition for color filter (resist)>
With respect to the obtained coloring composition for color filter (resist) (R-1 to 25), tests on sensitivity, surface wrinkle, and developing speed were performed by the following methods. Table 6 below shows the results of the evaluation test.

<Sensitivity evaluation>
The coloring composition was spin-coated on a glass substrate using a spin coater so that the dry film thickness became 2.4 μm, and prebaked at 90 ° C. for 120 seconds. Next, the substrate was cooled to room temperature, and then exposed to ultraviolet light through a photomask using an ultra-high pressure mercury lamp. Thereafter, the substrate was spray-developed with an aqueous solution of sodium carbonate at 23 ° C., washed with ion-exchanged water, air-dried, and post-baked in a clean oven at 230 ° C. for 30 minutes to form a stripe on the substrate. Colored pixels were formed.
The sensitivity of the coloring composition was evaluated based on the minimum irradiation exposure amount at which the pattern of the formed colored pixels was finished to the image size of the photomask. The ranking of the evaluation is as follows.
：: less than 100 mJ / cm ² : good level Δ: 100 or more, less than 150 mJ / cm ² : practicable level ×: 150 mJ / cm ² or more: practicable level

<Surface wrinkle evaluation>
The occurrence of wrinkles on the surface of the pattern after post-baking was observed with an optical microscope (magnification: 200 times). The evaluation criteria are as follows.
◎: No wrinkles are observed on the surface of the pattern. ○: Slight wrinkles are observed on the surface of the pattern, which is practically acceptable.

<Developing speed evaluation>
The coloring composition was spin-coated on a glass substrate using a spin coater to a dry film thickness of 1.0 μm, and dried at 70 ° C. for 20 minutes.
2 ml of a 2% by weight aqueous solution of potassium hydroxide was added dropwise to the above coating film, and the time until the coating thickness was not dissolved was measured to evaluate the developing speed of the coloring composition. The ranking of the evaluation is as follows.
：: Less than 25 seconds: good level Δ: 25 seconds or more, less than 35 seconds: practicable level ×: 35 seconds or more: practicable level

Reference Signs List 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 colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerizable initiator (D), a sensitizer (E), and an organic solvent,
A coloring composition for a color filter, wherein the sensitizer (E) is an anthracene compound.   The colored composition for a color filter according to claim 1, wherein the mass ratio of the photopolymerizable initiator (D) to the sensitizer (E) is D / E = 10/90 to 90/10.   The colored composition for a color filter according to claim 1 or 2, wherein the photopolymerizable initiator (D) is an oxime ester-based compound. A color filter, comprising: a base material; and a filter segment formed from the coloring composition for a color filter according to claim 1.