JP7052206B2 - Colored resin composition, color filter and image display device - Google Patents

Description

The present invention resides in a colored resin composition, a color filter and an image display device.

Flat panel displays such as liquid crystal displays and organic EL (Electroluminescence) display devices are widely used, and color filters are used in these displays. In keeping with the trend of energy saving, color filters are required to have higher color purity, higher brightness and higher contrast.
So far, a colored resin composition using a pigment has been mainly used as a material for forming a color filter. However, in order to obtain high brightness and high contrast, for example, in Non-Patent Document 1, the particle size of the pigment particles is set. A method of finely dispersing the color to less than 1/2 of the color-developing wavelength is disclosed.

On the other hand, dyes are also being developed as coloring materials used in colored resin compositions for color filters. For example, Patent Document 1 discloses a triarylmethane salt having an anion having a specific structure. Further, Patent Document 2 discloses a triarylmethane salt having a cation having a specific structure.

International Publication No. 2015/08217 Pamphlet Japanese Unexamined Patent Publication No. 2013-57052

Kiyoshi Hashizume, "Journal of the Japan Society of Color Material", December 1967, p608

However, in the method described in Non-Patent Document 1, since the blue pigment in particular has a shorter coloration wavelength than other red and green pigments, further fine dispersion is required in this case, which increases the cost and stabilizes after dispersion. Gender matters.
On the other hand, the colored resin composition using a dye is advantageous in terms of brightness as compared with the one using a pigment, but tends to be inferior in durability under exposure or heating, which is a process during film formation. Further, it has been pointed out that during heat film formation, the dye easily diffuses into the resin, so that a dye transfer phenomenon in which the color is transferred to an adjacent coloring pattern is likely to occur, and the brightness and color purity may decrease.
According to the studies by the present inventors, it has been found that when the triarylmethane-based compound described in Patent Document 1 is used, the prevention of dye transfer to the adjacent coloring pattern is insufficient.

Further, according to the study by the present inventors, it has been found that the heat resistance required in the manufacturing process of the color display is not sufficient when the triarylmethane-based compound described in Patent Document 2 is used.
The present invention has been made in view of the above-mentioned problems of the prior art, and a colored resin composition having high brightness, satisfying the heat resistance required in the manufacturing process of a color display, and having no transfer to an adjacent coloring pattern. The challenge is to provide.

Another object of the present invention is to provide a color filter having no dye transfer, high luminance, and satisfying heat resistance, and an image display device.

As a result of diligent studies by the present inventors, it has been found that the above-mentioned problems can be solved by using a novel triarylmethane-based compound having a specific structure, and the present invention has been completed.
That is, the gist of the present invention is as follows.

[1] A colored resin composition containing (A) a coloring material, (B) a solvent, and (C) a binder resin.
A colored resin composition, wherein the coloring material (A) contains a triarylmethane-based compound represented by the following general formula (I).

(In the above formula (I),
[A ^m- ] represents an m-valent anion. n represents an integer of 1 to 4.
R ¹ to R ⁵ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
R ⁶ represents a l-valent hydrocarbon group which may have a substituent. However, in R ⁶ , the l carbon atoms bonded to the adjacent N atoms are independently tertiary or quaternary carbon atoms. The methylene group in the hydrocarbon group in R ⁶ may be substituted with an oxygen atom and / or a carbonyl group.
l represents an integer of 2 or more and satisfies the relationship of l = m × n. )

[2] The colored resin composition according to [1], wherein the hydrocarbon group in R ⁶ has 6 or more carbon atoms.
[3] The colored resin composition according to [1] or [2], wherein the [A ^m- ] is an m-valent halogenoalkylsulfonylimide anion which may have a substituent.
[4] The colored resin composition according to any one of [1] to [3], wherein the [A ^m- ] is a monovalent halogenoalkylsulfonylimide anion which may have a substituent.

[5] The colored resin composition according to any one of [1] to [4], further containing (D) a polymerizable monomer.
[6] The colored resin composition according to any one of [1] to [5], further containing (E) a photopolymerization initiation component and / or (E') a thermal polymerization initiation component.
[7] The colored resin composition according to any one of [1] to [6], wherein the coloring material (A) further contains a pigment.

[8] A color filter having pixels formed by using the colored resin composition according to any one of [1] to [7].
[9] An image display device having the color filter according to [8].

[10] A triarylmethane-based compound represented by the following general formula (I).

(In the above formula (I),
[A ^m- ] represents an m-valent anion. n represents an integer of 1 to 4.
R ¹ to R ⁵ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
R ⁶ represents a l-valent hydrocarbon group which may have a substituent. However, in R ⁶ , the l carbon atoms bonded to the adjacent N atoms are independently tertiary or quaternary carbon atoms. The methylene group in the hydrocarbon group in R ⁶ may be substituted with an oxygen atom and / or a carbonyl group.
l represents an integer of 2 or more and satisfies the relationship of l = m × n. )

[11] The triarylmethane compound according to [10], wherein the hydrocarbon group in R ⁶ has 6 or more carbon atoms.
[12] The triarylmethane compound according to [10] or [11], wherein the [A ^m- ] is an m-valent halogenoalkylsulfonylimide anion which may have a substituent.
[13] The triarylmethane compound according to [12], wherein the [A ^m- ] is a monovalent halogenoalkylsulfonylimide anion which may have a substituent.

According to the present invention, it is possible to provide a colored resin composition having high brightness, satisfying the heat resistance required in the manufacturing process of a color display, and having no transfer to an adjacent coloring pattern.

FIG. 1 is a conceptual diagram of a transmission image photographing region in dye transfer measurement. FIG. 2 is a conceptual diagram of a light / dark profile acquired by dye transfer measurement. FIG. 3 is a light / dark profile of Example 1. FIG. 4 is a light / dark profile of Example 2. FIG. 5 is a light / dark profile of Comparative Example 3. FIG. 6 is a schematic cross-sectional view showing an example of an organic EL device having the color filter of the present invention.

Hereinafter, embodiments of the present invention will be described in detail, but the following description is an example of embodiments of the present invention, and the present invention is not limited to these contents.
In the present invention, "(meth) acrylic", "(meth) acrylate" and the like mean "at least one of acrylic and methacrylic", "at least one of acrylate and methacrylate" and the like, for example, "( "Meta) Acrylic acid" shall mean "at least one of acrylic acid and methacrylic acid".

Further, the "total solid content" means all the components of the colored resin composition of the present invention other than the solvent component described later.
Further, the "aromatic ring" shall mean both an "aromatic hydrocarbon ring" and an "aromatic heterocycle".
In addition, terms such as "CI pigment green" mean the names of color materials contained in the Color Index (CI).

The colored resin composition of the present invention contains (A) a coloring material, (B) a solvent and (C) a binder resin, and the (A) coloring material is a triaryl represented by the general formula (I) described later. It is characterized by containing a methane-based compound. Further, it is preferable to contain at least one of (D) a polymerizable monomer, and (E) a photopolymerization initiating component and (E') a thermal polymerization initiating component, and may contain other components as necessary. ..

[(A) Color material]
(Compound represented by the general formula (I))
The coloring material (A) contained in the colored resin composition of the present invention contains a triarylmethane-based compound represented by the following general formula (I).

In the above formula (I),
R ¹ to R ⁵ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
R ⁶ represents a l-valent hydrocarbon group which may have a substituent. However, in R ⁶ , the l carbon atoms bonded to the adjacent N atoms are independently tertiary or quaternary carbon atoms. The methylene group in the hydrocarbon group in R ⁶ may be substituted with an oxygen atom and / or a carbonyl group.
l represents an integer of 2 or more and satisfies the relationship of l = m × n.

As described above, it is considered that the use of the multimer of the triarylmethane compound increases the molecular weight, reduces the molecular motility in the colored resin film under heating, and improves the dye transfer. ..
In particular, in R ⁶ of the amino group (-NR ³ R ⁶ ) bonded to the naphthalene ring, the carbon atom bonded to the N atom is a tertiary or quaternary carbon atom, that is, the N is branched. Unpaired electrons on the atom are shielded, this activation is suppressed, it becomes easier to take a stable transition state at the time of heating or light irradiation, the brightness is high, the heat resistance is good, and the light resistance is also good. Is thought to be.

(R ¹ to R ⁵ )
R ¹ to R ⁵ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
Examples of the alkyl group in R ¹ to R ⁵ include a linear, branched or cyclic alkyl group. The number of carbon atoms is preferably 1 or more, more preferably 2 or more, more preferably 10 or less, still more preferably 6 or less, still more preferably 4 or less. When it is at least the lower limit value, the heat resistance tends to be improved, and when it is at least the upper limit value, the dye transfer tends to be improved.

Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylethyl group and 3-. Examples thereof include a methylbutyl group. Among these, a linear alkyl group is preferable from the viewpoint of heat resistance.
Specific examples of the alkyl group having a substituent include a phenethyl group, a 2-ethoxyethyl group, a 4,4,4-trifluorobutyl group and the like.

Examples of the aromatic ring group in R ¹ to R ⁵ include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms is preferably 6 or more, preferably 18 or less, more preferably 14 or less, still more preferably 10 or less. When it is set to the lower limit value or more, the brightness tends to be improved, and when it is set to the upper limit value or less, it tends to be easy to synthesize.

The aromatic hydrocarbon ring group may be a monocyclic ring or a fused ring, and may be, for example, a benzene ring, a naphthalene ring, anthracene ring, a phenanthrene ring, a perylene ring, or a tetracene having one free atomic value. Groups such as a ring, a pyrene ring, a benzpyrene ring, a chrysen ring, a triphenylene ring, an acenaphthene ring, a fluorantene ring, and a fluorene ring can be mentioned.
The aromatic heterocyclic group may be a monocyclic ring or a fused ring, and may be, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, or a pyrazole ring having one free atomic value. , Pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrrolobymidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrol ring, thienothiophene ring, flopyrol ring, furan ring, thienoflan ring, benzisoxazole ring. , Benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxalin ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline Groups such as rings, benzolinone rings, and azulene rings can be mentioned.

Among these, from the viewpoint of increasing the brightness, it is preferable that R ¹ and R ² are alkyl groups which may have a substituent.

Further, from the viewpoint of ensuring heat resistance, R ³ is preferably an alkyl group which may have a hydrogen atom or a substituent, and more preferably a hydrogen atom.

Further, from the viewpoint of light resistance, R ⁴ and R ⁵ are preferably aromatic ring groups which may have a substituent, and are aromatic hydrocarbon ring groups which may have a substituent. Is more preferable.

Examples of the substituent that the alkyl group in R ¹ to R ⁵ may have include those of the following substituent group W1. In addition, examples of the substituent that the aromatic ring group may have include those of the following substituent group W2.

(Substituent group W1)
Fluorine atom, chlorine atom, alkenyl group with 2 to 8 carbon atoms, alkoxyl group with 1 to 8 carbon atoms, phenyl group, mesityl group, trill group, naphthyl group, cyano group, acetyloxy group, alkyl with 2 to 9 carbon atoms A carbonyloxy group, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, an alkylcarbonyl group having 2 to 9 carbon atoms, a phenethyl group, a hydroxyethyl group, an acetylamide group, and an alkyl group having 1 to 4 carbon atoms are bonded. A dialkylaminoethyl group, a trifluoromethyl group, a trialkylsilyl group having 1 to 8 carbon atoms, a nitro group, and an alkylthio group having 1 to 8 carbon atoms.
Among them, an alkoxyl group having 1 to 8 carbon atoms, a cyano group, an acetyloxy group, an alkylcarboxyl group having 2 to 8 carbon atoms, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, and a fluorine atom are preferable. ..

(Substituent group W2)
Fluorine atom, chlorine atom, alkyl group with 1 to 8 carbon atoms, alkenyl group with 2 to 8 carbon atoms, alkoxyl group with 1 to 8 carbon atoms, phenyl group, mesityl group, trill group, naphthyl group, cyano group, acetyloxy Group, alkylcarbonyloxy group with 2-9 carbon atoms, sulfamoyl group, alkylsulfamoyl group with 2-9 carbon atoms, alkylcarbonyl group with 2-9 carbon atoms, hydroxyethyl group, acetylamide group, 1-carbon number A dialkylaminoethyl group, a trifluoromethyl group, a trialkylsilyl group having 1 to 8 carbon atoms, a nitro group, and an alkylthio group having 1 to 8 carbon atoms to which 4 alkyl groups are bonded.
Of these, an alkyl group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a cyano group, an acetyloxy group, an alkylcarboxyl group having 2 to 8 carbon atoms, a sulfamoyl group, and an alkylsul having 2 to 9 carbon atoms are preferable. It is a famoyl group and a fluorine atom.

(R ⁶ )
R ⁶ represents a l-valent hydrocarbon group which may have a substituent. However, in R ⁶ , the l carbon atoms bonded to the adjacent N atoms are independently tertiary or quaternary carbon atoms. The methylene group in the hydrocarbon group in R ⁶ may be substituted with an oxygen atom and / or a carbonyl group.
From the viewpoint of heat resistance, it is preferable that the l carbon atoms bonded to the adjacent N atoms in R ⁶ are independently tertiary carbon atoms.
The number of carbon atoms of the hydrocarbon group in R ⁶ is not particularly limited, but is preferably 2 or more, more preferably 4 or more, still more preferably 6 or more, particularly preferably 10 or more, and preferably 30 or less, preferably 20 or less. More preferably, 15 or less is further preferable. When the value is at least the lower limit value, the heat resistance tends to be improved, and when the value is not more than the upper limit value, the raw material tends to be easily obtained.

When l is 2, from the viewpoint of heat resistance, R ⁶ is preferably a divalent group represented by the following formula (I-1).

In the above formula (I-1), R ^1A represents an alkyl group which may independently have a substituent, and R ^2A represents an alkyl group which may independently have a hydrogen atom or a substituent. Represents. R ^3A represents a direct bond, an alkylene group which may have a substituent, or a divalent aromatic ring group which may have a substituent. The methylene group in the alkyl group in R ^1A and R ^2A may be substituted with an oxygen atom and / or a carbonyl group, and the methylene group in the alkylene group in R ^3A is substituted with an oxygen atom and / or a carbonyl group. May be good.
Further, adjacent R ^1A may be connected to each other to form a ring, R ^1A and R ^2A may be connected to form a ring, and R ^1A and R ^3A may be connected to form a ring. It may be formed. * Represents a bond with an N atom.

(R ^1A )
In formula (I-1), R ^1A represents an alkyl group which may independently have a substituent.
Examples of the alkyl group in R ^1A include linear, branched or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 2 or more, more preferably 30 or less, still more preferably 20 or less, still more preferably 10 or less. When the value is at least the lower limit value, the heat resistance tends to be improved, and when the value is not more than the upper limit value, the raw material tends to be easily obtained.

Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylethyl group and 3-. Examples thereof include a methylbutyl group. Among these, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group. Is preferable.

Examples of the substituent that the alkyl group in R ^1A may have include those of the above-mentioned substituent group W1.

(R ^2A )
In formula (I-1), R ^2A represents an alkyl group which may independently have a hydrogen atom or a substituent.
As the alkyl group in R ^2A , those listed as the alkyl group in R ^1A can be preferably adopted.
Among these, from the viewpoint of heat resistance, it is preferable that R ^2A is a hydrogen atom.

(R ^3A )
In formula (I-1), R ^3A represents a direct bond, an alkylene group which may have a substituent, or a divalent aromatic ring group which may have a substituent.
Examples of the alkylene group in R ^3A include a linear alkylene group, a branched chain alkylene group, a cyclic alkylene group, and a group in which these are bonded. The number of carbon atoms is not particularly limited, but is preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, particularly preferably 10 or less, and usually 1 or more. By setting the value to the upper limit or less, synthesis is easy.
Specific examples include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an n-nonylene group and an n-decylene group. , N-Undecylene group, n-Dodecylene group, n-Tridecylene group, n-Tetradecylene group, n-Pentadecylene group, n-Hexadecylene group, n-Heptadecilene group, n-Octadecylene group, n-Nonadecylene group, n-Icosylene group And so on. Among these, from the viewpoint of heat resistance, n-octylene group, n-nonylene group, and n-decylene group are preferable.
Examples of the substituent that the alkylene group may have include those of the above-mentioned substituent group W1.

Examples of the divalent aromatic ring group in R ^3A include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The number of carbon atoms is preferably 6 or more, preferably 18 or less, more preferably 14 or less, still more preferably 10 or less. When it is at least the above lower limit value, the heat resistance tends to be improved, and when it is at least the above upper limit value, the raw material tends to be easily obtained.
The aromatic hydrocarbon ring group may be a monocyclic ring or a fused ring, and may be, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, or a tetracene having two free atomic valences. Groups such as a ring, a pyrene ring, a benzpyrene ring, a chrysen ring, a triphenylene ring, an acenaphthene ring, a fluorantene ring, and a fluorene ring can be mentioned.
The aromatic heterocyclic group may be a monocyclic ring or a fused ring, and may be, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, or a pyrazole ring having two free atomic valences. , Pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrrolobymidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrol ring, thienothiophene ring, flopyrol ring, furan ring, thienoflan ring, benzisoxazole ring. , Benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxalin ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline Groups such as rings, benzolinone rings, and azulene rings can be mentioned.

Examples of the substituent that the aromatic ring group may have include those of the above-mentioned substituent group W2.

The methylene group in the alkyl group in R ^1A and R ^2A may be substituted with an oxygen atom and / or a carbonyl group, and the methylene group in the alkylene group in R ^3A is substituted with an oxygen atom and / or a carbonyl group. May be good. Examples of the group in which the methylene group is substituted with an oxygen atom and / or a carbonyl group include —O—, —CO—, —CO—O— and the like.

As described above, adjacent R ^1A may be connected to each other to form a ring, R ^1A and R ^2A may be connected to form a ring, and R ^1A and R ^3A may be connected to each other to form a ring. It may form a ring. For example, adjacent R ^1A 's are connected to each other to form a ring, and adjacent R ^2A 's are hydrogen atoms, or one R ^1A and R ^3A are connected to form a ring, and the other R ^1A and the other. Examples thereof include a mode in which R ^3A is connected to form a ring and adjacent R ^2A is a hydrogen atom.

Among the divalent groups represented by the formula (I-1), the divalent group represented by the following formula (I-1a) is preferable from the viewpoint of heat resistance.

In the above formula (I-1a), R ^4A represents a divalent aliphatic ring group which may independently have a substituent. R ^5A represents a direct bond, an alkylene group which may have a substituent, or a divalent aromatic ring group which may have a substituent.
The methylene group in the aliphatic ring group in R ^4A may be substituted with an oxygen atom and / or a carbonyl group, and the methylene group in the alkylene group in R ^5A may be substituted with an oxygen atom and / or a carbonyl group. good. * Represents a bond with an N atom.

(R ^4A )
In formula (I-1a), R ^4A represents a divalent aliphatic ring group which may independently have a substituent.
The number of carbon atoms of the divalent aliphatic ring group in R ^4A is not particularly limited, but is usually 3 or more, preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, and preferably 30 or less. It is preferably 25 or less, more preferably 20 or less, still more preferably 15 or less, and particularly preferably 10 or less. When the value is not less than the lower limit, the heat resistance tends to be improved, and when the value is not more than the upper limit, the raw material can be easily obtained and synthesized.

Specific examples of the divalent aliphatic ring group include 2-n-alkyl-1,4-cyclohexanediyl group such as 1,4-cyclohexanediyl group and 2-methyl-1,4-cyclohexanediyl group, 2, 2,6-Di-n-alkyl-1,4-cyclohexanediyl group such as 6-dimethyl-1,4-cyclohexanediyl group, 1,3-cyclobutanediyl group, 1,3-cyclopentanediyl group, 1, Examples thereof include a 5-cyclooctanediyl group. Among these, 1,4-cyclohexanediyl group and 2-n-alkyl-1,4-cyclohexanediyl group are preferable from the viewpoint of easy availability of raw materials.

Examples of the substituent that the divalent aliphatic ring group in R ^4A may have include those of the above-mentioned substituent group W1.

(R ^5A )
In formula (I-1), R ^5A represents a direct bond, an alkylene group which may have a substituent, or a divalent aromatic ring group which may have a substituent.
Examples of the alkylene group in R ^5A include a linear alkylene group, a branched chain alkylene group, a cyclic alkylene group, and a group in which these are bonded. The number of carbon atoms is not particularly limited, but is preferably 20 or less, more preferably 15 or less, still more preferably 10 or less, and usually 1 or more. When the value is not more than the upper limit, the raw material can be easily obtained.
Specific examples include a methylene group, an ethylene group, a propylene group and the like. Of these, a methylene group and an ethylene group are preferable from the viewpoint of obtaining raw materials.
Examples of the substituent that the alkylene group may have include those of the above-mentioned substituent group W1.

Examples of the divalent aromatic ring group in R ^5A include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The number of carbon atoms is preferably 6 or more, preferably 18 or less, more preferably 14 or less, still more preferably 10 or less. When it is at least the above lower limit value, the heat resistance tends to be improved, and when it is at least the above upper limit value, the raw material tends to be easily obtained.
The aromatic hydrocarbon ring group may be a monocyclic ring or a fused ring, and may be, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, or a tetracene having two free atomic valences. Groups such as a ring, a pyrene ring, a benzpyrene ring, a chrysen ring, a triphenylene ring, an acenaphthene ring, a fluorantene ring, and a fluorene ring can be mentioned.
The aromatic heterocyclic group may be a monocyclic ring or a fused ring, and may be, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, or a pyrazole ring having two free atomic valences. , Pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrrolobymidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrol ring, thienothiophene ring, flopyrol ring, furan ring, thienoflan ring, benzisoxazole ring. , Benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxalin ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline Groups such as rings, benzolinone rings, and azulene rings can be mentioned.

Examples of the substituent that the aromatic ring group may have include those of the above-mentioned substituent group W2.

Further, among the divalent groups represented by the formula (I-1), the divalent group represented by the following formula (I-1b) is preferable from the viewpoint of easy availability of raw materials.

In the above formula (I-1b), R ^6A represents a divalent aliphatic ring group which may have a substituent. The methylene group in the aliphatic ring group in R ^6A may be substituted with an oxygen atom and / or a carbonyl group. * Represents a bond with an N atom.

(R ^6A )
In formula (I-1b), R ^6A represents a divalent aliphatic ring group which may have a substituent.
The number of carbon atoms of the divalent aliphatic ring group in R ^6A is not particularly limited, but is usually 3 or more, preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, and preferably 30 or less. It is preferably 25 or less, more preferably 20 or less, still more preferably 15 or less, and particularly preferably 10 or less. When the value is not less than the lower limit, the heat resistance tends to be improved, and when the value is not more than the upper limit, the raw material tends to be easily obtained.

Specific examples of the divalent aliphatic ring group include 1,3-cyclobutanediyl group, 1,3-cyclopentanediyl group, 1,4-cyclohexanediyl group, 1,3-cyclohexanediyl group, and 2,5-. Dimethyl-1,4-cyclohexanediyl group, 2,4-dimethyl-1,4-cyclohexanediyl group, 1,4-cycloheptanediyl group, 1,5-cyclooctanediyl group, 2,6-dimethyl-1, Examples thereof include a 5-cyclooctanediyl group. Among these, 1,4-cyclohexanediyl group and 2,5-dimethyl-1,4-cyclohexanediyl group are preferable from the viewpoint of easy availability of raw materials.

Examples of the substituent that the divalent aliphatic ring group in R ^6A may have include those of the above-mentioned substituent group W1.

Further, among the divalent groups represented by the formula (I-1), the divalent group represented by the following formula (I-1c) is preferable from the viewpoint of easy availability of raw materials.

In the above formula (I-1c), R ^7A represents an alkyl group which may independently have a substituent. R ^8A represents a direct bond, an alkylene group which may have a substituent, or a divalent aromatic ring group which may have a substituent. The methylene group in the alkyl group in R ^7A may be substituted with an oxygen atom and / or a carbonyl group, and the methylene group in the alkylene group in R ^8A may be substituted with an oxygen atom and / or a carbonyl group. * Represents a bond with an N atom.

(R ^7A )
In formula (I-1c), R ^7A represents an alkyl group which may independently have a substituent.
As the alkyl group which may have a substituent in R ^7A , those listed as the alkyl group which may have a substituent in R ^1A in the formula (I-1) can be adopted.

(R ^8A )
In formula (I-1c), R ^8A represents a direct bond, an alkylene group which may have a substituent, or a divalent aromatic ring group which may have a substituent.
As the alkylene group which may have a substituent in R ^8A , the alkylene group which may have a substituent in R ^3A in the formula (I-1) can be adopted. Similarly, as the divalent aromatic ring group which may have a substituent in R ^8A , the divalent aromatic which may have a substituent in R ^3A in the formula (I-1). Those listed as ring groups can be adopted.

Specific examples of the divalent group represented by the formula (I-1) include the following.

On the other hand, when l is 3, it is preferable that R ⁶ is a trivalent group represented by the following formula (I-2) from the viewpoint of easy availability of raw materials and synthesis.

In the above formula (I-2), R ^1A and R ^2A are synonymous with those in the above formula (I-1). R ^9A represents a trivalent aliphatic hydrocarbon group or a trivalent aromatic ring group which may have a substituent. The methylene group in the trivalent aliphatic hydrocarbon group may be substituted with an oxygen atom and / or a carbonyl group.
Adjacent R ^1A may be connected to each other to form a ring, R ^1A and R ^2A may be connected to form a ring, and R ^1A and R ^9A may be connected to form a ring. May be. * Represents a bond with an N atom.

(R ^9A )
In formula (I-2), R ^9A represents a trivalent aliphatic hydrocarbon group which may have a substituent or a trivalent aromatic ring group.
Examples of the trivalent aliphatic hydrocarbon group in R ^9A include linear, branched or cyclic groups. The number of carbon atoms of the aliphatic hydrocarbon group is not particularly limited, but usually 1 or more, 2 or more is preferable, 4 or more is more preferable, 30 or less is preferable, 20 or less is more preferable, and 10 or less is further preferable. When the value is at least the lower limit value, the heat resistance tends to be improved, and when the value is not more than the upper limit value, the raw material tends to be easily obtained.

Specific examples of the trivalent aliphatic hydrocarbon group include a methine group; a 2-methyl-n-propyl group; a 3-ethyl-5-pentyl group; a 1,3,5-cyclohexylene group; 1,3,5. Examples thereof include a 1,3,5-trialkylcyclohexylene group such as a trimethyl-cyclohexylene group and a 1,3,5-triethyl-cyclohexylene group.

Examples of the substituent that the trivalent aliphatic hydrocarbon group in R ^9A may have include those of the above-mentioned substituent group W1.

Examples of the trivalent aromatic ring group in R ^9A include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms is preferably 3 or more, more preferably 6 or more, more preferably 18 or less, still more preferably 14 or less, still more preferably 10 or less. When it is set to the lower limit value or more, the brightness tends to be improved, and when it is set to the upper limit value or less, it tends to be easy to synthesize.

The aromatic hydrocarbon ring group may be a monocyclic ring or a fused ring, and may be, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, or a tetracene having three free atomic valences. Groups such as a ring, a pyrene ring, a benzpyrene ring, a chrysen ring, a triphenylene ring, an acenaphthene ring, a fluorantene ring, and a fluorene ring can be mentioned.
The aromatic heterocyclic group may be a monocyclic ring or a fused ring, and may be, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, or a pyrazole ring having three free atomic valences. , Pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrrolobymidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrol ring, thienothiophene ring, flopyrol ring, furan ring, thienoflan ring, benzisoxazole ring. , Benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxalin ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline Groups such as rings, benzolinone rings, and azulene rings can be mentioned.

Specific examples of the trivalent aromatic ring group include 1,3,5-phenylene group; 1,3,5-trimethylphenylene group, 1,3,5-triethylphenylene group and the like 1,3,5-tri. Examples thereof include 2,4,6-trialkyltriarylylene groups such as an alkylphenylene group; a 2,4,6-triadylene group; a 2,4,6-trimethyltriazilen group and a 2,4,6-triethyltriazilen group. ..

Examples of the substituent that the trivalent aromatic ring group in R ^9A may have include those of the above-mentioned substituent group W2.

As described above, adjacent R ^1A may be connected to each other to form a ring, R ^1A and R ^2A may be connected to form a ring, and R ^1A and R ^9A may be connected to each other to form a ring. It may form a ring. For example, an embodiment in which each R ^1A is connected to R ^9A to form three rings and each R ^2A is a hydrogen atom can be mentioned.

Among the trivalent groups represented by the formula (I-2), the trivalent group represented by the following formula (I-2a) is preferable from the viewpoint of ease of synthesis.

In the above formula (I-2a), R ^4A has the same meaning as that in the above formula (I-1a). R ^10A represents a trivalent aliphatic hydrocarbon group or a trivalent aromatic ring group which may have a substituent. The methylene group in the trivalent aliphatic hydrocarbon group may be substituted with an oxygen atom and / or a carbonyl group. * Represents a bond with an N atom.

(R ^10A )
In formula (I-2a), R ^10A represents a trivalent aliphatic hydrocarbon group which may have a substituent or a trivalent aromatic ring group.
Examples of the trivalent aliphatic hydrocarbon group in R ^10A include linear, branched or cyclic groups. The number of carbon atoms of the aliphatic hydrocarbon group is not particularly limited, but usually 1 or more, 2 or more is preferable, 4 or more is more preferable, 30 or less is preferable, 20 or less is more preferable, and 10 or less is further preferable. When the value is at least the lower limit value, the heat resistance tends to be improved, and when the value is not more than the upper limit value, the raw material tends to be easily obtained.

Specific examples of the trivalent aliphatic hydrocarbon group include a methine group; a 2-methyl-n-propyl group; a 3-ethyl-5-pentyl group; a 1,3,5-cyclohexylene group; 1,3,5. Examples thereof include a 1,3,5-trialkylcyclohexylene group such as a trimethyl-cyclohexylene group and a 1,3,5-triethyl-cyclohexylene group.

Examples of the substituent that the trivalent aliphatic hydrocarbon group in R ^10A may have include those of the above-mentioned substituent group W1.

Examples of the trivalent aromatic ring group in R ^10A include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms is preferably 3 or more, more preferably 6 or more, more preferably 18 or less, still more preferably 14 or less, still more preferably 10 or less. When it is set to the lower limit value or more, the brightness tends to be improved, and when it is set to the upper limit value or less, it tends to be easy to synthesize.

The aromatic hydrocarbon ring group may be a monocyclic ring or a fused ring, and may be, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, or a tetracene having three free atomic valences. Groups such as a ring, a pyrene ring, a benzpyrene ring, a chrysen ring, a triphenylene ring, an acenaphthene ring, a fluorantene ring, and a fluorene ring can be mentioned.
The aromatic heterocyclic group may be a monocyclic ring or a fused ring, and may be, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, or a pyrazole ring having three free atomic valences. , Pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrrolobymidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrol ring, thienothiophene ring, flopyrol ring, furan ring, thienoflan ring, benzisoxazole ring. , Benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxalin ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline Groups such as rings, benzolinone rings, and azulene rings can be mentioned.

Specific examples of the trivalent aromatic ring group include 1,3,5-phenylene group; 1,3,5-trimethylphenylene group, 1,3,5-triethylphenylene group and the like 1,3,5-tri. Examples thereof include 2,4,6-trialkyltriarylylene groups such as an alkylphenylene group; a 2,4,6-triadylene group; a 2,4,6-trimethyltriazilen group and a 2,4,6-triethyltriazilen group. ..

Examples of the substituent that the trivalent aromatic ring group in R ^10A may have include those of the above-mentioned substituent group W2.

Specific examples of the trivalent group represented by the above formula (I-2) include the following.

(L)
In the general formula (I), l represents an integer of 2 or more and satisfies the relationship of l = m × n.
l is usually 2 or more, preferably 4 or less, more preferably 3 or less, still more preferably 2 or less. By setting the value to the upper limit or less, the synthesis tends to be easy.

(About [A ^m- ])
In formula (I), [A ^m- ] represents an m-valent anion.

From the viewpoint of interaction with cations, m is usually 1 or more, preferably 4 or less, more preferably 3 or less, still more preferably 2 or less, and particularly preferably 1. By setting the value to the upper limit or less, the heat resistance tends to be improved.

The m-valent anion is not particularly limited, but is, for example, a halide ion such as F-, ^{Cl- ,} Br- ^, I- ^, etc.;
Boron anions such as (C ₆ H ₅ ) ₄ B- ^, (C ₆ F ₅ ) ₄ B- ^;
Carboxylic acid anions such as CH ₃ COO- ^, C ₂ H ₅ COO- ^, C ₆ H ₅ COO- ^;
Sulfate anions such as SO ₄ ^2- and HSO _4- ;
Phosphate anions such as HPO ₄ ^2- and PO ₄ ^3- ;
Examples include sulfonic acid anion.
The sulfonic acid anion may have a substituent such as trifluoromethanesulfonic acid, methanesulfonic acid, pentansulfonic acid, hexanesulfonic acid, heptanesulfonic acid, dodecanesulfonic acid, camphorsulfonic acid or the like. ;
Aromatic sulfonic acid anion which may have a substituent such as benzenesulfonic acid, p-toluenesulfonic acid, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid;
acid blue 80 (CI 61585), acid green 25 (CI 61570), acid blue 45 (CI 63010), acid blue 43 (CI 63000), acid blue 25 (C.I. 63000). Anion of anthraquinone-based dyes having a sulfonate group such as I.62055), acid blue 40 (CI65125);
Anions of phthalocyanine dyes having a sulfonato group such as direct blue 86 (CI 74810) and direct blue 199 (CI 14190);
Anion of indigo dye having a sulfonato group such as acid blue 74 (CI 73015);
Examples thereof include a halogenoalkylsulfonylimide anion and a halogenoalkylsulfonylmethide anion.

Among these, from the viewpoint of heat resistance, a halogenoalkylsulfonylimide anion which may have a substituent, a halogenoalkylsulfonylmethide anion which may have a substituent, (C ₆ F ₅ ) ₄ B ^- etc. Is preferable.

The number of carbon atoms of the halogenoalkyl group in the halogenoalkylsulfonylimide anion or the halogenoalkylsulfonylmethide anion is preferably 12 or less, more preferably 10 or less, further preferably 6 or less, and usually 1 or more. be. When it is set to the lower limit value or more, the charge of the anion tends to be dispersed and the anion tends to be stabilized. Tends to be possible.

The type of halogen atom contained in the halogenoalkyl group is not particularly limited, but is preferably fluorine, chlorine, bromine, or iodine, more preferably fluorine or chlorine, and even more preferably fluorine. By setting the type of halogen atom to the above, the charge of the anion tends to be more delocalized and the heat resistance of the coloring material can be improved.
The number of halogen atoms contained in the halogenoalkyl group is not particularly limited, but is preferably 27 or less, more preferably 12 or less, further preferably 6 or less, and usually 3 or more. When it is set to the lower limit value or more, the charge of the anion tends to be dispersed and the anion tends to be stabilized, and when it is set to the upper limit value or less, it has appropriate solubility and is affected by the steric repulsion with the cation. Tends to be smaller, allowing for stronger interactions with cations.

Specific examples of the halogenoalkylsulfonylimide anion include bistrifluoromethanesulfonylimide anion, bispentafluoroethanesulfonylimide anion, and bisnonafluorobutanesulfonylimide anion. From the viewpoint of anion heat resistance, bistrifluoro The methanesulfonylimide anion or the bispentafluoroethanesulfonylimide anion is preferable, and the bistrifluoromethanesulfonylimide anion is more preferable.

Specific examples of the halogenoalkylsulfonylmethide anion include tristrifluoromethanesulfonylimide anion, trispentafluoroethanesulfonylimide anion, and trisnonafluorobutanesulfonylimide anion, which are affected by steric repulsion with the cation. From the viewpoint of small size, tristrifluoromethanesulfonylimide anion or trispentafluoroethanesulfonylimide anion is preferable, and bistrifluoromethanesulfonylimide anion is more preferable.

Further, the substituent which the halogenoalkylsulfonylimide anion or the halogenoalkylsulfonylmethide anion may have is not particularly limited, but those exemplified as the above-mentioned substituent group W3 can be used, and among them, the anion. From the viewpoint of the stability of the charge distribution in the ring, an aromatic ring group which may have a substituent is preferable.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number is not particularly limited, but is preferably 30 or less, more preferably 12 or less, usually 4 or more, and preferably 6 or more. By setting the value to the upper limit or less, there is a tendency that steric hindrance with the cation can be suppressed and the anion can be stabilized.
The aromatic hydrocarbon ring group may be a monocyclic ring or a fused ring, and may be, for example, a benzene ring, a naphthalene ring, anthracene ring, a phenanthrene ring, a perylene ring, or a tetracene having one free atomic value. Groups such as a ring, a pyrene ring, a benzpyrene ring, a chrysen ring, a triphenylene ring, an acenaphthene ring, a fluorantene ring, and a fluorene ring can be mentioned.
The aromatic heterocyclic group may be a monocyclic ring or a fused ring, and may be, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, or a pyrazole ring having one free atomic value. , Pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrrolobymidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrol ring, thienothiophene ring, flopyrol ring, furan ring, thienoflan ring, benzisoxazole ring. , Benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxalin ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline Groups such as rings, benzolinone rings, and azulene rings can be mentioned.

Among these, a benzene ring, a naphthalene ring, a thiophene ring, or a triazine ring is preferable, a benzene ring or a triazine ring is more preferable, and a triazine ring is further preferable, from the viewpoint of suppressing steric hindrance with a cation. Since the triazine ring has high planarity, it is considered that the interaction with the aromatic moiety of the dye cation and the anion moiety existing in the same system tends to be strong. Further, since it has a sulfonylimide skeleton or a sulfonylmethide skeleton, it is considered that there is little steric repulsion with the cation and it is easy to form a stronger ion pair. As a result, since it is difficult to separate the cation and the anion, the heat resistance is high, it is easy to suppress the decrease in the interaction between the cation and the anion even in an electric field, and the voltage retention rate of the obtained pixel tends to be high. There is.
The number of substituents that the halogenoalkylsulfonylimide anion or the halogenoalkylsulfonylmethide anion may have is not particularly limited, but is preferably 1 to 3 from the viewpoint of suppressing steric hindrance. Is more preferable.

(Anions represented by formulas (A-1) and (A-2))
Among these, from the viewpoint of anion stabilization, the substituent is preferably at the end of the anion, and in particular, the anion represented by the following formula (A-1) or the following formula (A-2). It is preferably an anion.

In the above formula (A-1), R ^1a and R ^2a each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. ..
R ^3a represents a direct bond, an alkylene group which may have a substituent, or a divalent aromatic ring group which may have a substituent.
R ^4a represents a halogenoalkyl group.
Each of X ¹ to X ³ is independently bonded, at least one group selected from the group consisting of-(CH ₂ )-, -NH-, -O- and -S-, or a group in which two or more of these are bonded. Represents.

In the above formula (A-2), R ^5a and R ^6a each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. ..
R ^7a represents a direct bond, an alkylene group which may have a substituent, or a divalent aromatic ring group which may have a substituent.
R ^8a and R ^9a each independently represent a halogenoalkyl group.
Each of ^X4 to ^X6 is independently bonded, at least one group selected from the group consisting of-(CH ₂ )-, -NH-, -O- and -S-, or a group in which two or more of these are bonded. Represents.

(R ^1a , R ^2a , R ^5a , R ^6a )
R ^1a , R ^2a , R ^5a , and R ^6a each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
Among these, examples of the alkyl group include linear, branched or cyclic alkyl groups. The carbon number is preferably 8 or less, more preferably 5 or less, and preferably 2 or more, from the viewpoint of solubility in a solvent.
Specific examples include a methyl group, an ethyl group, an n-propyl group, a 2-propyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a 2-ethylhexyl group, a cyclohexyl group, a cyclohexylmethyl group and a cyclohexylethyl group. Examples thereof include a 3-methylbutyl group. From the viewpoint of the balance between the crystallinity and the solubility of the salt formed in these, a linear or branched alkyl group is preferable, and a linear alkyl group is more preferable.
Examples of the substituent that the alkyl group may have include those of the above-mentioned substituent group W1.

Among these, examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number is preferably 30 or less, more preferably 12 or less, preferably 4 or more, and 6 or more, from the viewpoint of the balance between crystallinity and solubility, from the viewpoint of suppressing steric hindrance. It is more preferable to have.
The aromatic hydrocarbon ring group may be a monocyclic ring or a fused ring, and may be, for example, a benzene ring, a naphthalene ring, anthracene ring, a phenanthrene ring, a perylene ring, or a tetracene having one free atomic value. Groups such as a ring, a pyrene ring, a benzpyrene ring, a chrysen ring, a triphenylene ring, an acenaphthene ring, a fluorantene ring, and a fluorene ring can be mentioned.
The aromatic heterocyclic group may be a monocyclic ring or a fused ring, and may be, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, or a pyrazole ring having one free atomic value. , Pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrrolobymidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrol ring, thienothiophene ring, flopyrol ring, furan ring, thienoflan ring, benzisoxazole ring. , Benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxalin ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline Groups such as rings, benzolinone rings, and azulene rings can be mentioned.
Among these aromatic ring groups, an aromatic hydrocarbon ring group is preferable from the viewpoint of ease of production.
Examples of the substituent that the aromatic ring group may have include those of the substituent group W2.

Among these, from the viewpoint of the stability of the colored resin composition, R ^1a and R ^2a each independently have an alkyl group which may have a substituent or an aromatic ring which may have a substituent. It is preferably a group.
R ^1a and R ^2a may be the same or different. For example, R ^1a and R ^2a may be alkyl groups which may each have an independent substituent, and R ^1a and R ^2a may each have an independent substituent. It may be a ring group, R ^1a may be an alkyl group which may have a substituent, and R ^2a may be an aromatic ring group which may have a substituent.
R ^5a and R ^6a may be the same or different. For example, R ^5a and R ^6a may be alkyl groups which may each have an independent substituent, and R ^5a and R ^6a may each have an independent substituent. It may be a ring group, R ^5a may be an alkyl group which may have a substituent, and R ^6a may be an aromatic ring group which may have a substituent.

(R ^3a , R ^7a )
R ^3a represents a direct bond, an alkylene group which may have a substituent, or a divalent aromatic ring group which may have a substituent.
Among these, examples of the alkylene group include a linear alkylene group, a branched chain alkylene group, a cyclic alkylene group, and a group in which these are bonded. The carbon number is preferably 8 or less, more preferably 5 or less, and usually 1 or more, from the viewpoint of suppressing charge bias.
Specific examples include a methylene group, an ethylene group, a propylene group and the like. Among these, a methylene group is preferable from the viewpoint of suppressing charge bias.
Examples of the substituent that the alkylene group may have include those of the substituent group W1.

Among these, examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. From the viewpoint of anion rigidity and heat resistance, the carbon number is preferably 30 or less, more preferably 12 or less, usually 4 or more, and preferably 6 or more.
The divalent aromatic hydrocarbon ring group may be a monocyclic ring or a fused ring, and may be, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, or perylene having two free atomic valences. Groups such as a ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysen ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring can be mentioned.
The aromatic heterocyclic group may be a monocyclic ring or a fused ring, and may be, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, or a pyrazole ring having two free atomic valences. , Pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrrolobymidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrol ring, thienothiophene ring, flopyrol ring, furan ring, thienoflan ring, benzisoxazole ring. , Benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxalin ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline Groups such as rings, benzolinone rings, and azulene rings can be mentioned.
Among these divalent aromatic ring groups, a divalent aromatic hydrocarbon ring group is preferable, and a benzene ring is more preferable, from the viewpoint of suppressing charge bias.
Examples of the substituent that the divalent aromatic ring group may have include those of the substituent group W2.

(R ^4a , R ^8a , R ^9a )
R ^4a , R ^8a , and R ^9a each independently represent a halogenoalkyl group.
The type of halogen atom contained in the halogenoalkyl group is not particularly limited, but is preferably fluorine, chlorine, bromine, or iodine, more preferably fluorine or chlorine, and even more preferably fluorine. By setting the type of halogen atom to the above, the charge of the anion tends to be more delocalized and the heat resistance of the coloring material can be improved.
The number of halogen atoms contained in the halogenoalkyl group is not particularly limited, but is preferably 27 or less, more preferably 12 or less, further preferably 6 or less, and usually 3 or more. When it is set to the lower limit value or more, the charge of the anion tends to be dispersed and the anion tends to be stabilized, and when it is set to the upper limit value or less, it has appropriate solubility and is affected by the steric repulsion with the cation. Tends to be smaller, allowing for stronger interactions with cations.
The number of carbon atoms of the halogenoalkyl group is not particularly limited, but is preferably 12 or less, more preferably 6 or less, and usually 1 or more. When it is set to the lower limit value or more, the charge of the anion tends to be dispersed and the anion tends to be stabilized. Tends to be possible.
Specific examples thereof include a trifluoromethyl group, a pentafluoroethyl group, a 1,1,1-trifluoroethyl group and the like, and a trifluoromethyl group is preferable from the viewpoint of suppressing charge bias.

(X ¹ to X ⁶ )
Each of X ¹ to X ⁶ is independently bonded, at least one group selected from the group consisting of-(CH ₂ )-, -NH-, -O- and -S-, or a group in which two or more of these are bonded. Represents.
That is, each of X ¹ to X ⁶ may be independently bonded to two or more divalent groups selected from the above group, or may be bonded to two or more of one type. The number of pieces to be combined is usually 2 or more, usually 15 or less, preferably 12 or less, and more preferably 10 or less.
Among these, from the viewpoint of ease of synthesis,-(CH ₂ )-or -NH- is preferable, and -NH- is more preferable.

Among these, bistrifluoro is highly heat resistant and has a small effect of steric repulsion with the cation, so that the interaction between the anion and the cation is large, the counterion is stabilized, and the heat resistance of the dye is improved. It is preferably a methanesulfonylimide anion, a trifluoromethanesulfonylmethide anion, or a 2,6-diphenylamino-4-butylamino-1,3,5-triazine ring-containing trifluoromethanesulfonylimide anion.

(N)
In the formula (I), n represents an integer of 1 to 4. n is not particularly limited as long as it satisfies the relationship of l = m × n. For example, if l is 2 and m is 2, n is 1, and if l is 2 and m is 1, n is 2.

Further, the present form of the triarylmethane-based compound represented by the above formula (I) in the colored resin composition is not particularly limited, and may be a dye and / or a pigment, from the viewpoint of luminance and contrast. Is preferably present in the form of a dye.

(Molecular weight)
In the triarylmethane-based compound represented by the general formula (I), the molecular weight of the triarylmethane cation is preferably 600 or more, more preferably 800 or more, and more preferably 3000 or less. It is more preferably 2000 or less, and even more preferably 1500 or less. When it is at least the above lower limit value, dye transfer tends to be improved, and when it is at least the above upper limit value, synthesis tends to be easy.

The total molecular weight of the cations and anions, that is, the total molecular weight of the general formula (I) is preferably 700 or more, more preferably 900 or more, and preferably 3000 or less, and 2500 or less. It is more preferable to have. When it is at least the above lower limit value, dye transfer tends to be improved, and when it is at least the above upper limit value, synthesis tends to be easy.

(Specific example of the compound represented by the formula (I))
As the superstructure of the cation portion of the compound represented by the formula (I) (meaning the portion above the naphthalene ring among the cation portions in the formula (I)), for example, those listed below are used. be able to.

Further, as the substructure of the cation portion of the compound represented by the formula (I) (meaning the portion below the naphthalene ring among the cation portions in the formula (I)), for example, those listed below are used. be able to.

Specific examples of the structure of the anion portion of the compound represented by the formula (I) include those represented below.

(Method for synthesizing the compound represented by the formula (I))
The compounds represented by the above formula (I) are, for example, "Overview Synthetic Dyes" (Horiguchi Hiroshi, Sankyo Publishing, 1968), "Theoretical Manufacturing Dye Chemistry" (Hosoda Yutaka, Gihodo, 1957), International Publication No. It can be synthesized according to the method described in the 2009/107734 pamphlet and the International Publication No. 2015/08217 pamphlet, but is not limited to this method.

(Content ratio of the compound represented by the formula (I))
The coloring material (A) in the colored resin composition of the present invention may contain one kind of triaryl methane-based compound represented by the formula (I), or may contain two or more kinds.
The content ratio of the coloring material (A) in the colored resin composition is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 1% by mass or more in the total solid content. 5% by mass or more is more preferable, 10% by mass or more is particularly preferable, 15% by mass or more is most preferable, 50% by mass or less is more preferable, 40% by mass or less is more preferable, and 30% by mass or less is further preferable. 20% by mass or less is particularly preferable. When it is at least the lower limit value, it tends to be easy to secure the coloring power, and when it is at least the above upper limit value, it is easy to obtain the chromaticity of a desired concentration, and there is a tendency that the film quality is improved.

Further, the content ratio of the compound represented by the formula (I) in the (A) coloring material is not particularly limited, but is preferably 50% by mass or more, more preferably 70% by mass or more with respect to the (A) coloring material. , 80% by mass or more is more preferable, 90% by mass or more is particularly preferable, and usually 100% by mass or less. By setting the value to the lower limit or higher, the dye transfer and the voltage holding rate tend to be good.

(Other color materials)
The coloring material (A) in the colored resin composition of the present invention may contain other coloring materials in addition to the triarylmethane-based compound represented by the general formula (I). Examples of other coloring materials include other dyes and pigments.
The content ratio is not particularly limited, but is preferably 70% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less in the total solid content. The content ratio with respect to the (A) coloring material is preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 10% by mass or less. Within the above range, the color tone, heat resistance, and light resistance of the obtained pixels are likely to be improved without significantly affecting the absorption waveform and the brightness in the colored resin composition, which is preferable.

(Other dyes)
Examples of other dyes include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, cyanine dyes, and triarylmethane dyes. Dipyrromethene dyes, xanthene dyes and the like are preferably mentioned.

Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Moldant Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples include Moldant Black 7.

Examples of the anthraquinone dye include C.I. I. Bat Blue 4, C.I. I. Acid Blue 25, C.I. I. Acid Blue 40, C.I. I. Acid Blue 80, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse blue 60 and the like can be mentioned.

In addition, as a phthalocyanine dye, for example, C.I. I. Direct Blue 86, C.I. I. Direct Blue 199, C.I. I. Batblue 5, JP-A-2002-14222, JP-A-2005-134759, JP-A-2010-191358, JP-A-2011-148950 and the like can be used as quinoneimine dyes, for example, C. .. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are used as quinoline dyes, for example, C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like can be used as nitro dyes, for example, C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like can be mentioned.

Further, as the triarylmethane dye, for example, C.I. I. Acid Blue 86, C.I. I. Acid Blue 88, C.I. I. Examples thereof include those described in Acid Blue 108, International Publication No. 2009/107734, and International Publication No. 2011/162217.
Further, examples of the cyanine-based dye include those described in Pamphlet No. 2011/162217 of International Publication No. 2011/162217, and preferred embodiments are also the same.

Examples of the dipyrromethene dye include JP-A-2008-292970, JP-A-2010-84009, JP-A-2010-84141, JP-A-2010-85454, JP-A-2011-158654, and JP-A. Examples thereof include those described in JP-A-2012-158739, JP-A-2012-224852, JP-A-2012-224489, JP-A-2012-224847, JP-A-2012-224846, and the like.

Examples of the xanthene dye include C.I. I. Acid Red 50, C.I. I. Acid Red 52, C.I. I. Acid Red 289, Japanese Patent No. 3387541, Japanese Patent Application Laid-Open No. 2010-32999, Japanese Patent No. 4492760, "Review Synthetic Dyes" (Horiguchi Hiroshi, Sankyo Publishing, 1968), pp. 326-348, etc. Can be mentioned.
In particular, when forming blue pixels, xanthene dyes, triarylmethane dyes, anthraquinone dyes, azo dyes, dipyrromethene dyes, cyanine dyes, and phthalocyanine dyes are preferable, and xanthene dyes are preferable from the viewpoint of durability. Alternatively, dipyrromethene dyes are more preferable, and xanthene dyes are even more preferable.
The colored resin composition of the present invention may contain only one type of other dye, or may contain two or more types.

(Pigment)
As the pigment, for example, when forming the pixels of a color filter or the like, pigments of various colors such as blue and purple can be used. Examples of the chemical structure include organic pigments such as phthalocyanine-based, quinacridone-based, benzimidazolone-based, dioxazine-based, indanthrone-based, and perylene-based. In addition to this, various inorganic pigments and the like can also be used. Hereinafter, specific examples of pigments that can be used are shown by pigment numbers.

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

Among these, from the viewpoint of heat resistance and light resistance, a phthalocyanine pigment having a central metal is preferable, and a blue copper phthalocyanine pigment is particularly preferable. Examples of the copper phthalocyanine pigment include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 and the like are preferable, and C.I. I. Pigment Blue 15: 6.
Therefore, when the colored resin composition of the present invention contains a blue pigment, 80% by mass or more, particularly 90% by mass or more, particularly 95 to 100% by mass, is C.I. I. Pigment Blue 15: 6 is preferred.

Examples of the purple pigment include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like can be mentioned.
Among these, a purple dioxazine pigment is preferable, and as the dioxazine pigment, C.I. I. Pigment Violet 19, 23 and the like are preferably mentioned, and more preferably C.I. I. Pigment Violet 23.

Therefore, when the colored resin composition of the present invention contains a purple pigment, 80% by mass or more, particularly 90% by mass or more, particularly 95 to 100% by mass, is C.I. I. Pigment Violet 23 is preferred.
One of these may be used alone, or two or more thereof may be mixed and used in any combination and ratio.

The pigment that can be used in the colored resin composition of the present invention preferably has a small average primary particle size from the viewpoint of forming pixels with high contrast, and specifically, the average primary particle size is 40 nm or less. Is preferable, and it is more preferably 35 nm or less.
In particular, the blue copper phthalocyanine pigment also preferably has an average primary particle size of 40 nm or less, more preferably 35 nm or less, and further preferably 20 to 30 nm.

For the dioxazine pigment, the average primary particle size is preferably 40 nm or less, more preferably 25 to 35 nm. From the viewpoint that the pigment is less likely to aggregate in the colored resin composition, it is preferable that the average primary particle size is not too small.
Here, the average primary particle size of the pigment can be a value measured and calculated by the following method.

First, the pigment is ultrasonically dispersed in chloroform, dropped onto a collodion film-attached mesh, dried, and observed with a transmission electron microscope (TEM) to obtain a primary particle image of the pigment. From this image, the particle size of each of a plurality of (usually about 200 to 300) pigment particles is obtained as the diameter equivalent to the area circle converted into the diameter of a circle having the same area.
Using the obtained primary particle size value, calculate the number average value according to the formula below to obtain the average particle size.

Particle size of individual pigment particles: X ₁ , X ₂ , X ₃ , X ₄ , ..., X _i , ... X _m (m is the number of particles)

Among the other coloring materials, it is preferable to contain other pigments from the viewpoint of improving heat resistance and light resistance, and it is more preferable to contain a blue pigment from the viewpoint of improving heat resistance and light resistance caused by the blue coloring material.

[(B) Solvent]
The solvent (B) contained in the colored resin composition of the present invention has a function of dissolving or dispersing each component contained in the colored resin composition and adjusting the viscosity.
The solvent (B) may be any solvent as long as it can dissolve or disperse each component constituting the colored resin composition, and it is preferable to select a solvent having a boiling point in the range of 100 to 200 ° C. More preferably, it has a boiling point of 120 to 170 ° C.

Examples of such a solvent include the following.
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol-monot-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, methoxymethylpentanol, propylene Glycol monoalkyl ethers such as glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol monomethyl ether;

Glycoldialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monoethyl Glycolalkyl ether acetates such as ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate;

Ethers such as diethyl ether, dipropyl ether, diisopropyl ether, diamil ether, ethylisobutyl ether, dihexyl ether;
Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone;
Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin;
Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;

Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amilformate, ethylformate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, cyclohexyl acetate, methylisobutyrate, ethylene glycol acetate, ethylpropionate, propylpropionate, butyl butyrate, isobutyl butyrate, isobutyric acid Methyl, ethyl caprilate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3- Chain or cyclic esters such as butyl methoxypropionate, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid, 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride, amilk chloride;
Etheretones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile:
These solvents may be used alone or in combination of two or more.

It is preferable to contain glycol monoalkyl ethers in the solvent from the viewpoints of adhesion between the substrate and the coating film and the ability to form a uniform film thickness of the coating film. Of these, propylene glycol monomethyl ether is particularly preferable from the viewpoint of solubility of various constituents in the colored resin composition.
Further, for example, when the above-mentioned other pigment is contained as an optional component, the balance of coatability, surface tension and the like is good, and the solubility of the component in the colored resin composition is relatively high, so that the glycol is further used as a solvent. It is more preferable to use a mixture of alkyl ether acetates. In the colored resin composition containing a pigment, glycol monoalkyl ethers have high polarity and tend to aggregate the pigment, which may reduce the storage stability such as increasing the viscosity of the colored resin composition. Therefore, it is preferable that the amount of the glycol monoalkyl ethers used is not excessively large, and the ratio of the glycol monoalkyl ethers in the solvent (B) is preferably 5 to 50% by mass, more preferably 5 to 30% by mass. ..

Further, from the viewpoint of suitability for the slit coating method corresponding to recent large substrates and the like, it is also preferable to use a solvent having a boiling point of 150 ° C. or higher in combination. In this case, the content of such a high boiling point solvent is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 5 to 30% by mass with respect to the whole solvent (B). If the amount of the high boiling point solvent is too small, for example, dye components may precipitate and solidify at the tip of the slit nozzle, causing foreign matter defects, and if it is too large, the drying speed of the composition slows down, and the color described later In the filter manufacturing process, there is a concern that it may cause problems such as poor tact in the vacuum drying process and pin marks on the pre-bake.

The solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers, and in this case, it is not necessary to separately contain a solvent having a boiling point of 150 ° C. or higher. ..
The colored resin composition of the present invention may be subjected to a color filter production by an inkjet method, but in the color filter production by an inkjet method, the ink emitted from the nozzle is very small, several to several tens of pL. Before landing around the nozzle opening or in the pixel bank, the solvent tends to evaporate and the ink tends to concentrate and dry. In order to avoid this, it is preferable that the boiling point of the solvent is high, and specifically, it is preferable that the solvent (B) contains a solvent having a boiling point of 180 ° C. or higher. In particular, it is preferable to contain a solvent having a boiling point of 200 ° C. or higher, particularly preferably a boiling point of 220 ° C. or higher. The high boiling point solvent having a boiling point of 180 ° C. or higher is preferably 50% by mass or more in the solvent (B). When the proportion of such a high boiling point solvent is 50% by mass or more, the effect of preventing evaporation of the solvent from the ink droplets tends to be sufficiently exhibited.

The content ratio of the solvent in the entire colored resin composition of the present invention is not particularly limited, but the upper limit thereof is usually 99% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less, and is used for coating. Considering suitable viscosity and the like, it is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more.

[(C) Binder resin]
In the colored resin composition of the present invention, the binder resin (C) is not limited as long as it is soluble in the above-mentioned solvent and can form a cured film having a sufficient degree of curing, but the pattern is formed by alkaline development. From the viewpoint of forming, an alkali-soluble resin is preferable. For example, JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118, The polymer compounds described in each publication such as JP-A-2003-233179 can be used, and among them, the following resins (C-1) to (C-5) are preferable.

(C-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. An alkali-soluble resin (hereinafter referred to as "resin (C-1)") obtained by adding a polybasic acid anhydride to at least a part of the added resin or the hydroxyl group generated by the addition reaction may be used. .)
(C-2): Carboxyl group-containing linear alkali-soluble resin (C-2) (hereinafter, may be referred to as "resin (C-2)").
(C-3): A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the resin (C-2) (hereinafter, may be referred to as "resin (C-3)").
(C-4): (Meta) acrylic resin (hereinafter, may be referred to as "resin (C-4)")
(C-5): Epoxy acrylate resin having a carboxyl group (hereinafter, may be referred to as "resin (C-5))."
Of these, resin (C-1) is particularly preferable, and the resin will be described below.

The resins (C-2) to (C-5) may be any as long as they are dissolved by an alkaline developer and have a solubility to the extent that the desired developing treatment can be carried out. It is the same as that described as the same item in Japanese Patent Publication No. 2009-025813. The same applies to the preferred embodiment.
(C-1): With respect to a polymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. An epoxy group is used as one of the particularly preferable resins of the alkali-soluble resin resin (C-1) obtained by adding a polybasic acid anhydride to at least a part of the added resin or the hydroxyl group generated by the addition reaction. The polymer containing 5 to 90 mol% of the (meth) acrylate and 10 to 95 mol% of the other radically polymerizable monomer is unsaturated to 10 to 100 mol% of the epoxy group contained in the copolymer. Examples thereof include a resin obtained by adding a monobasic acid, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to 10 to 100 mol% of the hydroxyl groups generated by the addition reaction.

Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. ) Acrylate glycidyl ether and the like can be exemplified. Of these, glycidyl (meth) acrylate is preferable. One of these epoxy group-containing (meth) acrylates may be used alone, or two or more thereof may be used in combination.

The other radically polymerizable monomer copolymerized with the epoxy group-containing (meth) acrylate is not particularly limited as long as the effect of the present invention is not impaired, and for example, vinyl aromatics, dienes, (meth). Examples thereof include acrylic acid esters, (meth) acrylic acid amides, vinyl compounds, unsaturated dicarboxylic acid diesters, monomaleimides, etc., and in particular, mono (meth) having a structure represented by the following formula (III). Acrylic is preferred.

The repeating unit derived from the mono (meth) acrylate having the structure represented by the following formula (III) contains 5 to 90 mol% of the repeating units derived from "another radically polymerizable monomer". It is preferable that the content is preferably 10 to 70 mol%, more preferably 15 to 50 mol%, and particularly preferably 15 to 50 mol%.

In the above formula (III), R ⁸⁹ represents a hydrogen atom or a methyl group, and R ⁹⁰ represents a structure represented by the following formula (IV).

In the above formula (IV), R ⁹¹ to R ⁹⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In addition, R ⁹⁶ and R ⁹⁸ may be connected to each other to form a ring.
The ring formed by connecting R ⁹⁶ and R ⁹⁸ is preferably an aliphatic ring, which may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.
Among them, as the structure represented by the formula (IV), the structure represented by the following structural formulas (IVa), (IVb), or (IVc) is particularly preferable.

As the mono (meth) acrylate having the structure represented by the formula (IV), one type may be used alone, or two or more types may be used in combination.
As the "other radically polymerizable monomer" other than the mono (meth) acrylate having the structure represented by the formula (IV), the colored resin composition can be improved in excellent heat resistance and strength. , Styrene, (meth) acrylate-n-butyl, (meth) acrylate-tert-butyl, (meth) acrylate cyclohexyl, (meth) acrylate isoboronyl, (meth) acrylate adamantyl, (meth) acrylate benzyl , (Meta) -2-hydroxyethyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, and the like.

The content of the repeating unit derived from at least one selected from the above-mentioned monomer group is preferably 1 to 70 mol%, more preferably 3 to 50 mol%.
A known solution polymerization method is applied to the copolymerization reaction between the epoxy group-containing (meth) acrylate and the other radically polymerizable monomer.
In the present invention, the copolymer of the epoxy group-containing (meth) acrylate and the other radically polymerizable monomer includes a repeating unit of 5 to 90 mol% derived from the epoxy group-containing (meth) acrylate, and the like. The repeating unit derived from the radically polymerizable monomer of the above is preferably 10 to 95 mol%, more preferably 20 to 80 mol% of the former and 80 to 20 mol% of the latter, and 30 to 30 to 20 of the former. Those consisting of 70 mol% and the latter 70 to 30 mol% are particularly preferable.

Within the above range, the amount of the polymerizable component and the alkali-soluble component described later is sufficient, and the heat resistance and the strength of the film are sufficient, which is preferable.
An unsaturated monobasic acid (polymerizable component) is further reacted with a polybasic acid anhydride (alkali-soluble component) on the epoxy group portion of the epoxy group-containing copolymer synthesized as described above.
Here, as the unsaturated monobasic acid added to the epoxy group, known ones can be used, and examples thereof include unsaturated carboxylic acids having an ethylenically unsaturated double bond.

Specific examples include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and the α-position is substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, a cyano group, or the like. Examples thereof include monocarboxylic acids such as (meth) acrylic acid. Of these, (meth) acrylic acid is preferable. These may be used alone or in combination of two or more.

By adding such a component, the binder resin used in the present invention can be imparted with polymerizable properties.
These unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy group of the copolymer, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. When it is within the above range, it is preferable because the colored resin composition is excellent in stability over time. As a method for adding an unsaturated monobasic acid to the epoxy group of the copolymer, a known method can be adopted.

Further, known polybasic acid anhydrides can be used as the polybasic acid anhydride added to the hydroxyl group generated when unsaturated monobasic acid is added to the epoxy group of the copolymer.
For example, dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone. Examples thereof include anhydrides of acids having three or more bases such as tetracarboxylic acid anhydride and biphenyltetracarboxylic acid anhydride. Of these, succinic anhydride and tetrahydrophthalic anhydride are preferred. One of these polybasic acid anhydrides may be used alone, or two or more thereof may be used in combination.

By adding such a component, alkali solubility can be imparted to the binder resin used in the present invention.
These polybasic acid anhydrides are usually added to 10 to 100 mol% of the hydroxyl groups generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer, preferably 20 to 90 mol. %, More preferably 30-80 mol%.

When it is within the above range, the residual film ratio and solubility at the time of development are sufficient, which is preferable.
As a method for adding the polybasic acid anhydride to the hydroxyl group, a known method can be adopted.
Further, in order to improve the photosensitivity, after the above-mentioned polybasic acid anhydride is added, glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group is added to a part of the generated carboxyl groups. May be. The structure of such a resin is described in, for example, Japanese Patent Application Laid-Open No. 8-297366 and Japanese Patent Application Laid-Open No. 2001-89533.

The polystyrene-equivalent weight average molecular weight (Mw) of the above-mentioned binder resin (C) measured by GPC (gel permeation chromatography) is preferably 3000 or more, more preferably 5000 or more, and preferably 100,000 or less, preferably 50,000 or less. The following is more preferable, 30,000 or less is further preferable, and 10,000 or less is particularly preferable. When it is within the above range, it is preferable in that heat resistance, film strength, and solubility in a developing solution are good.
As a guideline for the molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 2.0 to 5.0.

The acid value of the binder resin (C) is preferably 10 mg-KOH / g or more, more preferably 30 mg-KOH / g or more, further preferably 50 mg-KOH / g or more, and preferably 200 mg-KOH / g or less. 150 mg-KOH / g or less is more preferable, and 100 mg-KOH / g or less is further preferable. When it is set to the lower limit value or more, the solubility in a developing solution tends to be good, and when it is set to the upper limit value or less, the film roughness tends to be suppressed.

The content ratio of the binder resin (C) in the colored resin composition is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and particularly preferably 30% by mass or more. It is preferable, 80% by mass or less is preferable, 70% by mass or less is more preferable, 60% by mass or less is further preferable, 50% by mass or less is further preferable, and 40% by mass or less is particularly preferable. When it is set to the lower limit value or more, an appropriate film thickness for pattern formation by development tends to be secured, and when it is set to the upper limit value or less, the sensitivity tends to be appropriate for pattern formation by development.

[(D) Polymerizable Monomer]
The colored resin composition of the present invention preferably contains (D) a polymerizable monomer. The polymerizable monomer (D) is not particularly limited as long as it is a polymerizable low molecular weight compound, but may be referred to as an addition polymerizable compound having at least one ethylenic double bond (hereinafter, referred to as “ethylenic compound”). There is.).
The ethylenic compound is a compound having an ethylenic double bond such that when the colored resin composition of the present invention is irradiated with active light, it is addition-polymerized and cured by the action of a photopolymerization initiating component described later. The (D) polymerizable monomer in the present invention means a concept opposite to a so-called polymer substance, and includes dimers, trimers, and oligomers in addition to monomers in a narrow sense.

In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated bonds in one molecule. The number of ethylenically unsaturated bonds contained in the polyfunctional ethylenically monomer is not particularly limited, but is preferably 2 or more, more preferably 3 or more, still more preferably 5 or more, and preferably 15 or less, more preferably 10 or more. It is as follows. When it is at least the above lower limit value, the polymerizable property tends to be improved and the sensitivity tends to be high, and when it is at least the above upper limit value, the developability tends to be better.

Examples of the ethylenic compound in the (D) polymerizable monomer include unsaturated carboxylic acids such as (meth) acrylic acid; esters of monohydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds and unsaturated carboxylic acids. Esters; Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; Estherization of unsaturated carboxylic acids with polyvalent carboxylic acids and polyvalent hydroxy compounds such as the above-mentioned aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds. Examples thereof include an ester obtained by the reaction; an ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth) acryloyl group-containing hydroxy compound; and the like.

Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylol propanetri (meth) acrylate, and trimethylol ethanetri (meth) acrylate. , Pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) Examples thereof include (meth) acrylic acid esters such as acrylate and glycerol (meth) acrylate. Further, an itaconic acid ester in which the (meth) acrylic acid portion of these (meth) acrylic acid esters is replaced with an itaconic acid moiety, a crotonic acid ester in which the crotonic acid moiety is replaced, a maleic acid ester in which the maleic acid moiety is replaced, or the like. Can be mentioned.

Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include hydroquinone di (meth) acrylate, resorcindi (meth) acrylate, and pyrogalloltri (meth) acrylate.
The ester obtained by the esterification reaction of the unsaturated carboxylic acid with the polyvalent carboxylic acid and the polyvalent hydroxy compound may be a single substance or a mixture. Typical examples are (meth) acrylic acid, phthalic acid, and ethylene glycol condensates; (meth) acrylic acid, maleic acid, and diethylene glycol condensates; (meth) acrylic acid, terephthalic acid, and pentaerythritol condensation. Substances; Examples thereof include (meth) acrylic acid, adipic acid, butanediol, and condensates of glycerin.

Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; and alicyclics such as cyclohexane diisocyanate and isophorone diisocyanate. Formula diisocyanate; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, and (meth) acryloyl such as 2-hydroxyethyl (meth) acrylate and 3-hydroxy [1,1,1-tri (meth) acryloyloxymethyl] propane. Examples thereof include a reaction product with a group-containing hydroxy compound.

Other examples of the ethylenic compound used in the present invention include (meth) acrylamides such as ethylenebis (meth) acrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinylphthalate. ..
Among these, esters of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid are preferable, pentaerythritol or a (meth) acrylic acid ester of dipentaerythritol is more preferable, and dipentaerythritol hexa (meth) acrylate is particularly preferable.

Further, the ethylenic compound may be a monomer having an acid value. Examples of the monomer having an acid value are esters of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid is obtained by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. A polyfunctional monomer having a group is preferable, and particularly preferably, in this ester, the aliphatic polyhydroxy compound is at least one of pentaerythritol and dipentaerythritol.

Although one kind of these monomers may be used alone, a mixture of two or more kinds may be used because it is difficult to obtain a single compound in production.
Further, if necessary, (D) a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as the polymerizable monomer.
The acid value of the polyfunctional monomer having an acid group is preferably 0.1 to 100 mg-KOH / g, and particularly preferably 5 to 80 mg-KOH / g.

Within the above range, the developing and dissolving characteristics are less likely to deteriorate, and manufacturing and handling are easy. Further, it is preferable because the photopolymerization performance does not easily deteriorate and the curability such as the surface smoothness of the pixel is good.
In the present invention, the polyfunctional monomer having a more preferable acid group is, for example, a mixture containing, for example, a succinic acid ester of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate as a main component. This polyfunctional monomer can also be used in combination with other polyfunctional monomers.

In the colored resin composition of the present invention, the content ratio of these (D) polymerizable monomers is usually 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 30% by mass or more, based on the total solid content. Is 35% by mass or more, and is usually 90% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, and particularly preferably 50% by mass or less.
The ratio of the (D) polymerizable monomer to 100 parts by mass of the above-mentioned (A) coloring material is usually 1 part by mass or more, preferably 10 parts by mass or more, more preferably 50 parts by mass or more, still more preferably 100 parts by mass. The above is even more preferably 150 parts by mass or more, particularly preferably 200 parts by mass or more, and usually 500 parts by mass or less, preferably 400 parts by mass or less, and more preferably 300 parts by mass or less.
Within the above range, photocuring is moderate, adhesion failure during development is difficult to place, the cross section after development is difficult to form a reverse taper shape, and peeling phenomenon / removal failure due to reduced solubility is difficult to place. preferable.

[(E) Photopolymerization initiation component and (E') Thermal polymerization initiation component]
The colored resin composition of the present invention preferably contains at least one of (E) a photopolymerization initiation component and (E') a thermal polymerization initiation component for the purpose of curing the coating film. However, the curing method may be other than those using these initiators.
In particular, when the colored resin composition of the present invention contains a resin having an ethylenic double bond as the component (C) or contains an ethylenically compound as the component (D), it directly absorbs light or It is preferable to contain at least one of a photopolymerization initiating component having a function of photosensitizing and causing a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical and a thermal polymerization initiating component of generating a polymerization active radical by heat. .. In the present invention, the component (E) as the photopolymerization initiator is a photopolymerization initiator (hereinafter, optionally also referred to as “(E1) component”) and a polymerization accelerator (hereinafter, optionally, “(E2) component”). ”), A sensitizing dye (hereinafter, optionally also referred to as“ (E3) component ”) and other additives are used in combination.

[(E) Photopolymerization initiation component]
The (E) photopolymerization initiator component in the present invention is a mixture of (E1) a photopolymerization initiator and an additive such as (E2) polymerization accelerator and (E3) sensitizing dye added as needed. It is a component having a function of directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical.

Examples of the (E1) photopolymerization initiator constituting the photopolymerization initiator include the titanosen derivatives described in JP-A-59-152396, JP-A-61-15119, and the like; JP-A-10-300922. Hexaarylbiimidazole derivatives described in JP-A, JP-A-11-174224, JP-A-2000-56118, etc .; Radical activators such as s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone Derivatives; Examples thereof include oxime ester-based derivatives described in JP-A-2000-80068.

Specific examples thereof include the photopolymerization initiator described in Pamphlet No. 2009/107734 of International Publication No. 2009.
Among these photopolymerization initiators, α-aminoalkylphenone derivatives, oxime ester derivatives, biimidazole derivatives, acetophenone derivatives, and thioxanthone derivatives are more preferable.
Examples of oxime ester derivatives include 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone and O-acetyl-1- [6- (2-methylbenzoyl) -9. -Ethyl-9H-carbazole-3-yl] Etanone oxime and compounds represented by the following formula (V) can be mentioned.

(In the formula (V), R ¹⁰¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or a heteroaryl group having 4 to 25 carbon atoms. They represent alkyl groups, all of which may have substituents, or R ¹⁰¹ may be attached to X or Z to form a ring.
R ¹⁰² has an alkanoyl group having 2 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, an allylloyl group having 7 to 20 carbon atoms, and an alkoxycarbonyl group having 2 to 10 carbon atoms. , An aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a heteroallyloyl group having 3 to 20 carbon atoms or an alkylaminocarbonyl group having 2 to 20 carbon atoms, all of which are shown. It may have a substituent.

X represents at least one of a divalent aromatic hydrocarbon ring group and an aromatic complex group formed by condensing two or more rings which may have a substituent.
Z indicates an aromatic ring group which may have a substituent. )
Among the compounds represented by the above formula (V), compounds having a carbazole ring in which X may have a substituent are preferable, and specifically, compounds represented by the following formula (VI) and the like are used. Among them, the compound represented by the following formula (VII) is particularly preferable.

In formula (VI), R ¹⁰¹ , R ¹⁰² and Z are synonymous with the definitions in formula (V). R ¹⁰³ to R ¹⁰⁹ each independently represent a hydrogen atom or an arbitrary substituent.

In the formula (VII), R ^101a represents an alkyl group having 1 to 3 carbon atoms or a group represented by the following formula (VIIa).

In formula (VIIa), R ¹¹⁰ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or a heteroarylalkyl group having 4 to 25 carbon atoms. Shows the group. * Represents a binding site. )
R ^102a represents an alkanoyl group having 2 to 4 carbon atoms, and X ^a represents a 3,6-carbazolyl group in which the nitrogen atom may be substituted with an alkyl group of 1 to 4 carbon atoms. Z ^a represents a naphthyl group which may be substituted with a phenyl group or a morpholino group which may be substituted with an alkyl group.

Commercially available products may be used as the oxime-based initiator. Examples of commercially available products include OXE-01, OXE-02 (manufactured by BASF), TRONLYTR-PBG-304, TRONLYTR-PBG-309, TRONLYTR-PBG-305, TRONLYTR-PBG-314 (Tsunyu Powerful Electronic New Materials Limited). A company (manufactured by CANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD)) can be mentioned.

Other photopolymerization initiators include benzoin alkyl ethers, anthraquinone derivatives; acetophenone derivatives such as 2-methyl- (4'-methylthiophenyl) -2-morpholino-1-propanol, 2-ethylthioxanthone, 2 , 4-Dixanthone derivatives such as diethylthioxanthone, benzoic acid ester derivatives, aclysine derivatives, phenylazine derivatives, anthraquin derivatives and the like. Commercially available products may be used as these initiators.

Examples of commercially available products include IRGACURE 651, IRGACURE 184, DAROCURE 1173, IRGACURE 2959, IRGACURE 127, IRGACURE 907, IRGACURE 369, IRGACURE 379EG, LUCIRIN TPO, and IRGACURE 8 Is a registered trademark) and the like.

Among these photopolymerization initiators, α-aminoalkylphenone derivatives, thioxanthone derivatives, and oxime ester-based derivatives are more preferable. In particular, oxime ester-based derivatives are preferable.
Examples of the (E2) polymerization accelerator used as needed include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2-mercapto. Examples thereof include mercapto compounds having a heterocycle such as benzoxazole and 2-mercaptobenzimidazole; and mercapto compounds such as aliphatic polyfunctional mercapto compounds.

As these (E1) photopolymerization initiator and (E2) polymerization accelerator, one type may be used alone, or two or more types may be used in combination.
Further, the (E3) sensitizing dye is used for the purpose of increasing the sensitivity, if necessary. An appropriate sensitizing dye is used depending on the wavelength of the image exposure light source. For example, the xanthene dyes described in JP-A-4-221958, JP-A-4-219756, etc .; JP-A-3- Cmarin-based dyes having a heterocycle described in JP-A-239703, JP-A-5-289335, etc .; 3-Ketokumarin-based dyes described in JP-A-3-239703, JP-A-5-289335, etc .; Pyrromethene dyes described in JP-A-6-19240 and the like; JP-A-47-2528, JP-A-54-155292, JP-A-45-373777, JP-A-48-84183, JP-A. Japanese Patent Application Laid-Open No. 52-112681, Japanese Patent Application Laid-Open No. 58-15503, Japanese Patent Application Laid-Open No. 60-88805, Japanese Patent Application Laid-Open No. 59-56403, Japanese Patent Application Laid-Open No. 2-69, Japanese Patent Application Laid-Open No. 57-16888 , JP-A-5-107761, JP-A-5-210240, JP-A-4-288818, and the like, and examples thereof include dyes having a dialkylaminobenzene skeleton.
(E3) The sensitizing dye may also be used alone or in combination of two or more.

In the colored resin composition of the present invention, the content ratio of these (E) photopolymerization initiation components is usually 0.1% by mass or more, preferably 0.5% by mass or more, and more preferably 1% by mass in the total solid content. % Or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, particularly preferably 7% by mass or more, and usually 40% by mass or less, preferably 30% by mass or less, more preferably 20% by mass. % Or less, more preferably 15% by mass or less, and particularly preferably 12% by mass or less. When it is set to the lower limit value or more, the decrease in sensitivity to the exposed light tends to be suppressed, and when it is set to the upper limit value or less, the decrease in the solubility of the unexposed portion in the developer and the accompanying development defect can be suppressed. There is.

In the colored resin composition of the present invention, the content ratio of these (E1) photopolymerization initiators is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and 1% by mass or more in the total solid content. More preferably, 3% by mass or more is further preferable, 5% by mass or more is particularly preferable, 7% by mass or more is most preferable, 40% by mass or less is preferable, 30% by mass or less is more preferable, and 20% by mass or less. Is even more preferable, 15% by mass or less is even more preferable, and 12% by mass or less is particularly preferable. When it is set to the lower limit value or more, the decrease in sensitivity to the exposed light tends to be suppressed, and when it is set to the upper limit value or less, the decrease in the solubility of the unexposed portion in the developer and the accompanying development failure are suppressed. There is a tendency to be able to do it.

[(E') Thermal polymerization initiation component]
Specific examples of the (E') thermal polymerization initiator component that may be contained in the colored resin composition of the present invention include azo compounds, organic peroxides, hydrogen peroxide and the like. Of these, azo compounds are preferably used. More specifically, for example, the thermal polymerization initiation component described in International Publication No. 2009/107734 and the like can be used.
These thermal polymerization initiation components may be used alone or in combination of two or more.

[Other optional ingredients]
In addition to the above components, the colored resin composition of the present invention comprises at least one of a surfactant, an organic carboxylic acid and an organic carboxylic acid anhydride, a thermosetting compound, a plasticizing agent, a thermal polymerization inhibitor and a storage stabilizer. , A surface protectant, an adhesion improver, a development improver and the like may be contained. As these optional components, for example, various compounds described in JP-A-2007-113000 can be used. When the pigment is contained, a dispersant or a dispersion aid may be contained.

[Dispersant]
When the colored resin composition of the present invention contains a pigment, it is preferable that the colored resin composition further contains a dispersant.
The dispersant in the present invention is not particularly limited as long as the pigment can be dispersed and stable.
For example, cationic, anionic, nonionic, amphoteric and other dispersants can be used, but polymer dispersants are preferred. Specific examples thereof include block copolymers, polyurethanes, polyesters, alkylammonium salts or phosphate ester salts of polymer copolymers, and cationic comb-type graft polymers. Among these dispersants, block copolymers, polyurethanes, and cationic comb-type graft polymers are preferable. Particularly, a block copolymer is preferable, and among these, a block copolymer composed of an A block having a solvent-friendly property and a B block having a functional group containing a nitrogen atom is preferable.

Specifically, as the B block having a nitrogen atom-containing functional group, a unit structure having at least one of a quaternary ammonium base and an amino group in the side chain can be mentioned, while the quaternary A block has a quaternary solvent. Examples thereof include unit structures having no ammonium base or amino group.
The B block constituting the acrylic block copolymer has a unit structure having at least one of a quaternary ammonium base and an amino group, and is a site having a pigment adsorption function.

When the quaternary ammonium base is contained as the B block, the quaternary ammonium base may be directly bonded to the main chain, or may be bonded to the main chain via a divalent linking group. ..
Examples of such block copolymers include those described in JP-A-2009-025813.

Further, the colored resin composition of the present invention may contain a dispersant other than those described above. Examples of other dispersants include those described in JP-A-2006-343648.
When the colored resin composition of the present invention contains a pigment, the content ratio of the dispersant in the total solid content is 2 to 1000 parts by mass, particularly 5 to 500 parts by mass with respect to 100 parts by mass of the total content of the pigment. In particular, it is preferable to use it so as to be in the range of 10 to 250 parts by mass.
Within the above range, good pigment dispersibility can be ensured without affecting the heat resistance of the triarylmethane compound represented by the formula (I), and the dispersion stability of the pigment can be improved. It is preferable in that it becomes better.

[Dispersion aid]
The colored resin composition of the present invention may contain a dispersion aid. The dispersion aid referred to here may be a pigment derivative, and examples of the pigment derivative include JP-A-2001-22520, JP-A-2001-271004, JP-A-2002-179766, and JP-A-2007-. Various compounds and the like described in Japanese Patent Application Laid-Open No. 113000 and Japanese Patent Application Laid-Open No. 2007-186681 can be used.

The content ratio of the dispersion aid in the colored resin composition of the present invention is usually 0.1% by mass or more, usually 30% by mass or less, preferably 20% by mass or less, based on the total solid content of the pigment. It is preferably 10% by mass or less, more preferably 5% by mass or less. By controlling the addition amount within the above range, the effect as a dispersion aid is exhibited, and it is preferable that the dispersibility and dispersion stability are better.

[Preparation method of colored resin composition]
In the present invention, the colored resin composition can be prepared by an appropriate method, and for example, the (A) coloring material and (C) containing the triarylmethane-based compound represented by the general formula (I). It can be prepared by mixing the binder resin with (B) a solvent and, if necessary, any component used.

Further, a color material-containing liquid containing (A) a color material and (B) a solvent may be prepared, and (C) a binder resin and an arbitrary component may be mixed therewith.
In addition, as a preparation method when a pigment is contained, for example, in a solvent containing a pigment, in the presence of a dispersant and a dispersion aid added as needed, with a part of (C) a binder resin, for example, paint. A pigment dispersion is prepared by mixing and dispersing while pulverizing using a shaker, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. By adding (C) a binder resin,, if necessary, (D) a polymerizable monomer, (E) at least one of a photopolymerization initiating component and a thermal polymerization initiating component, and the like to the pigment dispersion, and mixing them. The method of preparation can be mentioned.
On the other hand, when the pigment is not contained, for example, when only the dye is used as the coloring material, the coloring resin does not require a dispersant or a dispersion aid and does not require a complicated pigment dispersion step. The composition can be produced at low cost.

[Method for evaluating transfer dyeing of colored resin composition]
The transfer dye transfer evaluation method is not particularly limited, but as described in Examples described later, a substrate having a solid cured film having a hue different from that of the colored resin composition of the present invention is prepared, and the colored resin composition of the present invention is prepared. Is applied onto the solid film, exposed, developed, and cured through a mask to form a pattern having rectangular or dot-shaped holes, and a transmission image including the holes and their edges is obtained, and the light and darkness thereof is obtained. It can be evaluated by analyzing the profile. In this case, it is desirable that the hole has a diameter of about 30 to 40 μm from the viewpoint of development and the resolution of the optical microscope. Further, the analysis of the light / dark profile may be a line analysis, or a surface analysis targeting a surface including a hole and its edge is desirable from the viewpoint of suppressing noise.
As another method, an evaluation method using an optical system such as Otsuka Denshi's microspectroscopy device "Highly delicate CF substrate optical measuring device LCF-100MA-SE", in which the beam is sufficiently narrowed and the light collection is good, is used. , The above-mentioned method of performing the light-dark profile analysis after obtaining the correlation curve with the microspectroscopy.

[Application of colored resin composition]
The colored resin composition of the present invention is usually in a state in which all the constituent components are dissolved or dispersed in a solvent. Such a colored resin composition is supplied onto the substrate, and constituent members such as a color filter, a liquid crystal display device, and an organic EL display device are formed.
Hereinafter, as an application example of the colored resin composition of the present invention, an application of a color filter as a pixel and an image display device using them will be described. Specific examples of the image display device include a liquid crystal display device (panel) and an organic EL display device.

<Color filter>
The color filter of the present invention has pixels formed by using the colored resin composition of the present invention.
Hereinafter, a method for forming the color filter of the present invention will be described.
The pixels of the color filter can be formed by various methods. Here, a case of forming by a photolithography method using a photopolymerizable colored resin composition will be described as an example, but the production method is not limited to this.

First, a black matrix is formed on the surface of the substrate so as to partition the portion forming the pixel, if necessary, and the colored resin composition of the present invention is applied onto the substrate and then prebaked. The solvent is evaporated to form a coating film. Next, the coating film is exposed via a photomask, then developed with an alkaline developer to dissolve and remove the unexposed portion of the coating film, and then post-baked to obtain red, green, and blue colors. A color filter can be produced by forming a pixel pattern.

In the present invention, it is particularly preferable that the pixels formed by using the colored resin composition of the present invention are blue pixels.
The substrate used for forming the pixels is not particularly limited as long as it is transparent and has appropriate strength, but for example, a polyester resin, a polyolefin resin, a polycarbonate resin, an acrylic resin, and a thermoplastic resin. Examples include sheets, epoxy resins, thermosetting resins, and various types of glass.

Further, if desired, these substrates may be subjected to appropriate pretreatment such as a thin film forming treatment with a silane coupling agent or a urethane resin, a surface treatment such as a corona discharge treatment or an ozone treatment.
When the colored resin composition is applied to the substrate, examples thereof include a spinner method, a wire bar method, a flow coat method, a slit and spin method, a die coat method, a roll coat method, and a spray coat method. Of these, the slit-and-spin method and the die coat method are preferable.

The thickness of the coating film is usually 0.2 to 20 μm, preferably 0.5 to 10 μm, and particularly preferably 0.8 to 5.0 μm as the film thickness after drying.
Within the above range, it is preferable in that the gap adjustment in the pattern development and the liquid crystal cell formation step is easy, and the desired color development is easy.
As the radiation used for exposure, for example, visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like can be used, but radiation having a wavelength in the range of 190 to 450 nm is preferable.

The light source for using the radiation having a wavelength of 190 to 450 nm used for image exposure is not particularly limited, but for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, and the like. Lamp light sources such as medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps; laser light sources such as argon ion lasers, YAG lasers, excima lasers, nitrogen lasers, helium cadmium lasers, and semiconductor lasers can be mentioned. An optical filter can also be used when irradiating light of a specific wavelength for use.

The exposure amount of radiation is preferably 10 to 10,000 J / m ² .
Examples of the alkaline developing solution include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, and sodium phosphate. Inorganic alkaline compounds such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide; mono-ethanolamine, di-ethanolamine, tri-ethanolamine, mono-methylamine, Di-methylamine, tri-methylamine, mono-ethylamine, di-ethylamine, tri-ethylamine, mono-isopropylamine, di-isopropylamine, n-butylamine, mono-isopropanolamine, di-isopropanolamine, tri-isopropanolamine , Ethyleneimine, ethylenedimin, tetramethylammonium hydroxide (TMAH), an aqueous solution of an organic alkaline compound such as choline is preferable.

An appropriate amount of a water-soluble organic solvent such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, or a surfactant can be added to the alkaline developer. After alkaline development, it is usually washed with water.
As the developing method, any one of a dipping developing method, a spray developing method, a brush developing method, an ultrasonic developing method and the like can be used. The developing conditions are preferably 5 to 300 seconds at room temperature (23 ° C.).

The conditions of the development process are not particularly limited, but the development temperature is usually in the range of 10 ° C. or higher, particularly 15 ° C. or higher, further 20 ° C. or higher, and usually 50 ° C. or lower, particularly 45 ° C. or lower, further 40 ° C. or lower. Is preferable. The developing method can be any one of a dipping developing method, a spray developing method, a brush developing method, an ultrasonic developing method and the like.

When the color filter produced in this way is used in a liquid crystal display device, a transparent electrode such as ITO is formed on the image in this state as it is, and used as a part of parts such as a color display and a liquid crystal display device. Although it is used, in order to improve surface smoothness and durability, a top coat layer such as polyamide or polyimide can be provided on the image if necessary. Further, in some applications such as a plane orientation type drive system (IPS mode), a transparent electrode may not be formed. Further, in the vertically oriented drive system (MVA mode), ribs may be formed. Further, instead of the bead spraying type spacer, a pillar structure (photospacer) by a photolithography method may be formed.

<Image display device>
The image display device of the present invention has the color filter of the present invention. Examples of the image display device include a liquid crystal display device and an organic EL display device.

<Liquid crystal display device>
The liquid crystal display device of the present invention uses the above-mentioned color filter of the present invention. The model and structure of the liquid crystal display device of the present invention are not particularly limited, and the liquid crystal display device of the present invention can be assembled according to a conventional method using the color filter of the present invention.
For example, the liquid crystal display device of the present invention can be formed by the method described in "Liquid Crystal Display Handbook" (Nikkan Kogyo Shimbun, published on September 29, 1989, by the 142nd Committee of the Japan Society for the Promotion of Science).

<Organic EL display device>
When creating an organic EL display device having the color filter of the present invention, for example, as shown in FIG. 7, on a transparent support substrate 10 on a blue color filter in which pixels 20 are formed by the colored resin composition of the present invention. A multicolored organic EL element is manufactured by laminating the organic illuminant 500 via the organic protective layer 30 and the inorganic oxide film 40.

As a method of laminating the organic illuminant 500, a method of sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 on the upper surface of the color filter, or Examples thereof include a method of bonding the organic light emitter 500 formed on another substrate onto the inorganic oxide film 40. The organic EL element 100 produced in this way can be applied to both a passive drive type organic EL display device and an active drive type organic EL display device.

Next, the present invention will be described in more detail with reference to synthetic examples, examples and comparative examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.

<Dye synthesis>
(Synthesis Example 1: Synthesis of Dye 1)

4,4'-Biohexanone (Tokyo Kasei Co., Ltd. product, 2.00 g, 10.3 mmol) and 1-naphthylamine (Tokyo Kasei Co., Ltd. product, 3.24 g, 22.6 mmol) were diluted with methylene chloride (60 mL) and acetic acid (60 mL) was used. 2.4 mL) was added. Sodium Triacetoxyborohydride (Tokyo Kasei Co., Ltd., 10.9 g, 41.2 mmol) was added to the ice-cooled solution, the temperature was raised to room temperature, and the mixture was stirred for 16 hours. 1N hydrochloric acid (20 mL) was added to the reaction solution, 1N aqueous sodium hydroxide solution (20 mL) was further added, water (100 mL) was added, the mixture was extracted with chloroform (100 mL), and the solvent was distilled off. Methanol (60 mL) and ethyl acetate (3 mL) were added to the obtained residue, the mixture was stirred for 30 minutes, and the precipitated solid was filtered to obtain powdery compound 1 (6.5 g, yield: quantitative). ..

Compound 2 was synthesized by the method described in JP-A-2015-127407. This compound 2 (2.06 g, 4.90 mmol) and compound 1 (1.0 g, 2.23 mmol) were diluted with toluene (40 mL), and phosphorus oxychloride (manufactured by Kishida Chemical Co., Ltd., 0.52 mL, 5.58 mmol). Was added, and the mixture was heated under reflux for 20 hours. After cooling the reaction solution to room temperature, the supernatant was removed by decantation, water (150 mL) and chloroform (500 mL) were added to the solid portion for extraction, and the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (N60 silica gel neutral 500 mL manufactured by Kanto Kagaku Co., Ltd., chloroform: methanol (volume ratio) = 100/6 to 100/10), and the obtained solid was further purified by ethyl acetate (N60 silica gel neutral 500 mL, chloroform: methanol (volume ratio) = 100/6 to 100/10). It was washed with 200 mL) and filtered to obtain compound 3 (820 mg, yield 28%) as a blue powder.

Compound 4 was synthesized by the method described in Synthesis Example 1 of JP2013-087248. Water (17 mL) was added to compound 4 (2.72 mmol), and a solution of cyanuric chloride (0.5 g, 2.72 mmol manufactured by Wako Chemical Co., Ltd.) suspended in acetone (2 mL) was 0 at pH = 4-6. The mixture was added while maintaining ~ 5 ° C., and the mixture was further stirred for 1.5 hours. Then, at room temperature at pH = 6-7, a solution of a mixture of aniline (0.25 g, 2.72 mmol) and 35 mass% hydrochloric acid (0.28 mL) in water (1 mL) was added, and an additional 0.5 was added. Stir for hours. Then, a solution prepared by dissolving a mixture of aniline (1.0 g, 10.88 mmol) and 35 mass% hydrochloric acid (1.12 mL) in water (2 mL) was added, and the pH was set to 70 ° C. at an outside temperature of 70 ° C. for 8 hours. Stirred. The obtained reaction solution was cooled to room temperature and then filtered to obtain Compound 5 (1.22 g, yield 76%).

Compound 3 (400 mg, 0.30 mmol) was diluted with methanol (200 mL), compound 5 (pure content of 580 mg, 0.69 mmol with a purity of 70%) was added, and the mixture was stirred at room temperature for 18 hours. The reaction solution was added to water (300 mL), the precipitated solid was collected by filtration, and silica gel column chromatography (N60 silica gel neutral 200 mL manufactured by Kanto Kagaku Co., Ltd., chloroform: methanol (volume ratio) = 100/6 to 100/10) To obtain dye 1 (110 mg, yield 25%).
By mass spectrometry (MALDI-MS), 1/2 of the molecular ion of the divalent target cation part and the molecular ion of the monovalent target anion part were confirmed, and the dye (dye 1) represented by the above formula was used. Identified to be.

(Synthesis Example 2: Synthesis of Dye 2)

1-bromonaphthalene (Tokyo Kasei Co., Ltd., 26.0 g, 126 mmol), 4,4'-methylenebis (2-methylcyclohexielamine) (isomer mixture) (Tokyo Kasei Co., Ltd. product, 10.0 g, 41.9 mmol) Toluene (200 mL), tert-butoxysodium (16.4 g, 168 mmol), (±) -2,2'-bis (diphenylphosphino) -1,1'-binaphthyl (Tokyo Kasei Co., Ltd., 390 mg). , 0.63 mmol), tris (dibenzylideneacetone) dipalladium (0) (384 mg, 0.42 mmol) was added, and the mixture was heated and refluxed for 1 hour under a nitrogen atmosphere. After cooling the reaction solution, water (200 mL) was added, and the mixture was extracted with ethyl acetate (200 mL). The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (N60 silica gel neutral 600 mL manufactured by Kanto Kagaku Co., Ltd., normal hexane: ethyl acetate (volume ratio) = 100/5 to 100/10) to purify the compound. 6 (9.9 g, yield 50%) was obtained.

Compound 7 was synthesized from compound 6 and compound 2 in the same manner as in compound 3.

Dye 2 was synthesized from compound 7 and compound 5 in the same manner as dye 1.
By mass spectrometry (MALDI-MS), 1/2 of the molecular ion of the divalent target cation part and the molecular ion of the monovalent target anion part were confirmed, and the dye (dye 2) represented by the above formula was used. Identified to be.

(Synthesis Example 3: Synthesis of Comparative Dye 1)

Compound 8 was synthesized by the method described in International Publication No. 2012/144520, and compound 9 was synthesized from compound 2 and compound 8 by the same method as that for compound 3.

Comparative dye 1 was synthesized from compound 9 and compound 5 by the same method as for dye 1.

(Synthesis Example 4: Synthesis of Comparative Dye 2)

Compound 11 was obtained from compound 10 and compound 2 in the same manner as in compound 3.

The comparative dye 2 was obtained from the compound 11 and the compound 5 by the same method as that of the dye 1.

(Synthesis Example 5: Synthesis of Comparative Dye 3)

The compound 12 was synthesized by the method described in JP-A-2015-127407, and the comparative dye 3 was synthesized from the compound 12 and the compound 5 by the same method as that of the dye 1.

(Synthesis Example 6: Synthesis of Resin A)
145 parts by mass of PGMEA (propylene glycol monomethyl ether acetate) was stirred while substituting with nitrogen, and the temperature was raised to 120 ° C. To this, 10 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate and 66 parts by mass of monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were added dropwise, and 2.2'-azobis-2-methyl. 8.47 parts by mass of butyronitrile was added dropwise over 3 hours, and stirring was continued at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was replaced with air, 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 43.2 parts by mass of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Then, 56.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added, and the mixture was reacted at 100 ° C. for 3.5 hours. The weight average molecular weight Mw of the resin A thus obtained measured by GPC was about 8400, and the acid value in terms of solid content was 80 mgKOH / g. PGMEA was added to this resin solution so that the solid content was 44% by mass, and the resin A was used.

(Synthesis Example 7: Synthesis of Dispersed Resin A)
A separable flask equipped with a cooling tube was prepared as a reaction vessel, 400 parts by mass of propylene glycol monomethyl ether acetate was charged, and after nitrogen substitution, the temperature of the reaction vessel was raised to 90 ° C. by heating in an oil bath while stirring. bottom.

On the other hand, in the monomer tank, 30 parts by mass of dimethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, 60 parts by mass of methacrylic acid, 110 parts by mass of cyclohexyl methacrylate, and t-butylperoxy-2-ethyl. 5.2 parts by mass of hexanoate and 40 parts by mass of propylene glycol monomethyl ether acetate were charged, and 5.2 parts by mass of n-dodecylmercaptan and 27 parts by mass of propylene glycol monomethyl ether acetate were charged in the chain transfer agent tank, and the temperature of the reaction tank was charged. Was stabilized at 90 ° C., and then dropping was started from the monomer tank and the chain transfer agent tank to start the polymerization. The dropping was carried out over 135 minutes while keeping the temperature at 90 ° C., and 60 minutes after the dropping was completed, the temperature was raised to 110 ° C.

After maintaining 110 ° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 5/95 (v / v) mixed gas was started. Next, 39.6 parts by mass of glycidyl methacrylate, 0.4 parts by mass of 2,2'-methylenebis (4-methyl-6-t-butylphenol), and 0.8 parts by mass of triethylamine were charged in the reaction vessel, and the temperature was 110 ° C. as it was. Was reacted for 9 hours.
The mixture was cooled to room temperature to obtain a polymer solution (solid content concentration 40% by mass, PGMEA solution) having a weight average molecular weight (Mw) of 8000 and an acid value of 101 mgKOH / g.

(Synthesis Example 8: Synthesis of Photopolymerizable Monomer A)
In the presence of 49 parts by mass of succinic anhydride, 2.5 parts by mass of triethylamine, and 0.25 parts by mass of hydroquinone in 1000 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 51 mgKOH / g). Photopolymerizable at 100 ° C. for 5 hours and containing the anhydrous succinic acid modified product of dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate shown below at a ratio of 25:25:50 (mass ratio). Monomer A was obtained, and PGMEA was further added to bring the solid content concentration to 50% by mass.

(Synthesis Example 9: Initiator Synthesis)
3- (2-Acetoxyimino-1,5-dioxo-5-methoxypentyl) -9-ethyl-6- (o-toroil) -9H-carbazole was synthesized by the method described in International Publication No. 2009/131189. ..

<Preparation of blue colored resin composition>
The above-mentioned dyes 1 and 2, the comparative dyes 1, 2 and 3 and the resin A obtained in Synthesis Example 6 are mixed with other components so as to have the composition shown in Table 1 below to obtain a colored resin composition. Prepared.

The numerical values in the upper part of Table 1 represent the content ratio (mass%) of each component to be added in the colored resin composition, and the numerical values in () in the lower part indicate the content ratio of each component in the total solid content. Represents (mass%).
At the time of mixing, the mixture was stirred for 1 hour or more until each component was sufficiently mixed, and finally filtered through a 5 μm piece-shaped filter to remove foreign substances.
Dyes 1 and 2 were used for the colored resin compositions of Examples 1 and 2, and comparative dyes 1, 2 and 3 were used for the colored resin compositions of Comparative Examples 1, 2 and 3.

Each compound in Table 1 is as follows.
DPHA: Dipentaerythritol hexaacrylate F559: Perfluoroalkyl group-containing oligomer (manufactured by DIC Corporation)
PGMEA: Propylene Glycol Monomethyl Ether Acetate

<Preparation of blue dye solution>
The dye 2 and the comparative dyes 1 and 2 are weighed by 2.5 parts by mass, mixed with 97.5 parts by mass of cyclohexanone, stirred for about 30 minutes until each dye is sufficiently dissolved, and then ultrasonically dispersed for 10 minutes. Filtration was performed with a 0.2 μm piece-shaped filter to obtain blue dye solutions 1 to 3.

<Preparation of red pigment dispersion>
Propylene glycol monomethyl ether acetate (PGMEA) 73.48 parts by mass, as a red pigment C.I. I. 13.89 parts by mass of Pigment Red (PR) 254, 5.26 parts by mass of DISPERBYK-LPN6919 (solid content concentration 60% by mass, manufactured by Big Chemie) and dispersion resin A (solid content concentration 40% by mass) as a dispersant. 7.37 parts by mass of PGMEA solution) was mixed and stirred with a stirrer for 3 hours to prepare a mill base having a solid content concentration of 20% by mass.
This mill base was dispersed using 600 parts by mass of 0.5 mmφ zirconia beads in a bead mill apparatus at a peripheral speed of 10 m / s and a residence time of 4 hours to obtain a red pigment dispersion liquid.

<Preparation of red colored resin composition>
The resin A obtained in Synthesis Example 6 was mixed with the red pigment dispersion obtained by the above method with other components so as to have the composition shown in Table 2 below to prepare a red colored resin composition. ..
Upon mixing, the mixture was stirred for 30 minutes until each component was sufficiently mixed, then ultrasonically dispersed for 10 minutes, and finally filtered through a 5 μm piece-shaped filter to remove foreign substances.

Each compound in Table 2 is as follows.
PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether F559: Perfluoroalkyl group-containing oligomer (manufactured by DIC Corporation)

<Evaluation of brightness and heat resistance>
Each colored resin composition prepared in the above <Preparation of blue colored resin composition> was spin-coated on a glass substrate cut into 5 cm squares, and the chromaticity after firing at 230 ° C. for 30 minutes was sx = 0. It was applied so that 140 and sy = 0.120. Next, after drying under reduced pressure, it was prebaked on a hot plate at 80 ° C. for 3 minutes. Then, after full exposure with an exposure amount of 60 mJ / cm ² , firing was performed at 230 ° C. for 30 minutes in a clean oven.

The spectral transmittance of the coated sample prepared by the above method was measured with a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.), and the chromaticity (C light source) and the brightness in the XYZ color system were calculated. Further, the above-mentioned coated sample is further baked in a clean oven at 230 ° C. for 30 minutes, the spectral transmittance is measured with a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.), and the chromaticity (C light source) in the XYZ color system is measured. The color difference (ΔE * ab) after 30 minutes at 230 ° C and 60 minutes at 230 ° C was evaluated as heat resistance, and the results are summarized in Table 3.

<Evaluation of light resistance>
Each blue dye solution prepared in the above <Preparation of blue dye solution> is applied onto a glass substrate cut into 5 cm squares by a spin coating method so that the film thickness is about 2 μm, and then dried under reduced pressure. , Bake on a hot plate at 100 ° C. for 5 minutes to obtain a blue colored film. The spectral transmittance of the obtained film was measured with a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.), and the chromaticity and brightness were calculated. Next, it was set on a weatherometer Ci4000 (manufactured by Atlas) via a polarizing plate and irradiated with pseudo-sunlight for 20 hours. The absorption maximums of the absorption spectra before and after 20-hour irradiation were compared, and the value (%) calculated as the absorbance after irradiation / the absorbance before irradiation × 100 was evaluated as light resistance and summarized in Table 3.

<Method of preparing a sample with a pattern for dye transfer evaluation>
After UV / O ₃ treatment on a glass substrate cut into 5 cm squares for 1 minute, the red colored resin composition prepared in the above <Preparation of red colored resin composition> is applied by a spin coating method, and dried under reduced pressure. It was prebaked on a hot plate at 80 ° C. for 3 minutes, then exposed to the entire surface at an exposure amount of 60 mJ / cm ² , and then baked in a clean oven at 230 ° C. for 30 minutes to provide a red cured layer.

The surface was subjected to UV / O ₃ treatment for 30 seconds, and each of the colored resin compositions of Examples 1 and 2 and Comparative Examples 1 to 3 was spin-coated under the condition that the film thickness was about 3 μm, and the surface was spin-coated onto the red cured layer. A two-layer sample on which the blue coating layer was laminated was obtained, dried under reduced pressure, and then prebaked on a hot plate at 80 ° C. for 3 minutes. Further, a mask having a negative pattern (coating portion) of dots having a diameter of 30 to 35 μm is placed on the film surface via a spacer, exposed at an exposure amount of 60 mJ / cm ² , and then a potassium hydroxide developer (developed by Hayashi Pure Chemical Industries, Ltd.). Develop with (2.2 g of liquid 75KH02PC 2.2 g diluted with 200 cc of water), wash with water, dry with compressed air, bake at 230 ° C. for 30 minutes in a clean oven, and cure blue with holes on the red cured layer. A sample having a layered pattern for dye transfer evaluation was obtained.
In Comparative Examples 1 and 2, the heat resistance was poor, and the absorbance at the maximum absorption wavelength decreased by 27% and 66% in the absorption spectrum by firing at 230 ° C. for 30 minutes, which was necessary for the dye transfer evaluation, and the fading was remarkable. Therefore, the evaluation of dye transfer could not be carried out.

<Dye transfer measurement method>
Using the sample having the pattern for dye transfer evaluation prepared in the above <Method for producing a sample having a pattern for dye transfer evaluation>, the dye transfer measurement was carried out by the following procedure.
First, using a transmission microscope equipped with a digital CCD camera (Nikon LSI inspection microscope Eclipse L200D, camera is 3CD digital MEGA pixels ADP-240), a transmission image of the field of view including the hole and the blue pattern surrounding it is taken as shown in FIG. bottom.

Next, in the transmission image, a rectangular area including both edges of the hole and the blue pattern surrounding the hole as shown in FIG. 1C and including about half of the hole is targeted, and the light and darkness thereof is used by image analysis software. The profile was analyzed and a graph as shown in FIG. 2 was obtained.

Originally, the red dot pattern has high brightness, but when the dye contained in the blue pattern causes dye transfer, the blue dye is mixed into the red dot pattern from the edge of the blue pattern as a starting point, and the red dot is used. The brightness of the pattern decreases. Therefore, the brightness plot profile obtained by the above analysis is a steep convex profile in which the brightness increases sharply from the edge toward the center of the pattern as shown in FIG. 2a when there is no dye transfer. Therefore, when the dye transfer is clearly present, the profile has a convex shape in which the brightness gradually increases from the edge toward the center of the pattern as shown in FIG. 2b. However, when dye transfer is progressing, blue is also mixed in the center of the red dot pattern, the maximum brightness of the convex profile decreases, and both ends of the plot profile tend to tilt slowly. Be done.

The plot profiles of the transfer evaluation results of Examples 1 and 2 and Comparative Example 3 are shown in FIGS. 3, 4 and 5, respectively. The horizontal axis of the profile represents the distance, and the distance per memory is 27 μm. The vertical axis represents gray scale.
The dye transfer determination was made based on the closeness between the trapezoidal figure drawn by connecting the horizontal line corresponding to the maximum brightness and the tangent line at the half value of the maximum brightness in the plot profile and the plot profile. The results are shown in Table 3.

From Table 3, the colored resin compositions of Examples 1 and 2 contain a triarylmethane-based compound having a specific multimer structure represented by the general formula (I), and thus have luminance, heat resistance, and transfer. It was found that all of the dye-suppressing properties were good. It was also found that the colored resin composition of Example 2 had good light resistance.

On the other hand, although the colored resin compositions of Comparative Examples 1 and 2 contain a triarylmethane-based compound having a dimeric structure linked at the terminal of a naphthyl group, the carbon atom adjacent to the amine on the naphthyl group is a secondary carbon atom. The heat resistance and light resistance were extremely low and insufficient. This is because the carbon atom adjacent to the amine on the naphthyl group is not branched, which promotes the activation of the unpaired electron of the amine, making it easier to take an unstable transition state during heating or light irradiation. It is thought that it was a result.

Further, the colored resin composition of Comparative Example 3 has a triarylmethane-based compound having a monomer structure as a coloring material, and although the luminance is good, the dye transfer inhibitory property and the heat resistance are insufficient. there were. This is considered to be insufficient due to the low molecular weight.

On the other hand, the colored resin compositions of Examples 1 and 2 contain a triarylmethane-based compound having a multimeric structure linked at the terminal of a naphthyl group, and the compound is added because it is a high molecular weight compound. It is considered that the molecular motility in the colored resin film under the temperature was lowered and the dye transfer inhibitory property was improved. Furthermore, the branching of the carbon atom adjacent to the amine on the naphthyl group further shields the amine moiety, suppresses the activation of the unpaired electron of the amine, and maintains a stable transition state during heating and light irradiation. It is considered that it became easier to take, the brightness was high, and the heat resistance and light resistance were improved.

From the above, the colored resin composition of the present invention is a colored resin composition having high brightness, satisfying the heat resistance required in the manufacturing process of a color display, and having no transfer to an adjacent coloring pattern. Therefore, it is a color filter. It is suitable for an image display device using the same.

According to the present invention, it is possible to provide a coloring composition having high brightness, satisfying the heat resistance required in the manufacturing process of a color display, and having no transfer to an adjacent coloring pattern. Further, according to the present invention, it is possible to provide a color filter and an image display device that have no dye transfer, have high luminance, and satisfy heat resistance. Therefore, the present invention is useful in applications such as color filters and image display devices.

100 Organic EL element 10 Transparent support substrate 20 pixels 30 Organic protective layer 40 Inorganic oxide film 50 Transparent anode A Red layer B Blue pattern C Transfer analysis area BB Transfer zone

Claims (9)

A colored resin composition containing (A) a coloring material, (B) a solvent, and (C) a binder resin.
A colored resin composition, wherein the coloring material (A) contains a triarylmethane-based compound represented by the following general formula (I).

(In the above formula (I),
[ ^Am- ] is represented by the anion represented by the following formula (A-1) or the following formula (A-2).
Anion . n represents an integer of 1 to 4.
R ¹ to R ⁵ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
R ⁶ represents a l-valent hydrocarbon group which may have a substituent (however, the hydroxyl group is excluded as the substituent). However, in ^R6 , the l carbon atoms bonded to the adjacent N atoms are
Each is a tertiary or quaternary carbon atom independently.
l represents an integer of 2 or more and satisfies the relationship of l = m × n. )

(In the above formula (A-1), R ^1a and R ^2a may independently have a hydrogen atom and a substituent.
Represents an aromatic ring group which may have an alkyl group or a substituent.
R ^3a may have a direct bond, an alkylene group which may have a substituent, or a substituent.
Represents a good divalent aromatic ring group.
R ^4a represents a halogenoalkyl group.
X ¹ to X ³ are independently bonded directly from-(CH ₂ )-, -NH-, -O- and -S-.
Represents at least one group selected from the group, or a group to which two or more of these are bonded. )

(In the above formula (A-2), R ^5a and R ^6a may independently have a hydrogen atom and a substituent.
Represents an aromatic ring group which may have an alkyl group or a substituent.
R ^7a may have a direct bond, an alkylene group which may have a substituent, or a substituent.
Represents a good divalent aromatic ring group.
R ^8a and R ^9a each independently represent a halogenoalkyl group.
X4 to X6 are independently bonded directly from-(CH ^{2 )} -, _-NH- , -O- and -S-.
Represents at least one group selected from the group, or a group to which two or more of these are bonded. ) The colored resin composition according to claim 1, wherein the hydrocarbon group in R ⁶ has 6 or more carbon atoms. The colored resin composition according to claim 1 or 2 , further containing (D) a polymerizable monomer. Claim 1 further contains (E) a photopolymerization initiation component and / or (E') a thermal polymerization initiation component.
The colored resin composition according to any one of 3 to 3 . The colored resin composition according to any one of claims 1 to 4 , wherein the coloring material (A) further contains a pigment. A color filter having pixels formed by using the colored resin composition according to any one of claims 1 to 5 . An image display device having the color filter according to claim 6 . A triarylmethane compound represented by the following general formula (I).

(In the above formula (I),
[ ^Am- ] is represented by the anion represented by the following formula (A-1) or the following formula (A-2).
Anion . n represents an integer of 1 to 4.
R ¹ to R ⁵ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
R ⁶ represents a l-valent hydrocarbon group which may have a substituent (however, the hydroxyl group is excluded as the substituent). However, in ^R6 , the l carbon atoms bonded to the adjacent N atoms are
Each is a tertiary or quaternary carbon atom independently.
l represents an integer of 2 or more and satisfies the relationship of l = m × n. )

(In the above formula (A-1), R ^1a and R ^2a may independently have a hydrogen atom and a substituent.
Represents an aromatic ring group which may have an alkyl group or a substituent.
R ^3a may have a direct bond, an alkylene group which may have a substituent, or a substituent.
Represents a good divalent aromatic ring group.
R ^4a represents a halogenoalkyl group.
X ¹ to X ³ are independently bonded directly from-(CH ₂ )-, -NH-, -O- and -S-.
Represents at least one group selected from the group, or a group to which two or more of these are bonded. )

(In the above formula (A-2), R ^5a and R ^6a may independently have a hydrogen atom and a substituent.
Represents an aromatic ring group which may have an alkyl group or a substituent.
R ^7a may have a direct bond, an alkylene group which may have a substituent, or a substituent.
Represents a good divalent aromatic ring group.
R ^8a and R ^9a each independently represent a halogenoalkyl group.
X4 to X6 are independently bonded directly from-(CH ^{2 )} -, _-NH- , -O- and -S-.
Represents at least one group selected from the group, or a group to which two or more of these are bonded. ) The triarylmethane-based compound according to claim 8 , wherein the hydrocarbon group in R ⁶ has 6 or more carbon atoms.

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