JP7131089B2 - Coloring composition for color filter and color filter - Google Patents

Description

The present invention provides a color liquid crystal display device, a color solid-state imaging device, an organic EL display device, a quantum dot display device, and a coloring composition used in the manufacture of color filters used in electronic paper and the like, and a coloring composition, and this The present invention relates to a color filter comprising filter segments formed using

The color filter is formed by arranging two or more kinds of fine strip-shaped filter segments with different hues in parallel (stripe) or intersecting each other on a transparent substrate such as a glass substrate. are arranged such that two or more kinds of fine filter segments having different values are arranged in order in the longitudinal direction and the lateral direction. The filter segments have small dimensions of several microns to several hundred microns, and are orderly arranged in a predetermined array for each hue.
Currently, the mainstream method for producing color filters is a method called a pigment dispersion method, in which pigments having excellent resistance to light and heat are used as coloring agents. In addition, in the pigment dispersion method, a color filter is manufactured by the following method. First, a coloring composition (pigment resist) obtained by dispersing a pigment in a photosensitive transparent resin solution is applied to a transparent substrate such as glass. After removing the solvent from the coating by drying, the coating is exposed with a pattern corresponding to filter segments of a certain color. Next, the unexposed portion of the coating film is removed by development, and then, if necessary, treatment such as heating is performed. As a result, a filter segment pattern for the first color is obtained. Then, by performing the same operation, filter segment patterns of other colors are formed to complete the color filter.

In recent years, high color reproducibility of displays has become an important trend. In order to improve the color reproducibility of displays, studies have focused on improving the color reproducibility of backlights, but it is also necessary to use very dark colors for color filters in order to improve the color reproducibility. In such a case, in the exposure process for forming the color filter pattern, the amount of light reaching the bottom of the coating film becomes weak, so photocuring tends to be insufficient, resulting in the problem of not being able to obtain a pattern of the desired shape. do.

Specifically, the dimension of the pattern obtained in the color filter manufacturing process, when the exposure dose in the exposure process is changed, the dimensional stability is required for the coloring composition so that the variation is within a certain extent. Colored compositions that achieve color reproduction tend to have poor dimensional stability. Similarly, a colored composition that achieves high color reproduction tends to deteriorate the linearity of the pattern.

Various methods have been examined so far to solve these problems. For example, in Patent Document 1, dimensional stability is ensured by adding a polymer having a specific structure to the coloring composition. In Patent Document 2, pattern shape and dimensional stability are realized by providing an anchor layer on a substrate. In Patent Document 3, a polymer having a specific structure is added to a coloring composition to realize stability of pattern dimensions at a low exposure dose. In Patent Document 4, dimensional stability is achieved by using a polymerization initiator having a specific structure. In Patent Document 5, dimensional stability against development is ensured by using a thiol-based compound.

JP 2013-254047 A JP 2013-073115 A JP 2012-108227 A JP 2011-002796 A JP 2010-039475 A JP 2008-089743 A

An object of the present invention is to achieve the following objects.
That is, an object of the present invention is to provide a coloring composition for a color filter that can form high-sensitivity and favorable pixels, and a color filter formed using the composition.

That is, the present invention provides a colorant containing a coloring agent (A), a binder resin (B), a polymerizable monomer (C), an oxime ester photopolymerization initiator (D), and a solvent (E). A coloring composition for a filter,
The coloring agent (A) contains an aluminum phthalocyanine pigment (A1), and
Solvent (E) is a coloring composition for color filters containing 0.1 to 10% by mass of a solvent (EH) that satisfies two or more of the following (1) to (3) in the total solvent.
(1) The boiling point at atmospheric pressure is 175° C. or higher and less than 230° C. (2) The viscosity at 25° C. is less than 2.0 mPa S (3) When the evaporation rate of n-butyl acetate is 100, the evaporation rate is 1 or more and 20 Less than

The present invention also relates to the coloring composition for color filters, wherein the solvent (EH) is one or more selected from the group consisting of alkyl alcohol ether acetate and alkyl alcohol ether.

Further, the present invention provides a colorant containing a coloring agent (A), a binder resin (B), a polymerizable monomer (C), an oxime ester photopolymerization initiator (D), and a solvent (E). A coloring composition for a filter,
The coloring agent (A) contains an aluminum phthalocyanine pigment (A1), and
The solvent (E) is selected from the group consisting of dipropylene glycol methyl ether acetate, dipropylene glycol methyl-n-propyl ether, and dipropylene glycol methyl ether. Containing 1 to 10% by mass, it relates to a coloring composition for color filters.

The present invention also relates to the coloring composition for color filters, wherein the coloring agent (A) further contains a yellow pigment component (A2) containing a quinophthalone pigment.

The present invention also relates to a color filter comprising a substrate and a filter segment formed from the coloring composition for a color filter.

According to the present invention, even in the exposure step after prebaking, the coloring composition for color filters, in which the fluidity of the functional groups of the polymerizable compound in the resist coating film is easily secured, that is, the fluidity of the functional groups is high. As a result, it is possible to provide a color filter coloring composition having high sensitivity and a high development speed.

Each constituent component of the coloring composition of the present invention is described below.
In the present application, when "(meth)acryloyl", "(meth)acryl", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide""acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide and/or methacrylamide", respectively, unless shall be represented.
Moreover, "C.I." mentioned in this specification means a color index (C.I.).

<Colorant (A)>
The coloring composition of the present invention contains, as a coloring agent (A), an aluminum phthalocyanine compound (A1) and either or both of an organic pigment and a dye.
<Aluminum phthalocyanine compound (A1)>
First, the aluminum phthalocyanine compound (A1) of the present invention will be described. The aluminum phthalocyanine compound of the present invention is represented by general formula (A1-2) and can be suitably used as a coloring agent, particularly a green coloring agent, for use in a coloring composition for color filters.

General formula (A1-2)

[In general formula (A1-2), X ₁ to X ₄ are each independently an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted a cycloalkyl group, an optionally substituted heterocyclic group, an optionally substituted alkoxyl group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, Alternatively, it represents an arylthio group which may have a substituent.
Y ₁ to Y ₄ each independently represent a halogen atom, a nitro group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group.
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 are each independently a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxyl group, or a substituted represents an aryloxy group which may have a group; R ₃ is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group or an optionally substituted hetero represents a cyclic group. R ₄ represents a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted heterocyclic group.
a ₁ , a ₂ , a ₃ , a ₄ , b ₁ , b ₂ , b ₃ and b ₄ each independently represents an integer of 0 to 4, 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. ]

The "alkyl group" of the optionally substituted alkyl group in X ₁ to X ₄ includes methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group and neopentyl group. , n-hexyl group, n-octyl group, stearyl group, 2-ethylhexyl group, and other linear or branched alkyl groups. methyl group, 2,2,2-trifluoroethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitro propyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-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, and the "aryl group having a substituent" includes a p-methylphenyl group, p- bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl 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-aminoanthraquinonyl group and the like.

The "cycloalkyl group" of the cycloalkyl group which may have a substituent includes a cyclopentyl group, a cyclohexyl group, an adamantyl group and the like. -dimethylcyclopentyl group, 4-tert-butylcyclohexyl group and the like.

The "heterocyclic group" of the heterocyclic group optionally having a substituent includes a pyridyl group, a pyrazyl group, a piperidino group, a pyranyl group, a morpholino group, an acridinyl group and the like. ” includes a 3-methylpyridyl group, an N-methylpiperidyl group, an N-methylpyrrolyl group, and the like.

The "alkoxyl group" of the alkoxyl group which may have a substituent includes 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, 2 , 3-dimethyl-3-pentyloxy, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group and other linear or branched alkoxyl groups. "group" includes a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, a 2,2-ditrifluoromethylpropoxy group, a 2- ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group and the like.

Examples of the "aryloxy group" of the aryloxy group which may have a substituent include a phenoxy group, a naphthoxy group, an anthryloxy group and the like, and examples of the "aryloxy group having a substituent" include p-methyl phenoxy group, p-nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, 2-methyl-4-chlorophenoxy group and the like.

Examples of the "alkylthio group" of the alkylthio group which may have a substituent include 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 and an octadecylthio group. Examples of "substituted alkylthio group" include methoxyethylthio group, aminoethylthio group, benzylaminoethylthio group, methylcarbonylaminoethylthio group, phenylcarbonylaminoethylthio group and the like.

The "arylthio group" of the optionally substituted arylthio group includes a phenylthio group, 1-naphthylthio group, 2-naphthylthio group, 9-anthrylthio group and the like. , chlorophenylthio group, trifluoromethylphenylthio group, cyanophenylthio group, nitrophenylthio group, 2-aminophenylthio group, 2-hydroxyphenylthio group and the like.

When the above X ₁ to X ₄ have substituents, the substituents may be the same or different, and specific examples thereof include halogen groups such as fluorine, chlorine, and bromine, amino groups, hydroxyl groups, nitro groups, and the like. In addition to groups, alkyl groups, aryl groups, cycloalkyl groups, alkoxyl groups, aryloxy groups, alkylthio groups, arylthio groups and the like can be mentioned. Moreover, these substituents may be plural.
The alkyl group, aryl group, cycloalkyl group, alkoxyl group, aryloxy group, alkylthio group and arylthio group have the same meanings as those described above for X1 to X4.

Specific examples of Y ₁ to Y ₄ include a halogen atom, a nitro group, a phthalimidomethyl group (C ₆ H ₄ (CO) ₂ N—CH ₂ —) which may have a substituent, a sulfamoyl group ( H ₂ NSO ₂ —). Further, a phthalimidomethyl group having a substituent represents a structure in which a hydrogen atom in the phthalimidomethyl group is substituted with a substituent, and a sulfamoyl group having a substituent represents a structure in which a hydrogen atom in the sulfamoyl group is substituted with a substituent. represents the constructed structure. Preferred Y ₁ to Y ₄ are halogen atoms and sulfamoyl groups. Aluminum phthalocyanine compounds in which b ₁ to b ₄ are 0 (that is, Y ₁ to Y ₄ are absent) can also be suitably used. Halogen atoms include fluorine, chlorine, bromine and iodine. The “substituent” of the optionally substituted phthalimidomethyl group and the optionally substituted sulfamoyl group is synonymous with the substituents X ₁ to X ₄ .

Among the structures of the aluminum phthalocyanine compound (A1-2), regarding the substituents on the phthalocyanine ring, a ₁ , a ₂ , a ₃ and a ₄ are 0, and Y ₁ to Y ₄ are halogen atoms. A structure represented by (A1-3) is preferred.

General formula (A1-3)

[In general formula (A1-3), Y represents a halogen atom, and b represents the average value of the number of substituents on 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 are each independently a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxyl group, or a substituted represents an aryloxy group which may have a group; R ₃ is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group or an optionally substituted hetero represents a cyclic group. R ₄ represents a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted heterocyclic group. ]

The “halogen atom” in general formula (A1-3) includes fluorine, bromine, chlorine and iodine, with bromine and chlorine being preferred.

In applications where color density is strongly required, an aluminum phthalocyanine compound in which b is 0 and which is not substituted with halogen at all is excellent from the viewpoint of color density, and is therefore preferable. On the other hand, in applications where the requirement for color density is not strong, b is preferably 8 to 15 from the viewpoint of hue and fastness.

In the aluminum phthalocyanine compound represented by the general formula (A1-2), from the viewpoint of fastness and color properties, Z is -OP(=O)R ₁ R ₂ , -OC(=O)R ₃ or OS (=O) ₂ R ₄ is preferred, and -OP(=O)R ₁ R ₂ is more preferred. At least one of R ₁ and R ₂ is preferably an optionally substituted aryl group or an optionally substituted aryloxy group, and R ₁ and R ₂ are preferably is more preferably an aryl group or an aryloxy group, and both R ₁ and R ₂ are more preferably a phenyl group or a phenoxy group. Also, R ₃ and R ₄ are preferably an aryl group which may have a substituent or a heterocyclic group which may have a substituent.

Alkyl groups for R ₁ to R ₄ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, neopentyl group, n-hexyl group, n-octyl group and stearyl group. , 2-ethylhexyl group and the like, and alkyl groups having 1 to 6 carbon atoms are preferred. Examples of substituents of the substituted alkyl group include halogen atoms such as chlorine, fluorine and bromine, alkoxyl groups such as methoxy, aryl groups such as phenyl and tolyl, and nitro groups. Also, there may be a plurality of substituents. Accordingly, examples of substituted alkyl groups include trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2-dibromoethyl group, 2-ethoxyethyl group, 2-butoxy ethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group and the like.

Examples of the aryl group for R ₁ to R ₄ include monocyclic aromatic hydrocarbon groups such as phenyl group and p-tolyl group, and condensed aromatic hydrocarbon groups such as naphthyl group and anthryl group. Hydrocarbon groups are preferred. Also, an aryl group having 6 to 12 carbon atoms is preferable. Examples of substituents of the aryl group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkoxyl groups, amino groups and nitro groups. Also, there may be a plurality of substituents. Therefore, aryl groups having substituents include, for example, p-bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-dimethylaminophenyl group, 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.

Alkoxyl groups for R ₁ and R ₂ include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, neopentyloxy, 2,3-dimethyl-3- Linear or branched alkoxyl groups such as pentyloxy group, n-hexyloxy group, n-octyloxy group, stearyloxy group and 2-ethylhexyloxy group can be mentioned, and alkoxyl groups having 1 to 6 carbon atoms are preferred. Examples of substituents of the alkoxyl group having a substituent include halogen atoms such as chlorine, fluorine and bromine, aryl groups such as alkoxyl groups, phenyl groups and tolyl groups, and nitro groups. Also, there may be a plurality of substituents. Therefore, examples of substituted alkoxyl groups include a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, a 2,2- ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group and the like.

Examples of the aryloxy group for R ₁ and R ₂ include aryloxy groups consisting of monocyclic aromatic hydrocarbon groups such as phenoxy group and p-methylphenoxy group, and condensed aromatic hydrocarbon groups such as naphthaloxy group and anthryloxy group. and an aryloxy group consisting of a monocyclic aromatic hydrocarbon group is preferred. Also, an aryloxy group having 6 to 12 carbon atoms is preferable. Examples of substituents of the aryloxy group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkyl groups, alkoxyl groups, amino groups and nitro groups. Also, there may be a plurality of substituents. Therefore, the aryloxy group having a substituent includes, for example, p-nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, 2-methyl-4-chlorophenoxy group and the like. mentioned.

Cycloalkyl groups for R ₃ include monocyclic aliphatic hydrocarbon groups such as cyclopentyl group, cyclohexyl group, 2,5-dimethylcyclopentyl group and 4-tert-butylcyclohexyl group, and such as bornyl group and adamantyl group. Condensed aliphatic hydrocarbon groups are included. A cycloalkyl group having 5 to 12 carbon atoms is also preferred. Examples of substituents of the cycloalkyl group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkyl groups, alkoxyl groups, hydroxyl groups, amino groups and nitro groups. Also, there may be a plurality of substituents. Examples of substituted cycloalkyl groups include a 2,5-dichlorocyclopentyl group and a 4-hydroxycyclohexyl group.

Heterocyclic groups for R ₃ and R ₄ include aliphatic heterocyclic groups and aromatic heterocyclic groups such as pyridyl group, pyrazyl group, piperidino group, pyranyl group, morpholino group and acridinyl group. A heterocyclic group having 4 to 12 carbon atoms is preferred, and a heterocyclic group having 5 to 13 ring members is preferred. Examples of substituents of the heterocyclic group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkyl groups, alkoxyl groups, hydroxyl groups, amino groups and nitro groups. Also, there may be a plurality of substituents. A heterocyclic group having a substituent includes a 3-methylpyridyl group, an N-methylpiperidyl group, an N-methylpyrrolyl group, and the like.

Representative examples of Z in the general formula (A1-2) include the structures shown below (* represents the bonding position of the substituent with Al in the general formula (A1-2)); The invention is not limited to these. Cyclized isomers of the exemplified compounds are also included as preferred examples of the present invention.

[Method for producing aluminum phthalocyanine compound]
Next, a method for producing the aluminum phthalocyanine compound represented by the general formula (A1-2) of the present invention will be described, but the present invention is not limited to this production method.

The aluminum phthalocyanine compound represented by the general formula (A1-2) of the present invention is obtained by synthesizing a compound represented by the following general formula (A1-4) by a known method, followed by W ₁ P(=O)R ₁ R ₂ , It can be produced by reacting with an acidic compound represented by W ₂ C(=O)R ₃ or 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 atoms are synonymous with R ₁ , R ₂ , R ₃ , R ₄ and halogen atoms Y ₁ to Y ₄ in general formula (A1-2).

General formula (A1-4)

[In general formula (A1-4), X ₁ to X ₄ are each independently an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted a cycloalkyl group, an optionally substituted heterocyclic group, an optionally substituted alkoxyl group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, Alternatively, it represents an arylthio group which may have a substituent.
Y ₁ to Y ₄ each independently represent a halogen atom, a nitro group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group.
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 represents an integer of ₀ to 4, , 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. ]

<Other coloring agents>
In order to further adjust the chromaticity, the coloring composition of the present invention contains a coloring agent (organic pigment/dye) other than the aluminum phthalocyanine compound represented by the general formula (A1-2) within a range that does not impair the effects of the present invention. may contain. Although there are no particular restrictions on the colorant, a green pigment or yellow pigment is preferred, and a green pigment component (A3) or yellow pigment component (A2) is more preferred. These pigments and dyes can be used alone or in combination of two or more at any ratio as needed.

The content of the coloring agent is preferably 10% by mass or more, more preferably 15% by mass or more, and most preferably 15% by mass or more, based on the total non-volatile components of the coloring composition (100% by mass), from the viewpoint of obtaining sufficient color reproducibility. Preferably, it is 20% by mass or more. Moreover, from the viewpoint of the stability of the coloring composition, the content of the coloring agent is preferably 90% by mass or less, more preferably 80% by mass or less, and most preferably 70% by mass or less.
When the coloring agent contains a dye, the content of the dye is preferably 1 to 800 parts by mass with respect to 100 parts by mass of the pigment. More preferably, it is 5 to 400 parts by mass. When the added amount of the dye is within this range, the brightness and contrast ratio can be excellent.

<Green pigment (A3)>
Examples of green pigments include 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 2008- 19383, JP-A-2007-320986, JP-A-2004-70342, zinc phthalocyanine pigments described in JP-A-4893859, etc., and aluminum phthalocyanine pigments described in JP-A-4893859. Not limited. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Green 7, 36 and 58.
<Yellow pigment component (A2)>
In this specification, the yellow pigment component (A2) preferably contains quinophthalone (hereinafter sometimes referred to as quinophthalone compound). Quinophthalone is a compound represented by general formula (2).

general formula (2)

[In the general formula (2), X1 to X13 are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxyl group, a substituted aryl group, —SO ₃ H group, —COOH group, metal salt of —SO ₃ H group or —COOH group, alkylammonium salt of —SO ₃ H group or —COOH group, substituent It represents a phthalimidomethyl group which is good, or a sulfamoyl group which may have a substituent. Adjacent groups of X1 to X4 and/or X10 to X13 together form an aromatic ring which may have a substituent.

Here, halogen atoms include, for example, fluorine, chlorine, bromine, and iodine.

In addition, the alkyl group which may have a substituent includes 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 and an n-octyl group. linear or branched alkyl groups such as groups, stearyl groups, 2-ethylhexyl groups, trichloromethyl groups, trifluoromethyl groups, 2,2,2-trifluoroethyl groups, 2,2-dibromoethyl groups, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, pentyl group, 4-methylpentyl group, 4-tert-butylbenzyl group, 4-methoxy Alkyl groups having substituents such as a pentyl group, a 4-nitrobenzyl group and a 2,4-dichlorobenzyl group can be mentioned.

Examples of the alkoxyl group which may have a substituent include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isoptyloxy, tert-butyloxy, neopentyloxy, 2, In addition to linear or branched alkoxyl groups such as 3-dimethyl-3-pentoxy, n-hexyloxy, n-octyloxy, stearyloxy, and 2-ethylhexyloxy, trichloromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropyloxy group, 2,2-ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitro An alkoxyl group having a substituent such as a propoxy group and a benzyloxy group can be mentioned.

In addition, the aryl group which may have a substituent includes a phenyl group, a naphthyl group, an anthranyl group and the like, as well as a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group, a p- methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl 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 and 2-aminoanthraquinonyl group.

Examples of acidic groups include —SO ₃ H and —COOH. Monovalent to trivalent metal salts of these acidic groups include sodium salts, potassium salts, magnesium salts, calcium salts, iron salts and aluminum salts. etc. Examples of alkylammonium salts of acidic groups include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine and stearylamine; quaternary alkyl salts such as palmityltrimethylammonium, dilauryldimethylammonium and distearyldimethylammonium salts; Ammonium salts are mentioned.

_{The " substituent _ _ _} "" includes the above halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxyl group, an optionally substituted aryl group, and the like.

Adjacent groups of X1 to X4 and/or X10 to X13 in general formula (2) together form an aromatic ring which may have a substituent. The aromatic ring referred to herein includes aromatic hydrocarbon rings and heteroaromatic rings. Examples of aromatic hydrocarbon rings include benzene, naphthalene, anthracene, and phenanthrene rings. Examples of heteroaromatic rings include pyridine ring, pyrazine ring, pyrrole ring, quinoline ring, quinoxaline ring, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, oxazole ring, thiazole ring, imidazole ring, pyrazole ring, indole ring, carbazole ring and the like.

The compound represented by general formula (2) is preferably any one of general formulas (2A) to (2C) below.

General formula (2A)

General formula (2B)

General formula (2C)

[In general formulas (2A) to (2C), X14 to X28, X29 to X43, and X44 to X60 are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group, or a an alkoxyl group which may be substituted, an aryl group which may have a substituent, a -SO ₃ H group, a -COOH group, a metal salt of a -SO ₃ HH group or a -COOH group, a -SO ₃ H group or a -COOH group is an alkylammonium salt of, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group.

Furthermore, X14 to X28, X29 to X43, and X44 to X60 in general formulas (2A) to (2C) are more preferably hydrogen atoms or halogen atoms.

Specific examples of the compound represented by formula (2) include quinophthalone compounds (a) to (p) shown below.

The yellow pigment component (A2) can use other yellow pigments in addition to quinophthalone.

(Other yellow pigments)
As other yellow pigments, organic or inorganic pigments can be used alone or in combination of two or more types, and pigments with high color development and high heat resistance, particularly pigments with high heat decomposition resistance are preferred. Organic pigments are usually used. As the organic pigment, those generally available on the market can be used, and natural pigments and inorganic pigments can be used in combination according to the desired hue of the filter segment.

Specific examples of yellow organic pigments that can be used in the coloring composition are shown below. As a yellow pigment, 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 and yellow pigments such as quinophthalone pigments described in Japanese Patent No. 4993026 can be used. Especially from the viewpoint of the contrast ratio and brightness of the filter segment, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180185 and quinophthalone pigments described in Japanese Patent No. 4993026, preferably at least one selected from the group consisting of C.I. I. Pigment Yellow 138, 139, 150, 185 or quinophthalone pigments described in Japanese Patent No. 4993026 are more preferred.

The mass ratio of the green pigment component (A3) and the yellow pigment component (A2) is preferably (A3)/(A2)=40/60 to 90/10. When the above range is satisfied, brightness and color reproducibility are further improved.

When a green pigment is used in combination with the aluminum phthalocyanine compound represented by general formula (A1-2) or general formula (A1-3), from the viewpoint of brightness and hue, green pigment/general formula (A1-2) Alternatively, the mass ratio of the aluminum phthalocyanine compound represented by general formula (A1-3) is preferably in the range of 10/90 to 70/30. It is more preferably in the range of 20/80 to 40/60, still more preferably in the range of 20/80 to 35/65.

When a yellow pigment is used in combination with the aluminum phthalocyanine compound represented by general formula (A1-2) or general formula (A1-3), from the viewpoint of brightness and hue, yellow pigment / general formula (A1-2) or The weight ratio of the aluminum phthalocyanine compound represented by general formula (A1-3) is preferably in the range of 70/30 to 10/90. It is more preferably in the range of 70/30 to 25/75, still more preferably in the range of 70/30 to 40/60.

In addition to the above green pigment and yellow pigment, a red pigment and a blue pigment may also be contained within a range that does not impair the effects of the present invention.
(red pigment)
As a red pigment, 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-A-2011-523433, or JP-A-2013-161025 Naphthol azo pigments and the like described in JP-A-2004-200063 are included, but are not particularly limited to these. Among these, C.I. I. Pigment Red 177, 242, 254, 269 is preferably used.

(blue pigment)
Examples of blue pigments include C.I. I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, JP-A-2004-333817, Examples include aluminum phthalocyanine pigments described in Japanese Patent No. 4893859 and the like, and C.I. I. Purple pigments such as Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42 and 50 can be used in combination, but are not particularly limited thereto.
Among these, C.I. I. Pigment Blue 15:1, 15:6 are particularly preferred.

<Dye>
Any of acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, and the like can be used as dyes. Moreover, it may be in the form of a derivative of these or a lake pigment obtained by turning a dye into a lake.

Furthermore, in the case of acid dyes having an acidic group such as sulfonic acid or carboxylic acid, or in the form of direct dyes, inorganic salts of acid dyes, acid dyes and quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, Alternatively, a salt-forming compound with a nitrogen-containing compound such as a primary amine compound, or a salt-forming compound using a resin component having these functional groups, or a sulfonamidation and use as a sulfonic acid amide compound. In order to be excellent in resistance, it is possible to make a coloring composition excellent in fastness, which is preferable.
In addition, a salt-forming compound of an acid dye and a compound having an onium base is also preferable because of excellent fastness, and more preferably, the compound having an onium base is a resin having a cationic group in its side chain.

In the case of the form of a basic dye, it can be used by forming a salt using an organic acid, perchloric acid, or a metal salt thereof. Among them, salt-forming compounds of basic dyes are preferable because of their excellent resistance and compatibility with pigments. An anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or a salt-forming compound obtained by forming a salt with an acid dye can be used. It is more preferable.

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

Chemical structures of 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, etc.). dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinone imine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes Dyes, polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and metal complex dyes thereof.

Among these dye structures, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium Xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanines. A dye structure derived from a dye selected from the group of dyes is more preferable. Specific dye compounds capable of forming a dye structure are described in "Shinban Dye Handbook" (edited by the Society of Synthetic Organic Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyers and Colorists), "Dye Handbook" (Ogawara et al.). Ed.; Kodansha, 1986).

<Refinement of pigment>
When the coloring agent used in the coloring composition of the present invention is a pigment, it is preferably used in a fine form. The method of refining is not particularly limited, and for example, any of wet grinding, dry grinding, and dissolution precipitation method can be used. etc., and can be miniaturized. The average primary particle size of the pigment determined by TEM (transmission electron microscope) is preferably in the range of 5 to 90 nm. If it is smaller than 5 nm, it becomes difficult to disperse in an organic solvent, and if it is larger than 90 nm, it may not be possible to obtain a sufficient contrast ratio. For these reasons, the average primary particle size is more preferably in the range of 10 to 70 nm.

The salt milling process is performed by subjecting a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent to a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, a planetary mixer, or the like in a batch or continuous manner. In this treatment, the mixture is mechanically kneaded while being heated using a kneader, and then washed with water to remove the water-soluble inorganic salt and the water-soluble organic solvent. The water-soluble inorganic salt functions as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

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

The water-soluble organic solvent has the function of moistening the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (miscible in) water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120° C. or higher is preferable from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1,000 parts by mass, most preferably 50 to 500 parts by mass, per 100 parts by mass of the pigment.

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

<Dye derivative>
A known dye derivative having an acidic group, a basic group, a neutral group, or the like in the organic dye residue can be used in the coloring composition of the present invention. For example, compounds having an acidic substituent such as a sulfo group, a carboxyl group, and a phosphoric acid group, amine salts thereof, compounds having a basic substituent such as a sulfonamide group or a terminal tertiary amino group, a phenyl group, and phthalimide Examples thereof include compounds having a neutral substituent such as an alkyl group.
Examples of organic dyes include anthraquinone-based pigments, quinacridone-based pigments, dioxazine-based pigments, perinone-based pigments, perylene-based pigments, thiazineindigo-based pigments, triazine-based pigments, benzimidazolone-based pigments, and indole-based pigments such as benzoisoindole. , isoindoline-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, naphthol-based pigments, threne-based pigments, metal complex-based pigments, and azo-based pigments such as azo, disazo and polyazo.
Specifically, as diketopyrrolopyrrole dye derivatives, JP 2001-220520, WO2009/081930, WO2011/052617, WO2012/102399, JP 2017-156397, phthalocyanine As the dye derivative, JP-A-2007-226161, WO2016/163351 pamphlet, JP-A-2017-165820, Japanese Patent No. 5753266, as the anthraquinone dye derivative, JP-A-63-264674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009/025325 pamphlet, quinacridone dye derivatives, JP-A-48- 54128, JP 03-9961, JP 2000-273383, JP 2011-162662 as a dioxazine dye derivative, JP 2007-314785 as a thiazine indigo dye derivative Publications, as triazine dye derivatives, JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, JP-A-2007-314681, JP-A-2009-57478 as a benzoisoindole-based dye derivative, JP-A-2003-167112 as a quinophthalone-based dye derivative, JP-A-2006-291194, JP-A-2006-291194 2008-31281, JP 2012-226110, as a naphthol dye derivative, JP 2012-208329, JP 2014-5439, as an azo dye derivative, JP 2001-172520 Publication, JP 2012-172092, JP 2004-307854 as an acidic substituent, JP 2002-201377 as a basic substituent, JP 2003-171594, JP 2005 -181383, Japanese Patent Laid-Open No. 2005-213404, and other known dye derivatives. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply as a compound. A compound having a substituent such as a sexual group is synonymous with a dye derivative.
These dye derivatives can be used singly or in combination of two or more.

<Resin Dispersant>

The resin-type dispersant used in the present invention is a resin-type dispersant having a carboxyl group.
As for the shape of the resin-type dispersant having a carboxyl group, there are a straight-chain resin-type dispersant and a comb-shaped resin-type dispersant.
<Comb-shaped resin-type dispersant>
Comb-shaped resin-type dispersants having a carboxyl group include the following (J1) or (J2).
[Resin type dispersant (J1)]
The resin-type dispersant (J1) can be produced by known methods such as those disclosed in WO2008/007776, JP-A-2008-029901, JP-A-2009-155406, and the like.
For example, a resin-type dispersant that is a reaction product of a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of a tetracarboxylic dianhydride, or a hydroxyl group of a compound having a hydroxyl group and a tetracarboxylic dianhydride A resin-type dispersant that is a polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product with an acid anhydride group of a compound.

[Resin Dispersant (J2)]
The resin-type dispersant (J2) can be produced by known methods such as those disclosed in WO2008/007776, JP-A-2009-155406, JP-A-2010-185934, JP-A-2011-157416.
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, it has a hydroxyl group, a t-butyl group, an oxetane skeleton, a thermal cross-linking group such as a blocked isocyanate. A resin-type dispersant obtained by reacting an ethylenically unsaturated monomer and a resin-type dispersant having a side chain polymerized with other monomers and an ethylenically unsaturated monomer having an isocyanate group in the hydroxyl group of the side chain. .

<Linear resin-type dispersant>
Linear resin-type dispersants can all be produced using known methods. can be synthesized using a known method as shown in . As an example of a method for producing a linear dispersant, a dispersant having a carboxyl group can be produced by adding a tricarboxylic acid anhydride to the hydroxyl group of a vinyl polymer having one hydroxyl group at one end. can be done.

[Other resin-type dispersants]
Other resin-type dispersants have a colorant-affinity site that has the property of adsorbing to the additive colorant and a site that is compatible with the colorant carrier. Including those overlapping with the above, specifically, polyurethane, polycarboxylic acid ester such as polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid Acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, poly(lower alkyleneimine) Oil-based dispersants such as amides and their salts formed by the reaction of polyesters with free carboxyl groups, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers Water-soluble resins such as coalescence, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide/propylene oxide addition compounds, phosphate esters, etc. are used, and these can be used alone or in combination of two or more.
Examples of polymeric dispersants having basic functional groups include nitrogen atom-containing graft copolymers and nitrogen atom-containing polymers having functional groups containing tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, etc. in side chains. Examples include acrylic block copolymers and urethane polymer dispersants.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166 manufactured by BYK-Japan. or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, LPN6919, or Lactimon, Lactimon-WS or Bykumen, SOLSPERSE-3000, 9000, 13000, 13240 manufactured by Lubrizol Japan, 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、 EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408 manufactured by BASF, such as 56000, 76500 , 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., Ajinomoto Fine-Techno Co., Ltd. Ajisper PA111, PB711, PB821, PB822, PB824 and the like.

The resin-type dispersant is preferably used in an amount of about 5 to 200% by mass, more preferably in an amount of about 10 to 100% by mass, based on the total amount of the coloring agent.

<Polymerizable monomer (C)>
The coloring composition of the present invention contains a polymerizable monomer (C). The polymerizable monomer (C) includes monomers or oligomers that form a transparent resin by curing with ultraviolet light, heat, or the like.

Examples of monomers and oligomers that form transparent resins by curing with ultraviolet light or heat include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate ) acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethyleneglycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth) Acrylates, isocyanurate EO-modified di(meth)acrylate, isocyanurate EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6 - hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate ) acrylates, tricyclodecanyl (meth)acrylates, ester acrylates, methylolated melamine (meth)acrylates, epoxy (meth)acrylates, various acrylic and methacrylic acid esters such as 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, etc., but not necessarily limited to these not to be
These polymerizable monomers may be used singly or as a mixture of two or more at any ratio as required.

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

The blending amount of the polymerizable monomer is preferably 5 to 400 parts by mass based on the total mass of the colorant (100 parts by mass), and is preferably 10 to 300 parts by mass from the viewpoint of photocurability and developability. It is more preferable to have

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

Examples of the polymerizable monomer having an acid group include, for example, polyhydric alcohols and (meth)acrylic acid and free hydroxyl group-containing poly(meth)acrylates and esters of dicarboxylic acids; Esterified products with hydroxyalkyl (meth)acrylates and the like can be mentioned. Specific examples include monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. and free carboxyl group-containing monoesters with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid and terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4 - Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, 2-hydroxyethyl acrylate, 2- Monohydroxy monoacrylates such as hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, or free carboxyl group-containing oligoesters with monohydroxy monomethacrylates, etc., but the effects of the present invention are limited to these. not to be

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

These acid group-containing polymerizable monomers may be used singly or as a mixture of two or more at an arbitrary ratio as required.

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

(Meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, 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 Examples include methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction products of epoxy group-containing compounds and carboxy(meth)acrylate, and hydroxyl group-containing polyol polyacrylates.

Polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate and the like.

Although the structure of the alcohol is not limited, it is preferable to use a polyhydric alcohol because the degree of cross-linking of the cured coating increases and the resistance of the coating increases. Polyhydric alcohols include propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol and the like.

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

These urethane bond-containing polymerizable monomers may be used singly or as a mixture of two or more at any ratio as required.

<Oxime ester photoinitiator (D)>
When the oxime ester photoinitiator (D) absorbs ultraviolet rays, the N—O bond of the oxime is cleaved to generate an iminyl radical and an alkyloxy radical. Since these radicals are further decomposed to generate highly active radicals, a pattern can be formed with a small amount of exposure.

As the oxime ester photopolymerization initiator (D), a known compound can be used, and an oxime ester photopolymerization initiator represented by general formula (D-1) is preferred.

General formula (D-1)

In general formula (D-1), Y ¹ is a hydrogen atom or an optionally substituted alkenyl group, alkyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group;
Y ² is a hydrogen atom or an optionally substituted alkenyl group, alkyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkylsulfanyl group, arylsulfanyl group , an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, or an amino group.
Z is a direct bond or -CO- group,
Y ³ is a monovalent organic group containing a carbazole group which may have a substituent, a Ph-S-Ph- group (Ph represents a phenyl group or a phenylene group which may have a substituent); etc. are preferred.

Among the oxime ester photopolymerization initiators represented by the general formula (D-1), the oxime ester photopolymerization initiators represented by the following general formula (D-2) or (D-3) have excellent photosensitivity. more preferred.

[Oxime ester photopolymerization initiator represented by general formula (D-2)]
General formula (D-2)

General formula (D-2) corresponds to the case where Z in general formula (D-1) is a —CO— group, Y ³ is a Ph—S—Ph— group, Y ⁴ to Y ⁶ are hydrogen atoms, Alternatively, an alkyl group or an aryl group, which may have a substituent, is preferred. The optionally substituted alkyl group or optionally substituted aryl group for Y ⁴ to Y ⁶ is the same as the alkyl group or aryl group for Y ¹ and Y ² .

Furthermore, Y ¹ is an aryl group which may have a substituent, Y ² is an alkyl group having 1 to 20 carbon atoms which may have a substituent, and Y ⁴ and Y ⁶ are hydrogen atoms. Y ⁵ is preferably a hydrogen atom or a Y ⁷ --CO-- group, more preferably.

Y ⁷ includes, for example, a halogen group such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group, an ethoxy group and a tErt-butoxy group; an aryloxy group such as a phenoxy group and a p-tolyloxy group; Alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, acyloxy groups such as acetoxy group, propionyloxy group, benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, methoxalyl group, etc. Acyl group, methylsulfanyl group, alkylsulfanyl group such as tErt-butylsulfanyl group, phenylsulfanyl group, arylsulfanyl group such as p-tolylsulfanyl group, methylamino group, alkylamino group such as cyclohexylamino group, dimethylamino group , a diethylamino group, a morpholino group, a dialkylamino group such as a piperidino group, a phenylamino group, an arylamino group such as a p-tolylamino group, a methyl group, an ethyl group, a tErt-butyl group, an alkyl group such as a dodecyl group, a phenyl group, aryl groups such as p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group and benzofuranyl group; heterocyclic groups such as furyl group and thienyl group; mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammoniumyl group, dimethylsulfonyl Myl group, triphenylphenacylphosphoniumyl group and the like.

More preferred substituents for Y2 ^are cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclooctadecyl groups.

Specific examples of the oxime ester photopolymerization initiator represented by the general formula (D-2) include photopolymerization initiators represented by the following chemical formula (D-2-1) or (D-2-2). .

[Oxime ester photopolymerization initiator represented by general formula (D-3)]
General formula (D-3)

General formula (D-3) corresponds to the case where Y ³ in general formula (D-1) is a monovalent organic group containing a carbazole group which may have a substituent, and Y ⁷ to Y ¹⁴ are It has the same meaning as the substituent for Y ¹ and Y ² .

Furthermore, an optionally substituted alkyl group having 1 to 20 carbon atoms as Y ¹ may have an optionally substituted alkyl group having 1 to 20 carbon atoms or a substituent as Y ² A good aryl group is preferably a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group as Y ⁷ to Y ¹⁴ .

When Z in general formula (D-3) is a direct bond, an oxime ester photopolymerization initiator represented by general formula (D-3a) below is preferred.

"Oxime ester photopolymerization initiator represented by general formula (D-3a)"
General formula (D-3a)

General formula (D-3a) corresponds to the case where Z in general formula (1) is a direct bond, Y ³ is a monovalent organic group containing a carbazole group which may have a substituent, and general formula (D Y ⁷ to Y ¹⁰ and Y ¹² to Y ¹³ in -3) are hydrogen atoms.
Also, Y ¹¹ is preferably a Y ¹⁵ —CO— group or a nitro group. Y ¹⁵ has the same meaning as the substituent for Y ¹ and Y ² and is preferably an optionally substituted aryl group. The Y ¹⁵ —CO— group is preferably an acyl group which may further have a substituent, such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, and a methoxalyl group. A benzoyl group which may have a substituent or a nitro group is more preferred. Y ¹⁴ is preferably an optionally substituted alkyl group having 1 to 20 carbon atoms or an optionally substituted aryl group.

Further, as a substituent of the benzoyl group which may have a substituent, an alkyl group having 1 to 20 carbon atoms or an alkyloxy group is preferable. Further, the alkyl group is preferably a methyl group or an ethyl group. Among the alkyloxy groups, straight-chain, branched-chain, or alkyloxy groups having 2 to 18 carbon atoms and optionally interrupted by one or more -O- Monocyclic or condensed polycyclic alkyloxy groups are preferred, linear, branched, monocyclic or condensed polycyclic having 2 to 18 carbon atoms in Y ¹ and optionally interrupted by one or more —O— It is synonymous with alkyloxy group.

Y ² is preferably an optionally substituted alkyl group having 1 to 20 carbon atoms, and the substituents are preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, A cycloalkyl group such as a cyclooctadecyl group. Further, an aryl group which may have a substituent is preferable, and the substituent is preferably an alkyl group having 1 to 20 carbon atoms which may further have a substituent, a methoxy group, an ethoxy group, or a tErt-butoxy group. An alkoxy group such as is preferred.

Examples of the oxime ester photopolymerization initiator represented by the general formula (D-3a) include photopolymerization initiators represented by the following chemical formulas (D-3a-1) to (D-3a-6).

"Oxime ester photopolymerization initiator represented by general formula (D-3b)"
When Z in general formula (D-3) is a —CO— group, an oxime ester photopolymerization initiator represented by general formula (D-3b) below is preferred.

General formula (D-3b)

General formula (D-3b) corresponds to the case where Z in general formula (D-1) is a —CO— group and Y ³ is a monovalent organic group containing a carbazole group which may have a substituent, It is an oxime ester photopolymerization initiator having a keto-type carbazole group. Y ⁷ to Y ¹³ are preferably a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group, and Y ¹⁴ may have a substituent. A good aryl group is preferred. The aryl group which may have a substituent is preferably an acyl group such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, or a methoxalyl group, and more preferably a benzoyl group.

The oxime ester photopolymerization initiator represented by general formula (D-3b) is preferably a photopolymerization initiator represented by chemical formulas (D-3b-1) to (D-3b-4) below.

Commercially available oxime ester compounds are 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (IRGACURE OXE-01), ethanone, 1 from BASF. -[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) (IRGACURE OXE 02), N-1919 (manufactured by ADEKA), TRONLY TR -PBG-304, TRONLY TR-PBG-305, TRONLY TR-PBG-309 (all manufactured by Changzhou Tenryu New Materials Co., Ltd.) and the like. In addition, oxime ester-based photopolymerization described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-020998, etc. It is also possible to use an initiator. Furthermore, oxime ester photopolymerization initiators represented by the following chemical formulas (D-4-1) and (D-4-2) are also included.

The content of the oxime ester photopolymerization initiator (D) is preferably 0.5 to 10 parts by mass, more preferably 1 to 7 parts by mass, with respect to 100 parts by mass of the total mass of the color filter coloring composition excluding the solvent. . Photocurability and developability are further improved by using an appropriate amount.

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

<Other Photopolymerization Initiator (D1)>
In the colored composition, the oxime ester photopolymerization initiator (D) can be used in combination with another photopolymerization initiator (D1). Thereby, a color filter having a good pattern shape can be formed.

Other photopolymerization initiators (D1) include, 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, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one and other acetophenone compounds Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl Benzophenone compounds such as -4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2 Thioxanthone compounds such as ,4-diisopropylthioxanthone and 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2- (p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6 -bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s -triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, 2,4- Triazine compounds such as trichloromethyl-(4′-methoxystyryl)-6-triazine; bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-triazine phosphine compounds such as methylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; .

Other commercially available photopolymerization initiators (D1) include acetophenone compounds such as "IRGACURE 907" (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one), " IRGACURE 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, phosphine compounds are "IRGACURE819" (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide), "IRGACURETPO" (2, 4,6-trimethylbenzoyldiphenylphosphine oxide) and the like manufactured by BASF.

Other photopolymerization initiators (D1) can be used alone or in combination of two or more.

The content of the photopolymerization initiator (including the oxime ester photopolymerization initiator (D) and the optional other photopolymerization initiator (D1)) is 100 parts by weight, excluding the solvent, of the coloring composition for color filters. 0.5 to 20 parts by mass is preferable, and 3 to 10 parts by mass is more preferable. If a suitable amount of photopolymerization initiator is blended, photocurability and developability are further improved.

<Sensitizer>
The sensitizer contained in the coloring composition of the present invention has an absorbance of 0.01 or more and less than 1.0 at a wavelength of 380 to 420 nm. Sensitizers having such characteristics include, for example, thioxanthone derivatives. Specific examples include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, and 1-chloro-4-propoxythioxanthone. Commercially available products include "KAYACURE DETX-S" (2,4-diethylthioxanthone manufactured by Nippon Kayaku Co., Ltd.).

Sensitizers and other sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, and fluorene derivatives. , naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, Oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetra Quinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives , α-acyloxyester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone and the like.

More specifically, edited by Shin Okawara et al., "Dye Handbook" (1986, Kodansha), edited by Shin Okawara et al., "Chemistry of Functional Dyes" (1981, CMC), Chuzaburo Ikemori et al. Special Functional Materials" (CMC, 1986), but not limited thereto. In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region can also be included.

The content when using a sensitizer is preferably 3 to 200 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the coloring composition, and from the viewpoint of photocurability and developability, 5 More preferably, it is up to 50 parts by mass.

<Binder resin (B)>
The coloring composition of the present invention contains a binder resin (B). As the binder resin (B), a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength range of 400 to 700 nm is used. The binder resin (B) is classified according to its main curing method, and includes thermoplastic resins, thermosetting resins, active energy ray-curable resins having ethylenically unsaturated double bonds, etc. Active energy ray-curable resins may be a thermoplastic resin or a resin having a thermosetting function, and is preferably an alkali-soluble resin from the viewpoint of developability. It may also contain a thermoplastic resin that is not curable with active energy rays, and it is also preferably alkali-soluble. These may be used alone or in combination of two or more.

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

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

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

<Alkali-soluble resin having an ethylenically unsaturated double bond>
The alkali-soluble resin contained in the coloring composition of the present invention preferably has an ethylenically unsaturated double bond. In particular, by using a resin into which an ethylenically unsaturated double bond has been introduced by the method (i), (ii) or (iii) shown below, when forming a coating film by exposure to active energy rays, the resin is 3 Dimensional cross-linking increases cross-linking density and improves chemical resistance.

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

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

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

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. These may be used alone or in combination of two or more. I don't mind. If necessary, such as increasing the number of carboxyl groups, use a tricarboxylic anhydride such as trimellitic anhydride, or use a tetracarboxylic dianhydride such as pyromellitic dianhydride to remove the remaining anhydride. It is also possible to hydrolyze the group. Moreover, 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.

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

[Method (ii)]
As method (ii), an ethylenically unsaturated monomer having a hydroxyl group is used, and another unsaturated monobasic acid monomer having a carboxyl group or another monomer is copolymerized. There is a method of reacting the side chain hydroxyl groups of the resulting copolymer with the isocyanate groups of an ethylenically unsaturated monomer having an isocyanate group.

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

Ethylenically unsaturated monomers having an isocyanate group include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis[methacryloyloxy]ethyl isocyanate. However, without being limited to these, two or more kinds can be used together.

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

Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-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-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimide N-substituted maleimides such as hexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine,
Compounds represented by the following general formula (5), specifically EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, phenolic ethylene oxide (EO)-modified (meth)acrylate , EO- or propylene oxide (PO)-modified (meth)acrylates of paracumylphenol, EO-modified (meth)acrylates of nonylphenol, and PO-modified (meth)acrylates of nonylphenol.

General formula (5)

(In general formula (5), 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 optionally having a benzene ring. an alkyl group of numbers 1 to 20, and n is an integer of 1 to 15.)

A carboxyl group-containing ethylenically unsaturated monomer can also be used. Carboxyl group-containing ethylenically unsaturated monomers include, for example, acrylic acid, methacrylic acid, ε-caprolactone-added acrylic acid, ε-caprolactone-added methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid.

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

Phosphate ester group-containing ethylenically unsaturated monomers can also be used. Examples of the phosphate group-containing ethylenically unsaturated monomer include monomers that can be obtained by reacting the hydroxyl group of the hydroxyl group-containing ethylenically unsaturated monomer with a phosphoric acid esterifying agent such as phosphorus pentoxide and polyphosphoric acid. is mentioned.
[Method (iii)]
As method (iii), an unsaturated ethylenic double bond can be introduced by copolymerizing a side chain type cyclic ether-containing monomer and 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 includes tetrahydrofurfuryl (meth)acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, (meth)acrylic acid tetrahydrofuran-3-yl ester;
As the furan skeleton, 2-methyl-5-(3-furyl)-1-penten-3-one, furfuryl (meth)acrylate, 1-furan-2-butyl-3-en-2-one, 1-furan -2-butyl-3-methoxy-3-en-2-one, 6-(2-furyl)-2-methyl-1-hexene-3-one, 6-furan-2-yl-hex-1-ene -3-one, 2-furan-2-yl-1-methyl-ethyl acrylate, 6-(2-furyl)-6-methyl-1-hepten-3-one and the like;
As the tetrahydropyran skeleton, (tetrahydropyran-2-yl)methyl methacrylate, 2,6-dimethyl-8-(tetrahydropyran-2-yloxy)-oct-1-en-3-one, tetrahydropyran 2-methacrylate -2-yl esters, 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 and the like;
As the lactone skeleton, 2-methyl-tetrahydro-2-oxo-3-furanyl 2-propenoate, 2-methyl-7-oxo-6-oxabicyclo[3.2.1]oct-2-propenoate, 2-methyl-hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]furan-7-yl ester of 2-propenoic acid, 2-methyl-tetrahydro-2-oxo-2-propenoic acid 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-methyl-decahydro-8-oxo-5,9-methano-2H 2-propenoic acid -furo[3,4-g]-1-benzopyran-2-yl ester, 2-methyl-2-[(hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]furan 2-propenoate -6-yl)oxy]ethyl ester, 2-propenoic acid 3-oxo-3-[(tetrahydro-2-oxo-3-furanyl)oxy]propyl ester, 2-propenoic acid 2-methyl-2-oxy-1 -oxaspiro[4.5]dec-8-yl ester and the like.
Among these, tetrahydrofurfuryl (meth)acrylate is preferred from the viewpoint of coloration, pigment dispersibility, and availability. These side chain type cyclic ether-containing monomers may be used alone or in combination of two or more.

<Alkali-soluble resin having no ethylenically unsaturated double bond>
The coloring composition of the present invention may contain an alkali-soluble resin having no ethylenically unsaturated double bonds in order to adjust the degree of curing of the coating film. Synthesized using at least one carboxyl group-containing ethylenically unsaturated monomer and one or more of the other ethylenically unsaturated monomers, and by not imparting an ethylenically unsaturated bond to the side chain, ethylene Alkali-soluble resins having no polyunsaturated double bonds can be obtained.

The alkali-soluble resin in the present invention preferably has a spectral transmittance of 80% or more, more preferably 95% or more, in the entire wavelength range of 400 to 700 nm in the visible light region.

The weight-average molecular weight (Mw) of the alkali-soluble resin in the present invention is 2,000 or more and 40,000 or less, preferably 3,000 or more and 300,00 or less, in order to impart alkali developing solubility, and 4,000 More than 20,000 or less is more preferable. Also, the value of Mw/Mn is preferably 10 or less. If the weight-average molecular weight (Mw) is less than 2,000, the adhesiveness to the substrate is lowered and the exposed pattern is less likely to remain. If it exceeds 40,000, the solubility in alkali development will be lowered, and a residue will be generated to deteriorate the linearity of the pattern.
The acid value of the alkali-soluble resin in the present invention is 50 or more and 200 or less (KOHmg/g) for imparting alkali development solubility, preferably 70 or more and 180 or less, more preferably 90 or more and 170 or less. Range. If the acid value is less than 50, the solubility in alkali development is lowered, and residues are generated, which deteriorates the linearity of the pattern. If it exceeds 200, the adhesion to the substrate will be lowered, and the exposure pattern will be difficult to remain.

<Solvent (E)>
The coloring composition of the present invention is obtained by sufficiently dispersing and permeating a coloring agent in a coloring agent carrier, and coating the composition on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm to form a colored film. It is essential to include a solvent (E) to facilitate forming. The solvent (E) is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

The solvent (E) in the present invention contains 0.1 to 10% by mass of a solvent (EH) satisfying two or more of the following (1) to (3) with respect to the total amount of the solvent.
(1) Boiling point at atmospheric pressure of 175° C. or higher and less than 230° C.: hereinafter sometimes referred to as “boiling point” (2) Viscosity at 25° C. of less than 2.0 mPa S: hereinafter sometimes referred to as “viscosity” (3 ) When the evaporation rate of n-butyl acetate at 25 ° C. is 100, the evaporation rate is 1 or more and less than 20. The evaporation rate is determined by evaporating a certain amount of n-butyl acetate at 25 ° C. Then, the same amount of organic solvent was evaporated under the same conditions, and the time until complete evaporation was measured. Evaporation rate is calculated. Therefore, an organic solvent with an evaporation rate of less than 100 evaporates slower than n-butyl acetate, and an organic solvent with an evaporation rate of more than 100 evaporates faster than n-butyl acetate. (Hereafter, the evaporation rate under the condition (3) may be simply referred to as "evaporation rate")

Examples of the solvent (E) include 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol and 1,3-butylene glycol diacetate. , 1,4-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-methylbutylacetate, 3-methoxybutanol , 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n- Propyl acetate, 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 monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate , ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol Cole Methyl Ether Acetate, Dipropylene Glycol Monoethyl Ether, Dipropylene Glycol Monobutyl Ether, Dipropylene Glycol Monopropyl Ether, Dipropylene Glycol Monomethyl Ether, Diacetone Alcohol, Triacetin, Tripropylene Glycol Monobutyl Ether, Tripropylene Glycol Monomethyl Ether, Propylene Glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propio acetate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester and the like.
These solvents can be used singly or as a mixture of two or more at any ratio as required.

Among them, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol diacetate, and ethylene glycol monomethyl ether acetate are preferred because of their good dispersibility and permeability of the coloring agent and the applicability of the coloring composition. , ethylene glycol monoethyl ether acetate, 1,3-butylene glycol diacetate, cyclohexanol acetate, 1,4-butanediol diacetate, acetates such as butanediol diacetate, benzyl alcohol, diacetone alcohol, 1-methoxy- Alcohols such as 2-propanol and 3-methoxybutanol, ketones such as cyclohexanone, and ethyl 3-ethoxypropionate are preferably used.

<Solvent (EH)>
Examples of the solvent (EH) include the following (abbreviation/boiling point (°C)/viscosity (mPa·s)/evaporation rate). Dipropylene glycol methyl ether acetate (DPMA/213/1.7/1.5), dipropylene glycol methyl-n-propyl ether (DPMNP/203/1.4/unknown), dipropylene glycol methyl ether (DMM/175) /1.0/16), and the solvent (EH) contains one or more of these in an amount of 0.1 to 10% by mass based on the total amount of the solvent (E), the sensitivity is increased, and the development speed is increased. get faster. A more preferable content of the solvent (EH) is 1.0 to 10% by mass based on the total amount of the solvent (E).

In addition, the solvent (E) adjusts the viscosity of the coloring composition to an appropriate level, and can form a colored film having the desired uniform thickness. It is preferable to use

<Epoxy compound>
It is preferable to add an epoxy compound to the coloring composition of the present invention. As the epoxy compound to be used, a known compound having an epoxy group can be used without particular limitation.

Epoxy compounds include 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 epoxy resin. resins, bisphenol-A novolac type epoxy resins, naphthalene skeleton-containing epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, and the like.
Among these, it is preferable that the epoxy compound is an alicyclic epoxy resin from the viewpoint of improvement of water spots or heat resistance and chemical resistance.

Specific examples of the phenol novolak type epoxy resin include Epiclon N-740, Epiclon N-770, and Epiclon N-775 manufactured by DIC Corporation, and D.I. E. N438, Nippon Kayaku Co., Ltd. RE-306, Mitsubishi Chemical Co., Ltd. jER152, jER154 and the like.

Specific examples of cresol novolac epoxy resins include Epiclon N-660, Epiclon N-665, Epiclon N-670, Epiclon N-673, Epiclon N-680, Epiclon N-695, and Epiclon N-665-manufactured by DIC Corporation. EXP, Epiclon N-672-EXP, EOCN-102S, EOCN-103S, EOCN-104S manufactured by Nippon Kayaku Co., Ltd., UVR-6650 manufactured by Union Carbide Co., Ltd., ESCN-195 manufactured by Sumitomo Chemical Co., Ltd., and the like.

Specific examples of the trishydroxyphenylmethane type epoxy resin include EPPN-503, EPPN-502H, EPPN-501H manufactured by Nippon Kayaku Co., Ltd., TACTIX-742 manufactured by Dow Chemical Co., Ltd., and jER E1032H60 manufactured by Mitsubishi Chemical Corporation. mentioned.

Specific examples of the dicyclopentadiene phenol type epoxy resin include Epiclon EXA-7200 manufactured by DIC Corporation, TACTIX-556 manufactured by Dow Chemical Co., and the like.

Specific examples of bisphenol-type epoxy resins include jER828 and jER1001 manufactured by Mitsubishi Chemical Corporation, UVR-6410 manufactured by Union Carbide Co., Ltd., and D.I. E. R-331, bisphenol-A type epoxy resin such as YD-8125 manufactured by Shin Nikka Epoxy Manufacturing Co., Ltd., UVR-6490 manufactured by Union Carbide Co., Ltd., bisphenol-F type such as YDF-8170 manufactured by Shin Nikka Epoxy Manufacturing Co., Ltd. An epoxy resin etc. are mentioned.

Specific examples of biphenol-type epoxy resins include biphenol-type epoxy resins such as NC-3000 and NC-3000H manufactured by Nippon Kayaku Co., Ltd., and bixylenol-type epoxies such as jER YX-4000 and jER YL-6121 manufactured by Mitsubishi Chemical Corporation. Resin etc. are mentioned.

Specific examples of the bisphenol A novolac type epoxy resin include Epiclon N-880 manufactured by DIC Corporation and jER E157S75 manufactured by Mitsubishi Chemical Corporation.

Specific examples of naphthalene skeleton-containing epoxy resins include NC-7000 and NC-7300 manufactured by Nippon Kayaku Co., Ltd., and EXA-4750 manufactured by DIC Corporation.

Specific examples of alicyclic epoxy resins include Celoxide 2021P, 2081, 2000 manufactured by Daicel Corporation, Epolead PB3600, PB4700, GT401, EHPE-3150, Cycromer M100, TTA3150 manufactured by Kusumoto Kasei Co., Ltd., and the like.

Specific examples of heterocyclic epoxy resins include TEPIC-L, TEPIC-H and TEPIC-S manufactured by Nissan Chemical Industries, Ltd.

These epoxy compounds can be used singly or as a mixture of two or more at any ratio as required.

The content of the epoxy compound used in the coloring composition of the present invention is usually 0.5 to 50% by weight, preferably 1 to 40% by weight, based on 100% by weight of the solid content of the coloring composition. When the content of the epoxy compound is within the above range, the heat resistance is high and an excellent coating film can be obtained, which is preferable.

<Oxetane compound>
An oxetane compound is preferably added to the coloring composition of the present invention. As the oxetane compound, any known compound having an oxetane group can be used without particular limitation. Examples of the oxetane compound include those having a monofunctional oxetane group, those having a bifunctional oxetane group, and those having a bifunctional or higher oxetane group.

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

Examples of difunctional oxetane groups include 4,4′-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl) and 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[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene Glycose bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis( 3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) Ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3 -oxetanylmethyl)ether and the like.
Specific examples include OXBP, OXTP manufactured by Ube Industries, Ltd., OXT-121 and OXT-221 manufactured by Toagosei Co., Ltd., and the like.

As the oxetane group having a functionality of two or more,
Pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol penta Kiss (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified di Pentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing oxetane groups (e.g., oxetane-modified phenols described in Japanese Patent No. 3783462 Novolac resins, etc.) and polymers obtained by radical polymerization of (meth)acrylic monomers such as the aforementioned OXE-30. Such polymers can be obtained using known polymerization methods.

The content of the oxetane compound used in the coloring composition of the present invention is usually 0.5 to 50% by mass, preferably 1 to 40% by mass, based on 100% by mass of the solid content of the coloring composition. When the content of the oxetane compound is within the above range, it is preferable because a coating film having good water stain resistance and high chemical resistance can be obtained.

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

Also, polyfunctional aliphatic thiols bonded to aliphatic groups such as methylene and ethylene groups having two or more SH groups are preferred. More preferred are polyfunctional aliphatic thiols having 4 or more SH groups. By increasing the number of functional groups, the polymerization initiation function is improved, and it is possible to cure from the surface of the pattern to the vicinity of the substrate.

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

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

The content of the thiol-based chain transfer agent is preferably 0.1 to 10% by mass, more preferably 1.0 to 8.0% by mass, based on the total solid content of the coloring composition. Within this range, the effect of the chain transfer agent is increased, and the sensitivity, tapered shape, wrinkles, film shrinkage, etc. are improved.

<Ultraviolet absorber>
The coloring composition of the invention may also contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorbing function, and examples thereof include benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, cyanoacrylate-based organic compounds, and salicylate-based organic compounds. .

The content of the ultraviolet absorber is preferably 5 to 70% by weight based on the total 100% by weight of the photopolymerization initiator and the ultraviolet absorber. If the content of the UV absorber is less than the above, the effect of the UV absorber is small and resolution cannot be ensured. There may be a problem such as being stuck.

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

Further, the total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass based on 100% by mass of the solid content of the coloring composition. When the total content of the photopolymerization initiator and the ultraviolet absorber is less than the above range, the adhesion may be weakened and pixel peeling may occur.

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

Examples of benzotriazole-based organic compounds include 2-(5methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, octyl-3[3-tert-butyl -4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H -benzotriazol-2-yl)phenyl]propionate mixture, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tbutyl- 5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t- Octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoate, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4- Compound of hydroxy, C7-9 side chain and linear alkyl ester, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H- benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol.

More specifically, BASF "TINUVIN P", "TINUVIN PS", "TINUVIN 109", "TINUVIN 234", "TINUVIN 326", "TINUVIN 328", "TINUVIN 329", "TINUVIN 360", " TINUVIN 384-2", "TINUVIN 900", "TINUVIN 928", "TINUVIN 99-2", "TINUVIN 1130", "ADEKA STAB LA-29" manufactured by ADEKA, "RUNA-93" manufactured by Otsuka Chemical Co., Ltd. be done.

Triazine organic compounds include 2-[4,6-di(2,4-xylyl)-1,3,5-triazin-2-yl]-5-octyloxyphenol, 2-[4,6-bis (2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, 2-(2,4-dihydroxyphenyl)- Reaction product of 4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl-glycidate ester, 2,4-bis "2-hydroxy-4-butoxyphenyl" -6-(2,4-dibutoxyphenyl)-1,3-5-triazine and the like.

More specifically, "KEMIISORB 102" manufactured by Chemipro Kasei Co., Ltd., "TINUVIN 400" manufactured by BASF, "TINUVIN 405", "TINUVIN 460", "TINUVIN 477-DW", "TINUVIN 479", "TINUVIN 1577", "ADEKA STAB LA-46", "ADEKA STAB LA-F70" manufactured by ADEKA, "CYASORB UV-1164" manufactured by Sun Chemical Co., Ltd., and the like.

Benzophenone-based organic compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3 water temperature, 2-hydroxy-4-n- octoxybenzophenone, 2,2-di-hydroxy-4-methoxybenzophenone and the like.

More specifically, "KEMIISORB 10", "KEMIISORB 11", "KEMIISORB 11S", "KEMIISORB 12", "KEMIISORB 111" manufactured by Chemipro Kasei Co., Ltd., "SEESORB 101", "SEESORB 107" manufactured by Shipro Kasei Co., Ltd., ADEKA ADEKA STAB 1413 manufactured by ADEKA CORPORATION.

<Polymerization inhibitor>
The coloring composition of the present invention may contain a polymerization inhibitor in order to prevent exposure due to diffracted light from a mask during exposure. By adding a polymerization inhibitor, it is possible to obtain the effect of preventing curing from progressing outside the desired pattern due to chain polymerization due to photosensitivity.

Polymerization inhibitors include catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, and 2-propylcatechol. , 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert- Alkylcatechol compounds such as butylcatechol and 3,5-di-tert-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, alkylresorcinol compounds such as 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, 2, Alkylhydroquinone compounds such as 5-di-tert-butylhydroquinone, phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine and tribenzylphosphine, phosphines such as trioctylphosphine oxide and triphenylphosphine oxide Examples include oxide compounds, phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite, pyrogallol and phloroglucine. The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass with respect to 100 parts by mass of the coloring composition excluding the solvent. Within this range, the effect of the polymerization inhibitor is increased, and the straightness of the taper, the wrinkles of the coating film, the pattern resolution, etc. are improved.

<Antioxidant>
The coloring composition of the present invention can contain an antioxidant. The antioxidant prevents the photopolymerization initiator and thermosetting compound contained in the coloring composition from oxidizing and yellowing due to the thermal process during thermal curing and ITO annealing, and increases the transmittance of the coating film. be able to. In particular, when the colorant concentration of the coloring composition is high, the amount of the coating film cross-linking component is reduced, so measures such as using a highly sensitive cross-linking component and increasing the amount of the photopolymerization initiator will increase the yellowing of the thermal process. can be seen. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation during the heating process and obtain a high transmittance of the coating film.

The "antioxidant" in the present invention may be a compound having an ultraviolet absorption function, a radical scavenging function, or a peroxide decomposition function. , phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylic acid ester-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used. Moreover, the antioxidant used in the present invention preferably does not contain a halogen atom.

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

Hindered phenol antioxidants include 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-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2' thiodiethylbis-(3,5-di-t-butyl-4-hydroxyphenyl )-propionate, 1,1,3-tris-(2′-methyl-4′-hydroxy-5′-t-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. In addition, oligomer type and polymer type compounds having a hindered phenol structure can also be used.

Specific examples include Adekastab AO-20, AO-30, AO-40, AO50, AO60, AO80, AO320 manufactured by ADEKA Corporation, KEMINOX101, 179, 76, 9425 manufactured by Chemipro Corporation, IRGANOX1010, 1035 manufactured by BASF Corporation. , 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565, Cyanox CY-1790, CY-2777 manufactured by Sun Chemical Co., Ltd., and the like.

Hindered amine antioxidants include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, 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-piperidyl)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- Polycondensate with (2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N -(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine and the like. In addition, oligomer type and polymer type compounds having a hindered amine structure can also be used.
Specific examples include ADEKA Co., Ltd. ADEKA 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, KAMISTAB29, 62, 77, 29, 94 manufactured by Chemipro Kasei Co., Ltd., Tinuvin249 manufactured by BASF Corporation, TINUVIN111FDL, 123, 144, 292, 5100, Cyasorb UV-3346 manufactured by Sun Chemical Co., Ltd., UV -3529, UV-3853 and the like.

Phosphorus antioxidants include tris(isodecyl)phosphite, tris(tridecyl)phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi(tridecyl)phosphite, diphenylisooctylphosphite, diphenylisodecyl phosphite, diphenyltridecylphosphite, triphenylphosphite, tris(nonylphenyl)phosphite, 4,4' isopropylidenediphenol alkylphosphite, trisnonylphenylphosphite, trisdinonylphenylphosphite, tris(2 ,4-di-t-butylphenyl)phosphite, tris(biphenyl)phosphite, distearylpentaerythritol diphosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonyl phenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3- Tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodium bis(4-t-butylphenyl) Phosphite, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, ethyl bis(2, 4-di-tert-butyl-6-methylphenyl) and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.
Specific examples include Adekastab PEP-36, PEP-8, HP-10 manufactured by ADEKA Corporation, Adekastab 2112, 1178, 1500, C, 3013, TPP, IRGAFOS168 manufactured by BASF Corporation, HostanoxP-EPQ manufactured by Clariant Chemicals Co., Ltd., and the like. are mentioned.

Sulfur antioxidants include 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]- o-cresol, 2,4-bis[(laurylthio)methyl]-o-cresol, 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. In addition, oligomer type and polymer type compounds having a thioether structure can also be used.
Specific examples include ADEKA STAB AO-412S and AO-503 manufactured by ADEKA Corporation, and KEMINOXPLS manufactured by Chemipro Kasei Co., Ltd.

As the benzotriazole-based antioxidant, an oligomer-type or polymer-type compound having a benzotriazole structure can be used.
Specific examples include Adekastab LA-29, LA-31RG, LA-32, LA-36, and -412S manufactured by ADEKA Corporation, KEMISORB71, 73, 74, 79, and 279 manufactured by Chemipro Kasei Co., Ltd., and TINUVIN PS manufactured by BASF Corporation. , 99-2, 384-2, 900, 928, 1130 and the like.

Benzophenone antioxidants include 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. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.
Specific examples include Adeka Stab 1413 manufactured by ADEKA Corporation, KEMIISORB 10, 11, 11S, 12 and 111 manufactured by Chemipro Kasei Co., Ltd., UV-12 and UV-329 manufactured by Sun Chemical Co., Ltd., and the like.

Triazine-based antioxidants include 2,4-bis(allyl)-6-(2-hydroxyphenyl)1,3,5-triazine and the like. In addition, oligomer type and polymer type compounds having a triazine structure can also be used.
Specific examples include Adekastab LA-46 and F70 manufactured by ADEKA Corporation, KEMISORB102 manufactured by Chemipro Kasei Co., Ltd., TINUVIN400, 405, 460, 477, 479 manufactured by BASF Corporation, and Cyasorb UV-1164 manufactured by Sun Chemical Co., Ltd. .

Salicylic acid ester-based antioxidants include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate, and the like. In addition, oligomer type and polymer type compounds having a salicylic acid ester structure can also be used.

These antioxidants can be used singly or as a mixture of two or more at any ratio as required.

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

<Adhesion improver>
The coloring composition of the present invention may contain an adhesion improver such as a silane coupling agent in order to improve adhesion to the substrate. By improving the adhesion with the adhesion improving agent, the reproducibility of fine lines is improved and the resolution is improved.

Examples of adhesion improvers include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3- (Meth)acrylsilanes such as methacryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxysilane 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3- Epoxysilanes such as glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane , N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene ) aminosilanes such as propylamine, N-phenyl-3-aminopropyltrimethoxysilane, hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane; , mercaptos such as 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureides such as 3-ureidopropyltriethoxysilane, sulfides such as bis(triethoxysilylpropyl)tetrasulfide, Examples include silane coupling agents such as isocyanates such as 3-isocyanatopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, per 100 parts by weight of the colorant in the coloring composition. Within this range, the effect is enhanced and the balance between adhesion, resolution, and sensitivity is good, which is more preferable.

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

Examples of silicone-based surfactants include linear polymers composed of siloxane bonds and modified siloxane polymers in which organic groups are introduced into side chains or terminals.
Specific examples include BYK-300, BYK-306, BYK-310, BYK-313, BYK-315N, BYK-320, BYK-322, BYK-323, BYK-330, BYK-331 manufactured by BYK-Chemie Japan, BYK-333, BYK-342, BYK-345/346, BYK-347, BYK-348, BYK-349, BYK-370, BYK-377, BYK-378, BYK-3455, BYK-UV3510, BYK-3570, Dow Corning Toray Co., Ltd., FZ-7001, FZ-7002, FZ-2110, FZ-2122, FZ-2123], FZ-2191, FZ-5609, Shin-Etsu Chemical Co., Ltd. X-22-4952, X -22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF -6004 and the like.

Fluorinated surfactants include (surfactant or leveling) agents having a fluorocarbon chain.
Specific examples include AGC Seimi Chemical Co., Ltd. Surflon S-242, S-243, S-420, S-611, S-651, S-386, DIC Corporation Megafac F-253, F-477, F-551, F-552, F-555, F-558, F-560, F-570, F-575, F-576, R-40-LM, R-41, RS-72-K, DS- 21, FC-4430 and FC-4432 manufactured by Sumitomo 3M Limited, EF-PP31N09, EF-PP33G1 and EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., Ftergent 602A manufactured by Neos Co., Ltd., and the like.

Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myrister ether, polyoxyethylene octyldodecyl Ether, Polyoxyalkylene Alkyl Ether, Polyoxyphenylene Distyrenated Phenyl Ether, Polyoxyethylene Tribenzylphenyl Ether, Polyoxyethylene Polyoxypropylene Glycol, Polyoxyethylene Alkenyl Ether, Polyoxyethylene Nonylphenyl Ether, Polyoxyethylene Alkyl Ether phosphate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan monolaurate, sorbitan esquioleate, poly Oxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene orbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, tetra Polyoxyethylene sorbitol oleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol mooleate, polyoxyethylene hydrogenated castor oil, polyoxy Examples include ethylene alkylamine, alkylalkanolamide, alkylbetaine such as alkylimidazoline and alkyldimethylaminoacetic acid betaine.

Specific examples include 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, and Emulgen 320P manufactured by Kao Corporation. , 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, Rheodor SP-L10, Rheodor SP-P10, Rheodor SP-S10V, Rheodor SP-S20, Rheodor SP-S30V, Rheodor SP-O10V, Rheodor SP-O30V, Rheodor Super SP-L1, Rheodol AS-10V, Rheodol AO-10V, Rheodol AO-15V, Rheodol TW-L120, Rheodol TW-L106, Rheodol TW-P120, Rheodol TW-S120V, Rheodol TW-L106V, Rheodol TW-S320V, Rheodol TW-O120V, Rheodor TW-O106V, Rheodor TW-IS399C, Rheodor Super TW-L120, Rheodor 430V, Rheodor 440V, Rheodor 460V, Rheodor MS-50, Rheodor MS-60, Rheodor MO-60, Rheodor MS-165V, Emanon 1112, Emanon 3199V, Emanon 3299V, Emanon 3299RV, Emanon 4110, Emanon CH-25, Emanon CH-40, Emanon CH-60 (K), Amit 102, Amit 105, Amit 105A, Amit 302, Amit 320, Amino PK -02S, Aminone L-02, Homogenol L-95, Adeka Pluronic L-23, 31, 44, 61, 62, 6 manufactured by ADEKA Co., Ltd. 4, 71, 72, 101, 121, Adecapluronic TR-701, 702, 704, 913R and the like.

Examples of cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride and cetyltrimethylammonium chloride, and their ethylene oxide adducts.
Specific examples include Acetamine 24 and 26 manufactured by Kao Corporation, Kotamine 24P and 86P Conc, KP341 manufactured by Shin-Etsu Chemical Co., Ltd., and (meth)acrylic acid-based (co)polymer Polyflow No. 1 manufactured by Kyoeisha Chemical Co., Ltd. 75, No. 90, No. 95 and the like.

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

Specific examples include Futergent 100 and 150 manufactured by Neos Co., Ltd., Adeka Hope YES-25 manufactured by ADEKA Corporation, Adekacol TS-230E, PS-440E, EC-8600, and the like.

When the coloring composition of the present invention contains a surfactant, the amount of surfactant added is preferably 0.001 to 2.0% by mass with respect to 100% by mass of the total solid content of the composition of the present invention. , more preferably 0.005 to 1.0% by mass. Within this range, the coating properties of the coloring composition, the pattern adhesion, and the transmittance are well balanced.
The coloring composition of the present invention may contain only one type of surfactant, or may contain two or more types of surfactants. When two or more types are included, the total amount is preferably within the above range.

<Method for producing colored composition>
The coloring composition included in the present invention comprises a coloring agent, a dispersing agent, a coloring agent carrier such as a binder resin, and/or a solvent, preferably together with a dispersing aid (pigment derivative or surfactant), kneader, It can be produced by finely dispersing using various dispersing means such as a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor (colorant dispersion). At this time, two or more kinds of coloring agents and the like may be dispersed in the coloring agent carrier at the same time, or may be mixed separately dispersed in the coloring agent carrier. If the colorant such as dye has high solubility, specifically, if it has high solubility in the solvent to be used, and if it is dissolved by stirring and no foreign matter is confirmed, it is manufactured by finely dispersing as described above. No need.

When used as a coloring composition for color filters (resist material), it can be prepared as a solvent-developing or alkali-developing coloring composition. The solvent-developable or alkali-developable colored composition comprises the above-described colorant dispersion, a polymerizable monomer and/or a photopolymerization initiator, and optionally a solvent, other dispersing aids, 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.

<Dispersing aid>
When the colorant is dispersed in the colorant carrier, a dispersing aid such as a pigment derivative, a dispersant, or a surfactant may be contained as appropriate. Since the dispersing aid has a great effect of preventing the reaggregation of the colorant after dispersion, the coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersing aid has excellent brightness, contrast, and storage stability. becomes better. The dye derivative and dispersant are as described above.

<Surfactant>
Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenylether disulfonate. , monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, anionic surfactants such as polyoxyethylene alkyl ether phosphate; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; cationic surfactants such as quaternary ammonium salts and their ethylene oxide adducts; alkylbetaines such as alkyldimethylaminoacetic acid betaine; amphoteric surfactants such as alkylimidazoline; Although they can be mixed and used, they are not necessarily limited to these.

When a surfactant is added, it is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass, per 100 parts by mass of the colorant. If the amount of the surfactant is less than 0.1 parts by mass, it is difficult to obtain the effect of addition, and if the content is more than 55 parts by mass, the excess dispersant may affect dispersion. .

<Removal of coarse particles>
The colored dispersion or colored composition of the present invention is separated by means such as centrifugal separation, filtration with a sintered filter or a membrane filter, etc., to obtain coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more. It is preferable to remove coarse particles and mixed dust. Thus, the coloring composition preferably does not substantially contain particles of 0.5 μm or larger. More preferably, it is 0.3 μm or less.

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

<Manufacturing method of color filter>
A color filter can be manufactured by a printing method or a photolithography method.
Formation of filter segments by a printing method can be patterned simply by repeating printing and drying of a coloring composition prepared as a printing ink, and therefore, as a method for producing color filters, it is low cost and excellent in mass productivity. Furthermore, the development of printing technology has made it possible to print fine patterns with high dimensional accuracy and smoothness. For printing, it is preferable to have a composition that does not allow the ink to dry or solidify on the printing plate or blanket. In addition, it is also important to control the fluidity of the ink on the printing press, and it is also possible to adjust the viscosity of the ink using a dispersant or an extender.

When the filter segment is formed by photolithography, the colored composition prepared as the solvent-developable or alkali-developable colored resist material is applied onto the transparent substrate by spray coating, spin coating, slit coating, roll coating, or the like. Depending on the method, the coating is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed (irradiated with radiation) through a mask having a predetermined pattern provided in contact or non-contact with the film. After that, the film is immersed in a solvent or alkaline developer or sprayed with a developer to remove the uncured portion to form a desired pattern, and then the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to promote polymerization of the colored resist material, heating may be applied as necessary. According to the photolithography method, it is possible to manufacture a color filter with higher precision than the printing method.

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

The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an ink jet method, etc. in addition to the above methods, and the colored composition of the present invention can be used in any of these methods. The electrodeposition method is a method of manufacturing a color filter by using a transparent conductive film formed on a substrate to electrodeposit each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which filter segments are formed in advance on the surface of a removable transfer base sheet, and the filter segments are transferred to a desired substrate.

A black matrix can be formed in advance before forming each color filter segment on the transparent substrate or the reflective substrate. As the black matrix, 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 can be used, but is not limited to these. Alternatively, thin film transistors (TFTs) may be formed in advance on the transparent substrate or reflective substrate, and then each color filter segment may be formed. An overcoat film, a transparent conductive film, and the like are formed on the color filter of the present invention, if necessary.

The color filter of the present invention is laminated with a counter substrate using a sealing agent, liquid crystal is injected from an injection port provided in the sealing portion, the injection port is sealed, and if necessary, a polarizing film or a retardation film is attached to the substrate. A color liquid crystal display device is manufactured by laminating the film to the outside of the film. This color liquid crystal display device has Twisted Nematic (TN), Super Twisted Nematic (STN), In-Plane Switching (IPS), Vertically Aligned (VA), Optically Convened Bend (OCB). ) can be used in a liquid crystal display mode in which coloration is performed using a color filter.

In addition to color liquid crystal display devices, the color filter of the present invention can also be used to manufacture color solid-state imaging devices, organic EL display devices, quantum dot display devices, electronic paper, and the like.

The present invention will be described below based on Production Examples and Examples, but the present invention is not limited thereto. Unless otherwise specified, "parts" and "%" in Production Examples and Examples mean "mass parts" and "mass%". "PGMAC" means propylene glycol monomethyl ether acetate

(Identification of phthalocyanine)
Identification of phthalocyanine is 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, and , the ratio of carbon, hydrogen and nitrogen obtained using an elemental analyzer (2400CHN elemental analyzer, manufactured by Perkin-Elmer) and the theoretical values.

(Calculation of the average number of substituted halogen atoms)
The average value of the substitution number of halogen atoms in the pigment was obtained by burning the pigment in an oxygen combustion flask method, and applying the liquid obtained by absorbing the burned product in water using an ion chromatograph (ICS-2000 ion chromatography, manufactured by DIONEX). ) to quantify the amount of halogen and convert it into the average value of the number of substituted halogen atoms.

(Weight average molecular weight (Mw))
The weight average molecular weight (Mw) of the 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 "TSK-GEL SUPER HZM-N" was used as both packing materials, and the oven temperature was 40. °C, a THF solution was used as an eluent, and the flow rate was 0.35 ml/min. The sample was dissolved in a solvent consisting of 1 wt % of the above eluent and injected in 20 microliters. All molecular weights are polystyrene equivalent values.

(Acid value of resin)
The acid value is a value obtained by converting the measured acid value (mgKOH/g) into solid content based on the potentiometric titration method of JIS K 0070.

<Synthesis of Dispersion Resin Having Aromatic Carboxyl Group>
(Synthesis of dispersion resin R-1: A polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product of a compound having two hydroxyl groups and an acid anhydride group of an aromatic tetracarboxylic acid anhydride. )
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, 62 parts of PGMAc, 1,8-diazabicyclo 0.2 parts of -[5.4.0]-7-undecene was charged, and the contents were 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 is half-esterified by measuring the acid value, the temperature in the system is cooled to 70 ° C., 65 parts of methyl methacrylate, 5.0 parts of ethyl acrylate, t-butyl 53.5 parts of a PGMAC solution containing 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. . After confirming that the polymerization had progressed by 95% by measuring the solid content, the reaction was terminated. Propylene glycol monomethyl ether acetate was added to the previously synthesized dispersant so that the non-volatile content was 50% by weight to obtain a dispersion resin solution R-1 having an acid value of 70.5 and a weight average molecular weight of 10,000.

(Synthesis of dispersion resins R-2 to R-6 and R-13)
Dispersion resins R-2 to R-6 and R-13 were obtained by synthesizing in the same manner as R-1 except that the raw materials and charging amounts shown in Table 1 were used.

(Synthesis of dispersion resin R-7: reaction product of polymer having two hydroxyl groups at the ends and aromatic tetracarboxylic acid anhydride)
75 parts of methyl methacrylate, 20 parts of t-butyl acrylate, 5.0 parts of methacrylic acid, and 2.0 parts of 3-mercapto-1,2-propanediol were placed in a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer. , 0.1 part of 2,2′-azobisisobutyronitrile and 102 parts of PGMAC were added and reacted for 10 hours. Solid content measurement confirmed that 95% had reacted. Subsequently, 3.2 parts of pyromellitic anhydride, 6.0 parts of PGMAC, and 0.20 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added and reacted at 120° C. for 7 hours. let me It was confirmed by acid value measurement that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. Propylene glycol monomethyl ether acetate was added to the previously synthesized dispersant so that the non-volatile content was 50% by mass to obtain a dispersant resin R-7 having an acid value of 46.7 and a weight average molecular weight of 19,500.

(Synthesis of dispersion resins R-8 to R-12)
Dispersion resins R-8 to R-12 were obtained by synthesizing in the same manner as dispersion resin R-7 except that the raw materials and charged amounts shown in Table 2 were used.

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

(Synthesis of dispersion resin R-14: reaction product of polymer having one hydroxyl group at the end and aromatic tricarboxylic acid anhydride)
19.8 parts of xylene, 2.1 parts of octanol, 77.9 parts of ε-caprolactone, and 0.16 part of tetrabutyl titanate were placed in a four-necked flask equipped with a stirrer, a reflux condenser, a gas inlet tube, a thermometer, and a dropping funnel. The mixture was heated to 150 to 160° C. and reacted for 5 hours in a nitrogen gas atmosphere. 31.86 parts of the synthesized polyester monool and 0.98 parts of trimellitic anhydride were charged and reacted at 150 to 160° C. under a nitrogen atmosphere. When the acid value of the resin became 22.7 or less, 2.55 parts of YED122 (manufactured by Japan Epoxy Resin Co., Ltd., trade name: alkylphenol monoglycidyl ether, epoxy equivalent: 250) was added and the reaction was carried out at the same temperature. When the resin acid value became 1.1 or less, 1.96 parts of trimellitic anhydride was charged and the reaction was carried out at the same temperature. When the resin acid value became 38.7 or less, YED 122 and 5.1 parts and reacted at the same temperature, and when the resin acid value became 1.8 or less, 3.92 parts of trimellitic anhydride was charged and reacted at the same temperature, and the resin acid value became 60.1 or less. When it became cold, it was cooled, and 53.6 parts of xylene was added to terminate the reaction. Propylene glycol monomethyl ether acetate was added to the previously synthesized dispersant so that the non-volatile content was 50% by mass to obtain a dispersant resin R-14 having an acid value of 58.9 and a weight average molecular weight of 11,000.

(Synthesis of comparative dispersion resin S-1)
75 parts of methyl methacrylate, 20 parts of t-butyl acrylate, 5.0 parts of methacrylic acid, and 2.0 parts of 3-mercapto-1,2-propanediol were placed in a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer. , 0.1 part of 2,2′-azobisisobutyronitrile and 102 parts of PGMAC were added and reacted for 10 hours. Solid content measurement confirmed that 95% had reacted. Propylene glycol monomethyl ether acetate was added to the previously synthesized dispersant so that the non-volatile content was 50% by mass to obtain a comparative dispersant resin S-1 having an acid value of 32 and a weight average molecular weight of 10,000.

(Synthesis of Comparative Dispersion Resin S-2)
75 parts of methyl methacrylate, 5.0 parts of ethyl acrylate, 15 parts of t-butyl acrylate, 5.0 parts of methacrylic acid, 3-mercapto-1,2 were placed in a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer. -2.0 parts of propanediol, 0.1 parts of 2,2'-azobisisobutyronitrile and 102 parts of PGMAC were added and reacted for 10 hours. Solid content measurement confirmed that 95% had reacted. Propylene glycol monomethyl ether acetate was added to the previously synthesized dispersant so that the non-volatile content was 50% by mass to obtain a comparative dispersant resin S-2 having an acid value of 32 and a weight average molecular weight of 9,000.

Prior to the examples, a method for making the pigment finer and a method for producing the resin-type dispersant (J) liquid and the binder resin (B) liquid will be described.

<Method for Producing Raw Material Phthalocyanine Compound Represented by Formula (4)>
(Production of raw material phthalocyanine compound (Q-1))
In a reactor, 225 parts of phthalodinitrile and 78 parts of anhydrous aluminum chloride were mixed and stirred with 1250 parts of n-amyl alcohol. To this, 266 parts of DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene) was added, and the mixture was heated and refluxed at 136° C. for 5 hours. The reaction solution cooled to 30° C. with stirring was poured into a mixed solvent consisting of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine (Q-1). Elemental analysis of the obtained chloroaluminum phthalocyanine revealed that the calculated values (C) were 66.85%, (H) was 2.80%, and (N) was 19.49%, while the actual value (C) was 66.85%. 7%, (H) 3.0%, (N) 19.2% and identified as the desired compound.

(Production of raw material phthalocyanine compound (Q-2))
100 parts of the phthalocyanine compound (Q-1) was slowly added to 1200 parts of concentrated sulfuric acid 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. A 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))
100 parts of the above phthalocyanine compound (Q-1) was added to 1500 parts of concentrated sulfuric acid in an ice bath. Then, 108 parts of trichloroisocyanuric acid was gradually added, and the mixture was stirred at 25°C for 6 hours. Subsequently, this sulfuric acid solution is poured into 9,000 parts of cold water at 3° C., and the precipitate formed is filtered, washed with water, washed with a 1% sodium hydroxide aqueous solution, washed with water in that order, dried, and dried to obtain 165 parts of phthalocyanine. A 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 desired 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 -4) was produced. When the number of bromine substitutions was calculated, it was 6.0 on average, and a peak corresponding to the same molecular weight was also confirmed from the mass spectrum, thus identifying the target compound.

(Production of raw material phthalocyanine compound (Q-5))
In the production of the phthalocyanine compound (Q-3), the same procedure as in the production of the phthalocyanine compound (Q-3) was carried out, except that 108 parts of trichloroisocyanuric acid was changed to 249 parts of 1,3-dibromo-5,5-dimethylhydantoin. 187 parts of phthalocyanine pigment (Q-5) were prepared. When the number of bromine substitutions was calculated, it was 10.3 on average, and a peak corresponding to the same molecular weight was also confirmed from the mass spectrum, and it was identified as the desired 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 above phthalocyanine compound (Q-1) was added at 140°C. The temperature was raised to 160° C. and 190 parts of chlorine was blown thereinto. The above reaction solution is poured into 5000 parts of water, filtered, washed with warm water, washed with a 1% hydrochloric acid aqueous solution, washed with warm water, washed with a 1% sodium hydroxide aqueous solution, and washed with warm water in this order, and then dried for crude chlorination. 175 parts of aluminum phthalocyanine were obtained. The resulting 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 is poured into 7200 parts of water with stirring, heated to 70° C., filtered, washed with warm water, washed with a 1% sodium hydroxide aqueous solution, washed with warm water, dried and dried to give 165 parts of a phthalocyanine compound (Q-6 ) was manufactured. When the number of chlorine substitutions was calculated, it was 15.0 on average, and a peak corresponding to the same molecular weight was also confirmed from the mass spectrum, and it was identified as the target compound.

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

<Method for producing finely divided pigment> (Production of finely divided pigment (PY-1))
quinophthalone-based yellow pigment C.I. I. 200 parts of Pigment Yellow 138 (“Paliotol Yellow L 0960HD” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80° C. for 6 hours. Next, this kneaded product is put into 8 liters of hot water, stirred for 2 hours while heating to 80°C to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and dried at 85°C for a day and night. , to obtain a finely divided yellow pigment (PY-1).

(Production of micronized pigment (PY-2))
100 parts of the quinophthalone compound (b) described in JP-A-2012-226110, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 6 hours, Salt milled. The resulting kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70°C to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80°C for a day and night. , 98 parts of finely divided yellow pigment (PY-2) were obtained. The average primary particle size was 31.3 nm.

(Production of micronized pigment (PY-3))
C. I. Pigment Yellow 150 (PY150) ("E4GN" manufactured by Lanxess) 100 parts, sodium chloride 700 parts and diethylene glycol 180 parts were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80°C for 6 hours. This mixture was poured into 2000 parts of hot water and stirred for 1 hour while heating to 80°C to form a slurry, which was repeatedly filtered and washed with water to remove salt and solvent. A yellow pigment (PY-3) was obtained. The average primary particle size was 34.5 nm.

(Refined pigment (PR-1): PR254)
red pigment C.I. I. Pigment Red 254 (PR254) ("Irgafore Red B-CF" manufactured by BASF) 152 parts, 8 parts of the dye derivative 1 represented by the chemical formula (5), 1600 parts of sodium chloride, and 190 parts of diethylene glycol in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 10 hours. Next, this mixture is poured into 3 liters of hot water, heated to about 80° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, which is filtered and washed repeatedly to remove sodium chloride and the solvent. ℃ for one day to obtain a red treatment pigment (PR-1). The average primary particle size of the resulting pigment was 35 nm.

chemical formula (5)

<Production of dye derivative>
(Synthesis of dye derivative 1)
Dye derivative (1) was obtained according to the synthesis method described in JP-A-2004-307854.

dye derivative (1)

<Method for producing pigment composition>
[Production Example 1]
(Production of Pigment Composition A-1)
2000 parts of N,N-dimethylformamide, 100 parts of starting phthalocyanine compound (Q-2) and 52 parts of diphenyl phosphate were added to a reactor. After reacting at 85° C. for 3 hours, 31 parts of dispersion resin (R-1) solution was added so that the resin content in the pigment composition was 10%, and the mixture was stirred for 10 minutes. This solution was then poured into 8000 parts of water. The reaction product is filtered, washed with 16,000 parts of water, and dried at 60° C. under reduced pressure for a whole day and night. 148 parts of pigment composition A-1 with a proportion of 10% were obtained with a yield of 94%.

[Production Examples 2 to 32, Comparative Production Examples 1 to 13]
(Production of Pigment Compositions A-2 to A-32 and B-1 to B-13)
Pigment compositions A-2 to A-32 and B-1 to pigment compositions A-2 to A-32 and B-1 to were prepared in the same manner as for pigment composition A-1, except that the phthalocyanine compound, acidic compound, and dispersing resin were changed to the conditions shown in Table 3. B-13 was obtained. Table 3 shows the yield, the yield, the halogen atom X, and the number of halogen substituents n. B-1 to B-11 do not contain resin.

A structure list of the obtained phthalocyanine compound is shown.

<Production example of binder resin (B) liquid>
(Preparation of binder resin (B-1) solution)
A separable 4-necked flask equipped with a thermometer, a condenser tube, a nitrogen gas inlet tube, a dropping tube, and a stirring device was charged with 370 parts of cyclohexanone, heated to 80°C, and after replacing the inside of the flask with nitrogen, parachlorate was added from the dropping tube. Milphenol ethylene oxide-modified acrylate (Toagosei Aronix M110) 18 parts, benzyl methacrylate 10 parts, glycidyl methacrylate 18.2 parts, methyl methacrylate 25 parts, and 2,2'-azobisisobutyronitrile 2.0 The mixture of parts was added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 100°C for 3 hours, then a solution obtained 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 changed to air exchange, and 0.5 parts of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (100% of the glycidyl groups), and the mixture was heated at 120°C. The reaction was continued for 6 hours, and when the solid content acid value reached 0.5, the reaction was terminated to obtain a solution of an acrylic resin. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 parts of triethylamine were added and reacted at 120° C. for 3.5 hours to obtain an acrylic resin solution.
After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content. Acetate was added to prepare a binder resin (B-1) solution. The weight average molecular weight (Mw) was 19,000.

(Preparation of binder resin (B-2) solution)
196 parts of cyclohexanone was charged into a reaction vessel equipped with a separable 4-necked flask, a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirring device, heated to 80°C, and after replacing the inside of the reaction vessel with nitrogen, the mixture was added dropwise. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide-modified acrylate (manufactured by Toagosei Co., Ltd. "Aronix M110") 20.7 and 1.1 parts of 2,2'-azobisisobutyronitrile were added dropwise over 2 hours. After completion of dropping, the reaction was continued for 3 more hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content. was added to prepare a binder resin (B-2) solution. The weight average molecular weight (Mw) was 26,000.

(Preparation of binder resin (B-3) solution)
207 parts of cyclohexanone was charged into a reaction vessel equipped with a separable 4-necked flask, a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirring device, heated to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then dropped. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2'-azobis A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was continued for 3 hours to obtain a copolymer resin solution. Next, the nitrogen gas was stopped and the total amount of the copolymer solution obtained was stirred while injecting dry air for 1 hour, and then cooled to room temperature. A mixture of 6.5 parts of MOI, 0.08 parts of dibutyltin laurate and 26 parts of cyclohexanone was added dropwise at 70° C. over 3 hours. After the dropwise addition was completed, the reaction was continued for an additional hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180° C. for 20 minutes to measure the non-volatile content. to prepare a binder resin (B-3) solution. The weight average molecular weight (Mw) was 18,000.

<Preparation of Colorant Dispersion (Paste) for Color Filter>
[Production Example 51]
(Adjustment of Pigment Dispersion GMB-1))
After uniformly stirring and mixing the mixture of the following composition, using zirconia beads with a diameter of 0.5 mm, after dispersing for 5 hours with an Eiger mill (manufactured by Eiger Japan Co., Ltd. "Mini Model M-250 MKII"), 5.0 μm. A colorant dispersion (paste) (GMB-1) for a color filter was prepared by filtering through a filter.
Pigment composition (A-1): 11.4 parts Dye derivative 1: 0.6 parts Resin (R-1): 7.2 parts Binder resin (B-1): 22.0 parts PGMAC: 58.8 parts

[Production Examples 52 to 59]
(Adjustment of pigment dispersions GMB-2 to 5, YMB-1 to 3, and RMB-1)
Colorant dispersions (pastes) for color filters (GMB-2 to 5, YMB-1 to 3, RMB-1) were prepared according to Production Example 1 using the materials and their mass parts shown in Table 4.

<Coloring composition for color filter (resist adjustment)>
[Example 1]
A mixture having the following composition was uniformly stirred and mixed, and then filtered through a 1 μm filter to obtain a coloring composition for color filters (T-1).
Colorant dispersion for color filters (paste) (GMB-1) 50.0 parts Binder resin (B-1) liquid 24.95 parts Polymerizable monomer (C) 4.0 parts (Toagosei Co., Ltd.) manufactured by "Aronix M-402" dipentaerythritol penta and hexaacrylate)
- Oxime ester photopolymerization initiator (D) 0.40 parts (compound of chemical formula (3b-2))
-Other photopolymerization initiators (D1-1: BASF Corporation 0.20 parts each of the following mixture) 0.40 parts "IRGACURE 907" (2-methyl-1-[4-(methylthio) phenyl] -2- morpholinopropan-1-one)
"IRGACURE 379" (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one)
- Sensitizer (Z-1: a mixture of 0.1 parts each of the following) 0.20 parts "CHEMARK DEABP"(4,4'-bis (diethylamino) benzophenone, manufactured by Chemmark Chemical)
"KAYACURE DETX-S" (2,4-diethylthioxanthone manufactured by Nippon Kayaku Co., Ltd.)
・Propylene glycol monomethyl ether acetate (PGMEA) (solvent (E))
14.05 parts Dipropylene glycol methyl ether acetate (DPMA) (solvent (EH) EH-1) 5.00 parts Leveling agent solution (L-1: the following mixed solution) 1.00 parts BYK-Chemie Japan "BYK-330" 1 part, DIC Corporation "Megafac F-551" 1 part, Kao Corporation "EMULGEN 103" 1 part dissolved in propylene glycol monomethyl ether acetate (PGMEA) 97 parts mixed solution.

[Examples 2 to 22, Comparative Examples 1 to 3]
<Coloring composition for color filter (resist) (T-2 to 25)>
Each material was mixed in the same manner as in Example 1, and the corresponding colored compositions (resist) for color filters (T-2 to 25) were obtained in the same formulations as shown in Tables 5 and 6.
In Tables 5 and 6, EH (%) is mass % of the solvent (EH) with respect to the solvent contained in the entire composition.

Polymerizable monomer (C1)
(C-1): Dipentaerythritol penta and hexaacrylate ("Aronix M-402" manufactured by Toagosei Co., Ltd.)
(C-2): Trimethylolpropane triacrylate ("Aronix M-309" manufactured by Toagosei Co., Ltd.)
(C-3): Trimethylolpropane PO-modified triacrylate (“Aronix M-310” manufactured by Toagosei Co., Ltd.)
(C-4): Trimethylolpropane EO-modified triacrylate (“Aronix M-350” manufactured by Toagosei Co., Ltd.)
(C-5): general formula (16) m = 1, a = 3, b = 3
Caprolactone-modified dipentaerythritol hexaacrylate ("KAYARAD DPCA-30" manufactured by Nippon Kayaku Co., Ltd.)
general formula (16)

(C-6): A succinic anhydride adduct of a mixture of pentaerythritol triacrylate and dipentaerythritol triacrylate ("Aronix M-520" manufactured by Toagosei Co., Ltd. acid value: 30 mgKOH/g)
(C-7): Polyfunctional urethane acrylate according to the following: 432 g of pentaerythritol triacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and 84 g of hexamethylene diisocyanate were charged into a 1-liter, 5-necked reaction vessel, and the mixture was heated at 60°C. After reacting for 8 hours, a product containing polyfunctional urethane acrylate (C-7) having a (meth)acryloyl group was obtained. The proportion of the polyfunctional urethane acrylate (C-7) in the product was 70% by mass, and the remainder was occupied by other photopolymerizable monomers. It was confirmed by IR analysis that no isocyanate group was present in the reaction product.

・(EH-2): dipropylene glycol methyl-n-propyl ether ・(EH-3): dipropylene glycol methyl ether ・Antioxidant A: 0.1 parts each of the following mixture "IRGANOX 1010" (pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]
"IRGAFOS 168" (tris[2,4-di-(tert)-butylphenyl]phosphine)
- Thiol chain transfer agent A: pentaerythritol tetrakisthiopropionate

<Evaluation of coloring composition (resist) for color filter>
The obtained colored compositions for color filters (resists) (T-1 to 25) were tested for sensitivity and development speed by the following methods. Table 7 below shows the results of the evaluation test. If the result of sensitivity and development speed is ◯/◯, it is practically preferable, and if it is a combination of ◯/Δ, there is no practical problem. Also, the combination of Δ/Δ, Δ/x, and x/x is at a practically problematic level.

<Sensitivity evaluation>
The coloring composition was spin-coated on a glass substrate using a spin coater so as to give a dry film thickness of 2.4 μm, and prebaked at 90° C. for 120 seconds. After cooling the substrate to room temperature, it was exposed to ultraviolet light through a photomask using an extra-high pressure mercury lamp. Thereafter, the substrate was developed by spraying with an aqueous solution of sodium carbonate at 23° C., washed with deionized water, air-dried, and post-baked at 230° C. for 30 minutes in a clean oven to form stripes on the substrate. A colored pixel was formed.
The sensitivity of the colored composition was evaluated based on the minimum irradiation exposure amount at which the formed pattern of colored pixels was finished according to the image size of the photomask. The rank of evaluation is as follows.
○: Less than 50 mJ/cm ² △: 50 or more and less than 100 mJ/cm ² ×: 100 mJ/cm ² or more

<Development speed evaluation>
The coloring composition was spin-coated on a glass substrate using a spin coater so that the dry film thickness was 1.0 μm, and dried at 70° C. for 20 minutes.
2 ml of a 2% by mass potassium hydroxide aqueous solution was added dropwise to the coating film, and the time until the coating thickness was dissolved was measured to evaluate the development speed of the colored composition. The rank of evaluation is as follows.
○: Less than 25 seconds △: 25 seconds or more, less than 35 seconds ×: 35 seconds or more

Claims (5)

Colorant (A) (excluding C.I. Pigment Blue 15:6) , dispersion resin having aromatic carboxyl group, binder resin (B), polymerizable monomer (C), and oxime A coloring composition for a color filter containing an ester photopolymerization initiator (D) and a solvent (E),
The coloring agent (A) contains an aluminum phthalocyanine pigment (A1), and
The solvent (E) is selected from the group consisting of dipropylene glycol methyl ether acetate, dipropylene glycol methyl-n-propyl ether, and dipropylene glycol methyl ether. A coloring composition for color filters containing 1 to 10% by mass. 2. The coloring composition for color filters according to claim 1 , wherein the coloring agent (A) further contains a yellow pigment component (A2) containing a quinophthalone pigment. The coloring composition for color filters according to claim 1 or 2, wherein the polymerizable monomer (C) contains a triacrylate polymerizable monomer. Further, the coloring composition for color filters according to any one of claims 1 to 3, containing a polyfunctional thiol. A color filter comprising a substrate and a filter segment formed from the color filter coloring composition according to any one of claims 1 to 4.