JP6318920B2 - Colored resin composition, color filter, liquid crystal display device and organic EL display device - Google Patents

Description

  The present invention resides in a colored resin composition, a color filter, a liquid crystal display device, and an organic EL display device.

Flat panel displays such as liquid crystal display devices and organic EL (Electroluminescence) display devices are widely used, and color filters are used for these displays. With the trend of energy saving, color filters are required to have higher color purity, higher brightness, and higher contrast.
Up to now, coloring compositions using pigments have been mainly used as color filter forming materials. In order to obtain high brightness and high contrast, for example, Non-Patent Document 1 specifies the particle size of pigment particles as the color filter forming material. A method of finely dispersing the color to a half or less of the coloration wavelength is disclosed.

  On the other hand, a dye has been developed as a coloring material used in a colored resin composition for a color filter. Colored colored resin compositions for color filters are known in which pigment materials and dyes are blended in an arbitrary ratio in addition to pigment materials containing only pigment inks and dyes only. For example, Patent Documents 1 to 3 disclose a colored resin composition in which a pigment and a triarylmethane derivative dye are combined as a coloring material.

JP 2012-201694 A JP 2014-012814 A JP 2012-083552 A

Kiyoshi Hashizume, “Color Material Association”, December 1967, p608

However, in the method described in Non-Patent Document 1, since the blue pigment has a shorter coloration wavelength than other red and green pigments, in this case, further fine dispersion is required, which increases costs and stabilizes after dispersion. Sex matters.
Further, according to the study by the present inventors, the colored resin compositions described in Patent Documents 1 and 2 have a large decrease in luminance due to heating, and the heat resistance upon baking at 230 ° C. required for the color display manufacturing process. It was found that it was not enough. Moreover, with the colored resin composition described in Patent Document 3, it is difficult to achieve both the heat resistance upon baking at 230 ° C. required for the color display manufacturing process and the light resistance required for long-term reliability of the color display. It was found that

As a result of further diligent investigations by the inventors, when a triarylmethane compound having an imide anion or a methide anion and a pigment are used as a color material, the dispersion is one of the components of the pigment ink used as the color material. It has been found that depending on the type of the agent, the luminance drop upon heating changes greatly.
Accordingly, the present invention can greatly suppress the decrease in luminance during heating, satisfies the heat resistance required for the color display manufacturing process, and has a light resistance required for long-term reliability of the color display, It is an object to provide a color filter, a liquid crystal display device, and an organic EL display device.

As a result of intensive studies by the present inventors, when a triarylmethane-based compound having an imide anion or a methide anion is used as a colorant, a dispersant having an acidic group is used as a dispersant, and the triarylmethane-based compound is used. The inventors have found that the above-mentioned problems can be solved by making the substituent on the nitrogen atom of the compound specific, and have completed the present invention.
That is, the gist of the present invention is as follows.

[1] containing (A) a color material, (B) a solvent, (C) a dispersant and (D) a binder resin,
(A) The coloring material contains a triarylmethane compound represented by the following formula (I), and (C) the dispersing agent contains a dispersing agent having an acidic group. Resin composition.

(In the above formula (I),
A ⁻ represents an imide anion or a methide anion.
R ^{1 to} R ⁴ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
R ⁵ and R ⁶ each independently represents an aromatic ring group which may have a substituent.
Further, the benzene ring and naphthalene ring in the above formula (I) may further have an arbitrary substituent. )
[2] The colored resin composition according to [1], wherein the dispersant having an acidic group is a dispersant having an acid value larger than an amine value.
[3] The colored resin composition according to [1] or [2], wherein (A) the colorant further contains a pigment.
[4] The colored resin composition according to any one of [1] to [3], wherein A ⁻ in the formula (I) is a disulfonylimide anion.

[5] The colored resin composition according to any one of [1] to [4], further comprising (E) a polymerizable monomer.
[6] The colored resin composition according to any one of [1] to [5], further comprising (F) a photopolymerization initiation system and / or (F ′) a thermal polymerization initiation system.
[7] A color filter having pixels formed using the colored resin composition according to any one of [1] to [6].
[8] A liquid crystal display device comprising the color filter according to [7].
[9] An organic EL display device comprising the color filter according to [7].

  According to the present invention, it is possible to greatly suppress a decrease in luminance during heating, satisfy the heat resistance required for the color display manufacturing process, and have a light resistance required for long-term reliability of the color display. , Color filters, liquid crystal display devices, and organic EL display devices can be provided.

FIG. 1 is a schematic cross-sectional view showing an example of an organic EL element having the color filter of the present invention. FIG. 2 is a graph showing the transmittance of the polarizing plate used in the examples.

Embodiments of the present invention will be described in detail below, 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) acryl”, “(meth) acrylate” and the like mean “at least one of acrylic and methacryl”, “at least one of acrylate and methacrylate”, and the like, for example, “( “Meth) acrylic acid” means “at least one of acrylic acid and methacrylic acid”.

Further, “total solid content” means all components of the colored resin composition of the present invention other than the solvent components described later.
Furthermore, “aromatic ring” means both “aromatic hydrocarbon ring” and “aromatic heterocycle”.
A term such as “CI Pigment Green” means a color material name included in the color index (CI).

  The colored resin composition of the present invention contains (A) a color material, (B) a solvent, (C) a dispersant and (D) a binder resin, and (A) the color material is represented by the following formula (I). The triarylmethane-based compound is contained, and the (C) dispersant contains a dispersant having an acidic group. Furthermore, it is preferable to contain at least one of (E) a polymerizable monomer and (F) a photopolymerization initiation component and (F ′) a thermal polymerization initiation component, and may contain other components as necessary. .

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

In the above formula (I),
A ⁻ represents an imide anion or a methide anion.
R ^{1 to} R ⁴ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
R ⁵ and R ⁶ each independently represents an aromatic ring group which may have a substituent.
Further, the benzene ring and naphthalene ring in the above formula (I) may further have an arbitrary substituent.

(R ¹ ~R ⁴⁾
R ^{1 to} R ⁴ each independently represents 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 ⁴ include a linear, branched or cyclic alkyl group. The carbon number is preferably 30 or less, more preferably 12 or less, and usually 1 or more. By making the upper limit value or less, in the colored resin composition, the solubility of the triarylmethane-based compound can be appropriately adjusted, and since effective interaction between the cation and the anion occurs, the heat resistance and There is a tendency for light resistance to improve.

  Specific examples 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, phenethyl group, 3- A methylbutyl group, 2-ethoxyethyl group, etc. are mentioned. Among these, a linear alkyl group is preferable from the viewpoint of association between molecules represented by the formula (I) and electrostatic interaction with an anion.

Examples of the aromatic ring group in R ^{1 to} R ⁴ include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number is preferably 30 or less, more preferably 12 or less, and preferably 6 or more. By making it not more than the above upper limit value, the conjugate length becomes appropriate, and the absorption waveform near 500 nm becomes steep, so that a tendency to increase in brightness is seen, and in the colored resin composition, a triarylmethane compound, Since the interaction with other compounds constituting the composition is appropriate, the solubility tends to be adjusted appropriately.

The aromatic hydrocarbon ring group may be a single ring or a condensed ring. For example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene having one free valence. And groups such as a ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
The aromatic heterocyclic group may be a monocyclic ring or a condensed ring. For example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring having one free valence. , Pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring , Benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline Ring, quinazo Non rings include groups such as azulene ring.

Adjacent R ³ and R ⁴ may be linked to form a ring, and the ring may have a substituent. In addition, the ring may be a ring bridged with a heteroatom, and specific examples thereof include the following structures.

From the viewpoint of heat resistance, R ^{1 to} R ⁴ are preferably each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or an optionally substituted phenyl group. It is a group, or when adjacent R ³ and R ⁴ are connected to each other to form a ring. These substituents are also preferable in terms of luminance.

In terms of improving the heat resistance of the compound (I) and the heat resistance of the resulting color filter being excellent, R ¹ and R ² are optionally substituted alkyl groups having 1 to 12 carbon atoms or substituents. It is preferably a phenyl group which may have an alkyl group, and more preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent.

When R ¹ and R ² are an optionally substituted alkyl group having 1 to 12 carbon atoms, it is presumed that the charges in the cation are dispersed by hyperconjugation and the cation is stabilized.
More specifically, the number of carbon atoms of the alkyl group in R ¹ and R ² is such that it does not easily affect the conformation of the triarylmethane skeleton (has little effect on luminance), and the substituent on nitrogen is difficult to desorb. (Compound (I) is stable), preferably 8 or less, more preferably 4 or less, and preferably 2 or more.

In the case where R ¹ and R ² are phenyl groups which may have a substituent, the conjugated system is extended, so that the charge in the cation is dispersed and the cation is stabilized. As described above, it can be considered that as a result of stabilization of the cation, the heat resistance of the obtained color filter is further improved.

In view of excellent brightness of the compound (I), R ³ and R ⁴ are preferably at least one alkyl group which may have a substituent, and from the viewpoint of heat resistance, R ³ and R ⁴ It is preferable that any one of them is an alkyl group which may have a substituent, and the other is a hydrogen atom.
(Combination of R ³ and R ⁴ )

From the viewpoint of luminance, at least one of R ³ and R ⁴ is preferably a linear alkyl group which may have a substituent. Since at least one of R ³ and R ^{4 is} a linear alkyl group which may have a substituent, the solubility is improved, and thus the luminance is considered to be improved.
In this case, both R ³ and R ⁴ may be a linear alkyl group which may have a substituent, and either one of R ³ and R ⁴ may have a substituent. A good linear alkyl group may be used, and the other may be a hydrogen atom. From the viewpoint of heat resistance, it is preferable that either one of R ³ and R ^{4 is} a linear alkyl group which may have a substituent, and the other is a hydrogen atom.

  The linear alkyl group preferably has 12 or less carbon atoms, more preferably 6 or less, and preferably 1 or more, and more preferably 3 or more. Since the interaction with other components constituting the colored resin composition is appropriate by setting the upper limit value or less, the solubility tends to be adjusted appropriately, and the upper limit value or more. There exists a tendency which can suppress the thermal decomposition of a substituent and can improve heat resistance.

Specific examples include a methyl group, an ethyl group, a propyl group, and a butyl group. Among these, a butyl group is preferable from the viewpoint of heat resistance.
Examples of the substituent that the linear alkyl group may have include those in the substituent group W1 described below. Among these, from the viewpoint of heat resistance, a fluorine atom, a phenyl group, or a tolyl group is preferable, and a fluorine atom is more preferable. Specific examples of the linear alkyl group having a substituent include 4,4,4-trifluorobutyl group, 2-phenylethyl group, 2-tolylethyl group and the like. Among these, 4,4,4-trifluorobutyl group is preferable from the viewpoint of heat resistance.

On the other hand, at least one of R ³ and R ⁴ is preferably an alkyl group having a secondary carbon and optionally having a substituent. By making at least one of R ³ and R ⁴ an alkyl group having a secondary carbon and optionally having a substituent, the heat and light of the molecule represented by formula (I) This substituent is considered to contribute to the improvement of heat resistance and light resistance because the substituents inhibit attacks from other molecules that cause decomposition.
Further, both R ³ and R ⁴ may have a secondary carbon, may be an alkyl group optionally having a substituent, and either one of R ³ and R ⁴ may be a secondary carbon. It is good also as an alkyl group which may have a substituent, and making the other a group other than the alkyl group which has a secondary carbon and may have a substituent. If the substituents of R ³ and R ⁴ are large, steric hindrance may occur, inhibiting the association between molecules represented by the formula (I) and electrostatic interaction with anions, which may reduce heat resistance. Therefore, it is preferable that any one of R ³ and R ^{4 is} a secondary carbon-containing alkyl group which may have a substituent, and the other is a group other than the alkyl group. More preferably, one of them is a secondary carbon, an optionally substituted alkyl group, and the other is a hydrogen atom.

Note that “at least one of R ³ and R ⁴ is a secondary carbon, optionally having a substituent, and an alkyl group” means that at least one of R ³ and R ⁴ is The alkyl group which has a group represented by the following formula (II) and may have a substituent. In addition, * in a formula means a bond.
In the following formula (II), α and β each independently represents an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. The C-α bond represents a bond between the carbon atom and the carbon atom of the substituent α, and the C-β bond similarly represents a bond between the carbon atom and the carbon atom of the substituent β. Α and β may be linked to form a ring, and the ring may have a substituent.

  The alkyl group which has a secondary carbon and may have a substituent is not limited as long as it has a group represented by the above formula (II) and may have a substituent. May be, for example, a group itself represented by the above formula (II), or a group represented by the above formula (II) bonded to an alkylene group which may have a substituent. However, from the viewpoint of increasing the volume around the nitrogen atom, the group itself represented by the above formula (II) is preferable. That is, since this substituent inhibits attacks from other molecules that cause decomposition by light, it tends to contribute to improvement of various physical properties.

  Examples of the alkyl group for α and β include a linear, branched or cyclic alkyl group. The number of carbon atoms including α and β in the number of carbon atoms is preferably 30 or less, more preferably 12 or less, still more preferably 8 or less, and most preferably 6 or less. By setting it to the upper limit or less, in the colored resin composition, the solubility in the solvent of the formula (I) can be appropriately adjusted, and the association between the molecules represented by the formula (I) and cations Since effective interaction with an anion occurs, heat resistance and light resistance tend to be improved.

  Specific examples 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, phenethyl group, 3- A methylbutyl group, 2-ethoxyethyl group, etc. are mentioned. Among these, a linear alkyl group is preferable from the viewpoint of association between molecules represented by the formula (I) and electrostatic interaction with an anion.

  Examples of the aromatic ring group in α and β include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms is preferably 30 or less, more preferably 12 or less, and even more preferably 6 or less. By setting it to the upper limit or less, the solubility in the solvent of the formula (I) can be appropriately adjusted, and the association between the molecules represented by the formula (I) and effective mutual interaction between the cation and the anion can be achieved. Since the action occurs, heat resistance and light resistance tend to be improved.

The aromatic hydrocarbon ring group may be a single ring or a condensed ring. For example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene having one free valence. And groups such as a ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
The aromatic heterocyclic group may be a monocyclic ring or a condensed ring. For example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring having one free valence. , Pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring , Benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline Ring, quinazo Non rings include groups such as azulene ring.

α and β may be linked to form a ring, and the ring may have a substituent.
The ring may be a ring bridged with a heteroatom. The number of carbon atoms of the ring (including C atom bonded to α and β, α and β) is preferably 30 or less, more preferably 12 or less, and even more preferably 8 or less. By setting it to the upper limit or less, the solubility in the solvent of the formula (I) can be appropriately adjusted, and the association between the molecules represented by the formula (I) and effective mutual interaction between the cation and the anion can be achieved. Since the action occurs, heat resistance and light resistance tend to be improved.
In the case where α and β are connected to form a ring, specific examples of the alkyl group having a secondary carbon include the following structures.

Examples of the substituent that the alkyl group in α and β may have include those in the following substituent group W1. Moreover, as a substituent which the aromatic ring group may have, the following substituent group W2 is mentioned, for example. Furthermore, as a substituent which the ring formed by mutually connecting may have, the thing of the following substituent group W3 is mentioned, for example.
As α and β, α and β are preferably included in the number of carbon atoms, and each independently a linear alkyl group having 1 to 12 carbon atoms which may have a substituent, or α and β are linked to each other. To form a ring. More preferably, it is a case where an alkyl group having 2 to 6 carbon atoms which may have a substituent or adjacent α and β having 3 to 10 carbon atoms are connected to each other to form a ring. These substituents tend to improve heat resistance and light resistance because association between the compounds represented by formula (I) and effective interaction between the cation and the anion occur.

The total number of carbon atoms in the alkyl group having a secondary carbon in R ³ and R ⁴ is preferably 30 or less, more preferably 12 or less, further preferably 8 or less, and 6 or less. Most preferred. Usually, it is 3 or more, preferably 4 or more, more preferably 5 or more. By being within the above range, in the colored resin composition, the interaction between the molecules represented by the formula (I) and the electrostatic capacity of the cation and anion within the molecule in the compound represented by the formula (I). Interaction tends to be appropriate and durability can be improved.

  Specific examples of the alkyl group having a secondary carbon include isopropyl group, s-butyl group, 1-methylpropyl group, 1-ethylpropyl group, 1-methylbutyl group, cyclopentyl group, 1-methylpentyl group, 1- Ethylbutyl group, 1-propylbutyl group, 1-ethylpentyl group, 1-propylpentyl group, 1-butylpentyl group, 1-methylhexyl group, 1-ethylhexyl group, 1-propylhexyl group, 1-butylhexyl group, 1-propylhexyl group, cyclohexyl group, 2-methylcyclohexyl group, 2-ethylcyclohexyl group, 2-propylcyclohexyl group, 2-isopropylcyclohexyl group, 2-cyclopropylcyclohexyl group, 2-butylcyclohexyl group, 2 -S-butylcyclohexyl group, 2-t-butylcyclohexyl 2-isobutylcyclohexyl group, 2-cyclobutylcyclohexyl group, 2-pentylcyclohexyl group, 2-cyclopentylcyclohexyl group, 2-cyclohexylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 2,6- Dimethylcyclohexyl group, 2,4-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 2,3-dimethylcyclohexyl group, 3,3, 5-trimethylcyclohexyl group, 4-t-butylcyclohexyl group, 1-ethylheptyl group, 1-methylheptyl group, 1-propylheptyl group, 1-butylheptyl group, 1-pentylheptyl group, 1-hexyl Heptyl, cycloheptyl, 2-methylcycloheptyl, 3-methyl Loheptyl group, 4-methylcycloheptyl group, 2,7-dimethylcycloheptyl group, 1-cyclohexylethyl group, 1-methyloctyl group, 1-ethyloctyl group, 1-propyloctyl group, 1-butyloctyl group, 1 -Pentyloctyl group, 1-hexyloctyl group, 1-heptyloctyl group, cyclooctyl group, 1-methylcyclooctyl group, 2-methylcyclooctyl group, 3-methylcyclooctyl group, 4-methylcyclooctyl group, 2 -An adamantyl group and the like.

  Among these, isopropyl group, s-butyl group, 1-methylpropyl group, 1-ethylpropyl group from the viewpoint of improving durability due to association between molecules represented by formula (I) and electrostatic interaction with anions. Group, 1-methylbutyl group, 1-ethylbutyl group, 1-propylbutyl group, cyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 4-t-butylcyclohexyl group, cyclopentyl group, Or a cyclooctyl group is preferable.

On the other hand, when any one of R ³ and R ^{4 is} a secondary carbon and optionally substituted alkyl group, and the other is a group other than the alkyl group, Examples of the group include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a pentyl group and the like, an alkyl group having 1 to 5 carbon atoms, a hydroxyethyl group, a hydroxypropyl group and the like. 1 to 5 hydroxyalkyl groups, methoxyethyl groups, ethoxyethyl groups, ethoxypropyl groups, butoxyethyl groups, etc., C1-C5 alkoxyalkyl groups, 2-hydroxyethoxy groups, etc., C1-C5 hydroxyalkoxy groups , 2-methoxyethoxy group, 2-ethoxyethoxy group, etc., C1-C5 alkoxy (C1-C5) alkoxy group, 2-sulfoethyl group, carbo Examples include a xylethyl group and a cyanoethyl group.

As a substituent which the alkyl group in R < ¹ > -R < ⁴ > may have, the following substituent group W1 is mentioned, for example. Moreover, as a substituent which the aromatic ring group may have, the following substituent group W2 is mentioned, for example. Furthermore, as a substituent which the ring formed by mutually connecting may have, the thing of the following substituent group W3 is mentioned, for example.

(Substituent group W1)
Fluorine atom, chlorine atom, alkenyl group having 2 to 8 carbon atoms, alkoxyl group having 1 to 8 carbon atoms, phenyl group, mesityl group, tolyl group, naphthyl group, cyano group, acetyloxy group, alkyl having 2 to 9 carbon atoms Carbonyloxy group, sulfamoyl group, alkylsulfamoyl group having 2 to 9 carbon atoms, alkylcarbonyl group having 2 to 9 carbon atoms, phenethyl group, hydroxyethyl group, acetylamide group, and alkyl group having 1 to 4 carbon atoms 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, preferred are an alkoxyl group having 1 to 8 carbon atoms, a cyano group, an acetyloxy group, an alkyl carboxyl group having 2 to 8 carbon atoms, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, and a fluorine atom. .

(Substituent group W2)
Fluorine atom, chlorine atom, alkyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms, alkoxyl group having 1 to 8 carbon atoms, phenyl group, mesityl group, tolyl group, naphthyl group, cyano group, acetyloxy Group, C2-C9 alkylcarbonyloxy group, sulfamoyl group, C2-C9 alkylsulfamoyl group, C2-C9 alkylcarbonyl group, hydroxyethyl group, acetylamide group, C1-C1 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, preferably 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 alkyl carboxyl group having 2 to 8 carbon atoms, a sulfamoyl group, and an alkyl group having 2 to 9 carbon atoms. A famoyl group and a fluorine atom;

(Substituent group W3)
Fluorine atom, chlorine atom, alkyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms, alkoxyl group having 1 to 8 carbon atoms, phenyl group, mesityl group, tolyl group, naphthyl group, cyano group, acetyloxy Group, alkylcarbonyloxy group having 2 to 9 carbon atoms, sulfamoyl group, alkylsulfamoyl group having 2 to 9 carbon atoms, alkylcarbonyl group having 2 to 9 carbon atoms, phenethyl group, hydroxyethyl group, acetylamide group, carbon A dialkylaminoethyl group, a trifluoromethyl group, a trialkylsilyl group having 1 to 8 carbon atoms, a nitro group, or an alkylthio group having 1 to 8 carbon atoms, which is formed by bonding an alkyl group having 1 to 4 carbon atoms.
Among them, preferably 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 alkyl carboxyl group having 2 to 8 carbon atoms, a sulfamoyl group, and an alkyl group having 2 to 9 carbon atoms. A famoyl group and a fluorine atom;

(R ⁵ and R ⁶⁾
R ⁵ and R ⁶ are each independently an aromatic ring group which may have a substituent. In the triarylmethane compound represented by the general formula (I) used in the colored resin composition of the present invention, R ⁵ and R ⁶ are each independently an aromatic ring group which may have a substituent. For this reason, it is considered that the conjugated system of the cation spreads, the charge is stabilized, and the heat resistance and light resistance are improved.
Examples of the aromatic ring group in R ⁵ and R ⁶ include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms is preferably 30 or less, and more preferably 12 or less. The solubility in the solvent of the formula (I) can be appropriately adjusted by setting it to the upper limit or less, and the association between the molecules represented by the formula (I) and the effective interaction between the cation and the anion Therefore, heat resistance and light resistance tend to be improved.
The aromatic hydrocarbon ring group may be a single ring or a condensed ring. For example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene having one free valence. And groups such as a ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

The aromatic heterocyclic group may be a monocyclic ring or a condensed ring. For example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring having one free valence. , Pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring , Benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline Ring, quinazo Non rings include groups such as azulene ring.
R ⁵ and R ⁶ may be connected to R ¹ and R ² to form a ring, respectively, and the ring may have a substituent. The ring may be a ring bridged with a heteroatom. The number of carbon atoms is preferably 28 or less, more preferably 10 or less, and even more preferably 6 or less. Examples of the substituent that the rings formed by being connected to each other may have include those of the aforementioned substituent group W3. These substituents tend to improve heat resistance and light resistance because association between the compounds represented by formula (I) and effective interaction between the cation and the anion occur.

  Among these, from the viewpoint of steep absorption waveform around 500 nm, that is, high brightness, an aromatic hydrocarbon ring group having one free valence is preferable, and monocyclic or bicyclic aromatic carbonization is preferable. It is more preferably a hydrogen ring group, and further preferably a phenyl group.

Examples of the substituent that the aromatic ring group in R ⁵ and R ⁶ may have include those in the above substituent group W2. In particular, from the viewpoint of steep absorption waveform around 500 nm, that is, high brightness, and from the viewpoint of improving heat resistance and light resistance by stabilizing the cation by dispersion of charges in the cation by superconjugation, R ⁵ and R ⁶ The aromatic ring group in is preferably unsubstituted, has an alkyl group as a substituent, or has an alkoxyl group as a substituent, more preferably is unsubstituted or has an alkyl group as a substituent. The number of carbon atoms of the alkyl group and alkoxy group that the aromatic ring group may have is not particularly limited, but from the viewpoint of heat resistance, it is preferably 8 or less, more preferably 4 or less, still more preferably 2 or less, usually 1 That's it.

(Combination of R ^{1 to} R ⁶ )
R ^{1 to} R ⁶ may be appropriately selected from those described above. Specific examples of combinations include those described in Table 1. In addition, the alkyl group, the aromatic ring, and the heterocyclic ring listed in the following table may further contain an arbitrary substituent. C in the table means carbon number.
As a combination of R ^{1 to} R ⁶ , from the viewpoint of heat resistance, the compounds represented by formula (I) are likely to associate with each other, and from other molecules that cause thermal decomposition of the compound represented by formula (I). The number of carbon atoms in which R ³ is a hydrogen atom and R ⁴ may have a substituent, since the electrostatic interaction between the cation and anion due to the steric hindrance of the substituent is not reduced. R ¹ and R ² are each preferably an alkyl group of 1 to 12 and can inhibit attack from other molecules on the carbon atom to which the two benzene rings and naphthalene ring of the triarylmethane skeleton are bonded. An optionally substituted alkyl group having 1 to 12 carbon atoms, an optionally substituted aromatic hydrocarbon ring group having 6 to 12 carbon atoms, or a substituent. It is a good aromatic heterocyclic group having 4 to 12 carbon atoms. It is preferable.
On the other hand, from the viewpoint of steep absorption waveform around 500 nm, that is, high brightness, the spread of the π-conjugated system is avoided and the shape of the absorption spectrum becomes sharp. Therefore, R ¹ and R ² are each independently It is an alkyl group having 1 to 12 carbon atoms that may have a substituent, R ³ is a hydrogen atom, and R ⁴ is an alkyl group having 1 to 12 carbon atoms that may have a substituent. In addition, in addition, since there is no bias of the π-conjugated system and the shape of the absorption spectrum becomes sharp, R ⁵ and R ⁶ may each independently have a substituent having 6 to 12 carbon atoms. The aromatic ring group is more preferable.
The triarylmethane compound represented by the formula (I) is symmetrical in which a nitrogen atom is bonded to the para position of two benzene rings forming the triarylmethane skeleton, and a hydrogen atom is bonded to the ortho position and the meta position. Therefore, it is considered that the spectral shape is better and the luminance is higher than those of other structures having a substituent at the ortho position or the meta position. In addition, compared to the case where a substituent is present at the ortho-position or meta-position, it is considered that the molecular twist due to steric hindrance is reduced and the heat resistance is improved. From the viewpoint of contrasting the molecular structure, it is preferable that R ¹ and R ² are the same group and / or R ⁵ and R ⁶ are the same group.

The benzene ring and naphthalene ring forming the triarylmethane skeleton in formula (I) may have an arbitrary substituent, and examples of the optional substituent include those in the substituent group W2.
In particular, from the viewpoint of luminance, the benzene ring forming the triarylmethane skeleton in the formula (I) is preferably unsubstituted, and in addition, the naphthalene ring is more preferably unsubstituted.

(A ^- About)
In the formula (I), A ⁻ represents an imide anion or a methide anion.

  Since the counter anion of the triarylmethane cation is an imide anion or a methide anion, the charge of the anion is delocalized and the counter anion can be prevented from reacting with the triarylmethane cation by heat and light, improving durability. Tend to.

  Easy to manufacture, the negative charge is delocalized and the anion is stable, and the negative charge is delocalized and the electrostatic interaction with the triarylmethane cation is appropriate. And is preferably a disulfonylimide anion. Although it does not specifically limit about the structure of a disulfonyl imide anion, For example, what is represented by following formula (III) is mentioned.

R ¹¹ and R ¹² each independently represents an alkyl group which may have a substituent, or an alkenyl group which may have a substituent.
R ¹¹ and R ¹² may be connected to each other to form a ring, and the ring may have a substituent.

(About R ¹¹ and R ¹² )
R ¹¹ and R ¹² represent an alkyl group which may have a substituent, or an alkenyl group which may have a substituent.
Examples of the alkyl group for R ¹¹ and R ¹² include linear, branched, or cyclic alkyl groups. The carbon number is preferably 30 or less, more preferably 12 or less, and the carbon number of the linear or branched alkyl is usually 1 or more, and the carbon number of the cyclic alkyl group is usually 3 or more. It is. By setting it within the above range, the electrostatic interaction between the cation and the anion becomes appropriate, and the durability tends to be improved.
Specific examples 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, phenethyl group, 3- Examples thereof include a methylbutyl group, a 2-ethoxyethyl group, a trifluoromethyl group, and a perfluoroalkyl group having 1 to 12 carbon atoms.

Examples of the alkenyl group for R ¹¹ and R ¹² include linear, branched, or cyclic alkenyl groups. The carbon number is preferably 6 or less, and usually 2 or more. By setting it within the above range, the intermolecular interaction of the triarylmethane compound becomes appropriate, and the durability tends to be improved.
Specific examples include vinyl group, allyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, and 3-butenyl group.

Examples of the substituent that these groups may have include those described in the aforementioned substituent groups W1 and W2.
Among these, the alkyl group in R ¹¹ and R ¹² or the substituent of the alkenyl group, in particular, has a tendency that the charge of the anion is more delocalized and the heat resistance of the coloring material is improved. It preferably has a fluorine atom as a substituent.
That is, R ¹¹ and R ¹² are preferably a C 1-12 perfluoroalkyl group in that the anion charge is dispersed and the anion tends to be stabilized.

  More specifically, the anion represented by the formula (III) is preferably the one represented by the following formula (III-1).

  In said formula (III-1), n and n 'represent the integer of 1-8 each independently.

n and n ′ are integers of 1 to 8, but are preferably integers of 1 to 4. n and n ′ may be the same or different.
Specific examples of the sulfonylimide anion when n and n ′ are the same include bis (trifluoromethanesulfonyl) imide, bis (pentafluorobutanesulfonyl) imide and the like.
Specific examples of the sulfonylimide anion when n and n ′ are different include pentafluoroethanesulfonyl trifluoromethanesulfonylimide, trifluoromethanesulfonylheptafluoropropanesulfonylimide, fluorobutanesulfonyl trifluoromethanesulfonylimide, and the like.
Among these, bis (trifluoromethanesulfonyl) imide, where n = n ′ = 1, is particularly preferable because the anion is most stabilized.

On the other hand, in the formula (III), R ¹¹ and R ¹² may be connected to each other to form a ring.
In the case of forming a ring, the group formed by connecting R ¹¹ and R ¹² is particularly preferably a fluoroalkylene group having 2 to 12 carbon atoms.
That is, the anion represented by the formula (III) is preferably an anion represented by the following formula (III-2).

  In the above formula (III-2), n ″ represents an integer of 2 to 12.

n ″ is preferably an integer of 2 to 8 and more preferably 3 in terms of good heat resistance.
A molecular anion with a smaller number of n ″ has a smaller effect of steric repulsion and tends to allow stronger interaction. That is, it is presumed that the smaller the n ″, the greater the interaction between the anion and the cation, the more counterion is stabilized, and the heat resistance of the dye is improved.

  In addition, the metide anion is easy to manufacture, the negative charge is delocalized and the anion is stable, and the negative charge is delocalized and electrostatic interaction with the triarylmethane cation. A trisulfonylmethide anion is preferable in that the action is appropriate. Although it does not specifically limit about the structure of a trisulfonylmethide anion, For example, what is represented by following formula (IV) is mentioned.

R ¹³ , R ¹⁴ and R ¹⁵ each independently represents an alkyl group which may have a substituent, or an alkenyl group which may have a substituent.
R ¹³ , R ¹⁴ and R ¹⁵ may be linked by R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹³ to form a ring, and the ring has a substituent. You may do it.

(About R ¹³ , R ¹⁴ and R ¹⁵ )
R ¹³ , R ¹⁴ and R ¹⁵ represent an alkyl group which may have a substituent or an alkenyl group which may have a substituent.
Examples of the alkyl group for R ¹³ , R ^14, and R ¹⁵ include a linear, branched, or cyclic alkyl group. The carbon number is preferably 30 or less, more preferably 12 or less, and the carbon number of the linear or branched alkyl is usually 1 or more, and the carbon number of the cyclic alkyl group is usually 3 or more. It is. By setting it within the above range, the electrostatic interaction between the cation and the anion becomes appropriate, and the durability tends to be improved.
Specific examples 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, phenethyl group, 3- Examples thereof include a methylbutyl group, a 2-ethoxyethyl group, a trifluoromethyl group, and a perfluoroalkyl group having 1 to 12 carbon atoms.

Examples of the alkenyl group for R ¹³ , R ¹⁴ and R ¹⁵ include linear, branched or cyclic alkenyl groups. The carbon number is preferably 6 or less, and usually 2 or more. By setting it within the above range, the intermolecular interaction of the triarylmethane compound becomes appropriate, and the durability tends to be improved.
Specific examples include vinyl group, allyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, and 3-butenyl group.

Examples of the substituent that these groups may have include those described in the aforementioned substituent groups W1 and W2.
Among these, in particular, as the substituent of the alkyl group or alkenyl group in R ¹³ , R ¹⁴ and R ¹⁵ , the charge of the anion is more delocalized and the heat resistance of the coloring material tends to be improved. In this respect, it is preferable to have a fluorine atom as a substituent.
That is, R ¹¹ and R ¹² are preferably a C 1-12 perfluoroalkyl group in that the anion charge is dispersed and the anion tends to be stabilized.

  More specifically, the anion represented by the formula (IV) is preferably one represented by the following formula (IV-1).

(In the above formula (IV-1), n, n ′ and n ″ each independently represents an integer of 1 to 8.)

n, n ′ and n ″ are integers of 1 to 8, but are preferably integers of 1 to 4.
n, n ′, and n ″ may be the same or different.
Specific examples of the sulfonylmethide anion when n, n ′, and n ″ are all the same include tris (trifluoromethanesulfonyl) methide, tris (pentafluorobutanesulfonyl) methide, and the like.
Specific examples of the sulfonylmethide anion when n, n ′ and n ″ are different from each other include bis (pentafluoroethanesulfonyl) trifluoromethanesulfonylmethide and bis (trifluoromethanesulfonyl) heptafluoropropane. Examples include sulfonylmethide, bis (fluorobutanesulfonyl) trifluoromethanesulfonylmethide, fluorobutanesulfonylpentafluoroethylsulfonyltrifluoromethanesulfonylmethide, and the like.
Among these, tris (trifluoromethanesulfonyl) methide, where n = n ′ = n ″ = 1, is particularly preferable because the anion is most stabilized.

On the other hand, in the formula (IV), R ¹³ , R ¹⁴ and R ¹⁵ may be linked by R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , or R ¹⁵ and R ¹³ to form a ring.
When a ring is formed, the group formed by connecting R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹³ is particularly preferably a fluoroalkylene group having 2 to 12 carbon atoms. .

The compound represented by the formula (I) are, for example, from R ¹ to R ^6, stretched a linker, may form a like a dimer or trimer.
In addition, the presence form of the triarylmethane compound represented by the formula (I) in the colored resin composition is not particularly limited, and may be a dye and / or a pigment. From the standpoint of sufficient solubility of the dye, it is preferably present in the form of a dye.

(Molecular weight)
In the triarylmethane compound represented by the general formula (I), the molecular weight of the triarylmethane cation is preferably 270 or more, more preferably 470 or more, and usually 1970 or less. It is preferable that it is in the above-mentioned range in that the solubility in the colored resin composition is sufficient and the content in the colored resin composition can be reduced, so that the curability can be sufficiently secured.
The total molecular weight of the cation and the anion is preferably 300 or more, more preferably 500 or more, and usually 2000 or less. It is preferable that it is in the above-mentioned range in that the solubility in the colored resin composition is sufficient and the content in the colored resin composition can be reduced, so that the curability can be sufficiently secured.

(Specific examples of compounds represented by formula (I))
Examples of the compound represented by the formula (I) include those listed below. In the table, α represents bis (trifluoromethanesulfonyl) imide, and β represents tris (trifluoromethanesulfonyl) methide. Et represents an ethyl group, and Ph represents a phenyl group.

(Method for synthesizing compound represented by formula (I))
The triarylmethane compounds represented by the formula (I) include, for example, “reviewed synthetic dyes” (Horiguchi Hiroshi, Sankyo Publishing, 1968), “theoretical manufacturing dye chemistry” (Toyo Hosoda, Gihodo, 1957). Although it can synthesize | combine according to the method as described in international publication 2009/107734 pamphlet, it is not restricted to this method.

(Content ratio in the colored resin composition of the compound represented by the formula (I))
In the colored resin composition of the present invention, only one type of compound represented by the formula (I) may be contained in the color material (A), or two or more types may be contained. The compound represented by formula (I) in the total solid content is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 1% by mass or more, and further more preferably 5% by mass. As described above, it can be contained in a proportion of preferably 8% by mass or more, preferably 70% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and particularly preferably 20% by mass or less.
It is preferable for it to be less than or equal to the above upper limit value because the curability of the coating film is unlikely to decrease and the film strength tends to be sufficient. Moreover, since it is sufficient for coloring power to be more than the said lower limit, the chromaticity of a desired density | concentration is easy to be obtained, and since it is hard to become thick, it is preferable.

(Other color materials)
The color material (A) contained in the colored resin composition of the present invention contains a triarylmethane compound represented by the formula (I), but other color materials may be used as long as the effects of the present invention are not impaired. You may contain. Examples of the color material include dyes and pigments. A pigment is preferably included from the viewpoint of achieving both luminance and desired physical property values.

(Other dyes)
Other dyes include, for example, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, cyanine dyes, triarylmethane dyes, Preferred examples include dipyrromethene dyes and xanthene dyes.

  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. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.

  Examples of anthraquinone dyes 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 etc. are mentioned.

  Other examples of the phthalocyanine dye include C.I. I. Direct Blue 86, C.I. I. Direct Blue 199, C.I. I. Vat Blue 5, those described in JP-A No. 2002-14222, JP-A No. 2005-134759, JP-A No. 2010-191358 and JP-A No. 2011-148950 are examples of quinoneimine dyes such as C . I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

Examples of triarylmethane dyes include C.I. I. Acid Blue 86, C.I. I. Acid Blue 88, C.I. I. Acid Blue 108, International Publication No. 2009/107734 Pamphlet, International Publication No. 2011/162217 Pamphlet, and the like.
Furthermore, examples of the cyanine dye include those described in International Publication No. 2011/162217 pamphlet, and preferred embodiments thereof are also the same.

  Examples of dipyrromethene dyes include, for example, JP-A-2008-292970, JP-A-2010-84009, JP-A-2010-84141, JP-A-2010-85454, JP-A-2011-158654, and JP-A-2011-158654. Examples described in JP 2012-158739 A, JP 2012-224852 A, JP 2012-224849 A, JP 2012-224847 A, JP 2012-224846 A, and the like can be given.

Examples of xanthene dyes 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 Dye” (Horiguchi Hiroshi, Sankyo Publishing, 1968), pages 326 to 348, etc. Is mentioned.
In particular, when forming a blue pixel, xanthene dyes, triarylmethane dyes, anthraquinone dyes, azo dyes, dipyrromethene dyes, cyanine dyes, and phthalocyanine dyes are preferable. Furthermore, the interaction with the triarylmethane dye represented by the structural formula (I) of the present invention, high heat resistance and high light resistance based on the rigidity of the dye skeleton, compatibility with the resin composition, steep absorption wavelength From a viewpoint etc., it is preferable to use a xanthene dye.
In the colored resin composition of the present invention, as the color material (A), only one type of compound represented by the general formula (I) may be contained, or two or more types may be contained.
Similarly, only one other dye may be included, or two or more other dyes may be included.

(Content ratio of other dyes in the colored resin composition and coloring material)
The colored resin composition of the present invention may contain other dyes, and the content ratio is not particularly limited, but is preferably 70% by mass or less, more preferably 40% by mass or less, and still more preferably in the total solid content. 30% by mass or less. Moreover, the content rate with respect to (A) color material becomes like this. Preferably it is 50 mass% or less, More preferably, it is 30 mass% or less, More preferably, it is 10 mass% or less. Within the above range, it is preferable in that the color tone, heat resistance, and light resistance of the obtained pixel are likely to be better without greatly affecting the absorption waveform and luminance in the colored resin composition.

(Other pigments)
As the pigment, for example, when forming a pixel of a color filter, pigments of various colors such as blue and purple can be used. Examples of the chemical structure include organic pigments such as phthalocyanine, quinacridone, benzimidazolone, dioxazine, indanthrene, and perylene. In addition, various inorganic pigments can be used. Hereinafter, specific examples of usable pigments are indicated by pigment numbers.

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

Among these, 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.
For this reason, when the colored resin composition of this invention contains a blue pigment, it is 80 mass% or more with respect to the total content of a blue pigment, Especially 90 mass% or more, Especially 95-100 mass% is C.I. I. Pigment Blue 15: 6 is preferable.

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

For this reason, when the colored resin composition of this invention contains a purple pigment, it is 80 mass% or more with respect to the total content of a purple pigment, Especially 90 mass% or more, Especially 95-100 mass% is C.I. I. Pigment Violet 23 is preferable.
These may be used alone or in a combination of two or more 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 a pixel with high contrast, and specifically, the average primary particle size is 40 nm or less. Is preferable, and it is more preferable that it is 35 nm or less.
Particularly for the blue copper phthalocyanine pigment, the average primary particle size is preferably 40 nm or less, more preferably 35 nm or less, and still more preferably 20 to 30 nm.

Moreover, about a dioxazine pigment, an average primary particle diameter becomes like this. Preferably it is 40 nm or less, More preferably, it is 25-35 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 diameter 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 a primary particle image of the pigment is obtained by observation with a transmission electron microscope (TEM). From this image, the particle size of each pigment particle is determined for a plurality of (usually about 200 to 300) pigment particles, with the diameter corresponding to the area circle converted to the diameter of a circle having the same area.
Using the obtained primary particle size value, the number average value is calculated according to the following formula 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)

(Content ratio of other pigments in the colored resin composition and coloring material)
The colored resin composition of the present invention may contain other pigments, and the content ratio is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more in the total solid content. Moreover, it is preferably 70% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less. Further, the content ratio with respect to (A) the colorant is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably. Is 10% by mass or less. From the viewpoint of coexistence of luminance before heating and luminance change due to heating, it is preferable to be within the above range.

[Dispersion aid]
When the colored resin composition of the present invention contains a pigment as the colorant (A), it may contain a dispersion aid. The dispersion aid here may be a pigment derivative. Examples of the pigment derivative include JP-A Nos. 2001-220520, 2001-271004, 2002-179976, and 2007-. Various compounds described in Japanese Patent Application Publication No. 113000 and Japanese Patent Application Publication No. 2007-186681 can be used.

  The content 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. Preferably it is 10 mass% or less, More preferably, it is 5 mass% or less. By controlling the addition amount within the above range, it is preferable in that the effect as a dispersion aid is exhibited and the dispersibility and dispersion stability are better.

[(B) Solvent]
The solvent (B) contained in the colored resin composition of the present invention has a function of adjusting the viscosity by dissolving or dispersing each component contained in the colored resin composition.
(B) As a solvent, what is necessary is just to be able to melt | dissolve or disperse | distribute each component which comprises a colored resin composition, and it is preferable to select a thing whose boiling point is the range of 100-200 degreeC. More preferably, it has a boiling point of 120-170 ° C.

Examples of such solvents 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-mono t-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;

Glycol dialkyl 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 Glycol alkyl 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, diamyl ether, ethyl isobutyl 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;
Mono- 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;
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;

Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, cyclohexyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, isobutyric acid Methyl, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3- Linear or cyclic esters such as butyl methoxypropionate, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile:
These solvents may be used alone or in combination of two or more.

In the above solvent, it is preferable to contain glycol monoalkyl ethers from the viewpoint of adhesion between the substrate and the coating film, and the coating film can form a uniform film thickness. Among these, propylene glycol monomethyl ether is particularly preferable from the viewpoint of solubility of various components in the colored resin composition.
Further, for example, when the above-mentioned pigment is included as an optional component, the balance of coating properties, surface tension, etc. is good, and the glycol alkyl ether is further used as a solvent from the viewpoint of relatively high solubility of the constituent components in the colored resin composition. It is more preferable to use a mixture of acetates. In addition, in colored resin compositions containing pigments, glycol monoalkyl ethers are highly polar and tend to aggregate the pigment, which may reduce storage stability, such as increasing the viscosity of the colored resin composition. For this reason, it is preferable that the amount of glycol monoalkyl ethers used is not excessively large, and the proportion of 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 a slit coat method corresponding to a recent large substrate or the like, it is also preferable to use a solvent having a boiling point of 150 ° C. or higher. In this case, the content of the 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 total amount of the solvent (B). If the amount of the high boiling point solvent is too small, for example, a dye component may precipitate and solidify at the tip of the slit nozzle to cause foreign matter defects, and if it is too large, the drying speed of the composition will be slowed down. There is a concern that the filter manufacturing process may cause problems such as tact defects in the vacuum drying process and pin marks of prebaking.

The solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a solvent having a boiling point of 150 ° C. or higher may not be included separately. .
The colored resin composition of the present invention may be used for color filter production by the ink jet method, but in color filter production by the ink jet method, the ink emitted from the nozzle is very small, from several to several tens pL, There is a tendency for the solvent to evaporate and the ink to concentrate and dry before landing on the periphery of the nozzle opening or in the pixel bank. In order to avoid this, it is preferable that the solvent has a high boiling point. 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 220 ° C. or higher. Moreover, it is preferable that the high boiling point solvent whose boiling point is 180 degreeC or more is 50 mass% or more in (B) solvent. When the ratio of such a high boiling point solvent is less than 50% by mass, the effect of preventing evaporation of the solvent from the ink droplets may not be sufficiently exhibited.

  In the colored resin composition of the present invention, the content of the (B) solvent is not particularly limited, but the upper limit is usually 99% by mass. When the content of the solvent (B) in the composition exceeds 99% by mass, the concentration of each component excluding the solvent (B) may become too low to form a coating film. On the other hand, the lower limit of the content of the solvent (B) is usually 70% by mass, preferably 75% by mass, and more preferably 80% by mass in consideration of viscosity suitable for coating.

[(C) Dispersant]
The colored resin composition of the present invention contains (C) a dispersant. (C) The dispersant can also be used for the purpose of dispersing the above-mentioned other pigments in a solvent, and among the triarylmethane compounds represented by formula (I) and other dyes, the solubility in the solvent Can be used for the purpose of dispersing in the solvent.
The colored resin composition of the present invention is characterized in that the (C) dispersant contains a dispersant having an acidic group. Thus, it is thought that the influence on the pigment decomposition in the substrate heating can be reduced by using the dispersant having an acidic group. That is, since the electrostatic interaction with the cation and anion of the triarylmethane-based compound is small, it is considered that a decomposition reaction including a salt exchange reaction with an acidic group contained in the dispersant does not easily occur. For this reason, it is presumed that even when the substrate is heated, the pigment is hardly decomposed and the luminance can be maintained. On the other hand, a dispersant having no acidic group and having an amino group and ammonium has a large electrostatic interaction with a cation or anion of a triarylmethane compound, so that decomposition such as a salt exchange reaction occurs. Reaction is likely to occur. Therefore, it is presumed that heating the substrate promotes the decomposition reaction of the pigment, and the luminance is greatly reduced.

(Difference between acid value and amine value)
Based on the above estimation mechanism, it can be said that it is desirable that the dispersant contains more acidic groups than basic groups. Specifically, the acid value is preferably larger than the amine value, the difference between the acid value and the amine value is more preferably 0.1 mgKOH / g or more, further preferably 1 mgKOH / g or more, and 5 mgKOH. / G or more is most preferable. Usually, it is 150 mgKOH / g or less.

(Acid value range)
The acid value of the dispersant is preferably 150 mgKOH / g or less, more preferably 100 mgKOH / g or less, most preferably 80 mgKOH / g or less, and usually 5 mgKOH / g or more. This is from the viewpoint of both the dispersion stability of the pigment and the appropriate interaction between the dispersant and the dye.

  The acid value is represented by the mass of KOH equivalent to the amount of base per gram of solid content excluding the solvent in the dispersant sample. The measuring method is as described in “Japanese Industrial Standards JIS K2501: 2003 Petroleum Products and Lubricating Oils—Neutralization Test Method”.

(Amine value range)
When the dispersant has an amine value, it is preferably 150 mgKOH / g or less, more preferably 100 mgKOH / g or less, most preferably 80 mgKOH / g or less, and usually 5 mgKOH / g or more. This is in view of adsorption on the pigment surface and proper interaction between the dispersant and the dye.

  The amine value is represented by the mass of KOH equivalent to the amount of base per gram of solid content excluding the solvent in the dispersant sample. The measurement method is as described in “Japanese Industrial Standards JIS K1557-7: 2011 Plastics—Polyurethane Raw Material Polyol Test Method—Part 7: Determination of Basicity (Nitrogen Content and Total Amine Value Indication)”.

(Dispersant basic structure)
The basic structure of the dispersant is not particularly limited as long as the effects of the present invention are satisfied. For example, acrylic resin, polyethylene resin, polypropylene resin, polyvinyl chloride resin, polystyrene resin, polyvinyl acetate resin, polyether resin, urethane resin , Silicon resin, epoxy resin and the like.

(Dispersant basic skeleton polymerization method)
Examples of the main chain part of the dispersant include those obtained by copolymerizing one kind of monomer, and those obtained by synthesizing a plurality of kinds of monomers using random copolymerization, alternating copolymerization, block copolymerization, and graft copolymerization. It is done. In consideration of the adsorptivity with the pigment, the dispersibility and dispersion stability of the pigment, and the interaction with the dye, those obtained by randomly copolymerizing or alternately copolymerizing a plurality of types of monomers are preferable. When copolymerization is performed using a plurality of monomer species, the number of monomer species is preferably 5 or less, more preferably 4 or less, most preferably 3 or less, and usually 2 or more. This is from the viewpoint of making the viscosity and coatability of the colored resin composition appropriate.

(Detailed backbone structure)
Examples of the monomer used for the main chain portion of the dispersant include acrylate, methacrylate, acrylic acid, acrylonitrile, styrene, ethylene, propylene, 1,3-butadiene, isoprene, vinyl chloride, vinyl acetate, vinyl silane, vinyl ester, N- Examples include vinylpyrrolidone, vinylidene chloride, maleimide, acenaphthylene, vinylene carbonate, acrylamide, ethylene glycol, ethylene oxide, urethane, and silanol. From the viewpoint of compatibility in the colored resin composition and dispersion stability and viscosity when used when dispersing the pigment, a resin having acrylate, methacrylate, or acrylic acid as a monomer is preferable.

(Functional group)
The acidic group preferably has a sulfonic acid group, a carboxyl group, or a phosphoric acid group, and the basic group preferably has an amino group. This is because, when used for the purpose of dispersing the pigment, from the viewpoint of the adsorption property to the pigment and the dispersion stability of the pigment. Moreover, these functional groups may contain not only one type but also a plurality.

(Molecular weight)
The weight average molecular weight (Mw) of the dispersant is preferably 20000 or less, more preferably 15000 or less, still more preferably 12000 or less, and usually 3000 or more. This is to maintain a viscosity that can be applied to the glass substrate with an appropriate film thickness when the colored resin composition is formed.

(Concrete example)
Although it will not specifically limit if it has an acidic group as a dispersing agent, For example, the following are mentioned as a specific example.
(Bic Chemie, acid value only)
DISPERBYK (registered trademark, the same shall apply hereinafter) -102, DISPERBYK-106, DISPERBYK-110, DISPERBYK-111, DISPERBYK-118, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-2096, BYK-P P104S, BYK-P105, BYK-9076, BYK-220S,
(Bic Chemie, acid value> amine value)
DISPERBYK-190, DISPERBYK-194N, DISPERBYK-199, DISPERBYK-2015, ANTI-TERRA-204, DISPERBYK-142, DISPERBYK-145, DISPERBYK-191,

(Enomoto Kasei Co., Ltd., acid value only)
ED518W, 300-255, 300-026, ED110, ED111, ED112, ED151, ED152, ED153, ED350, ED420, 300-243, ED5155W, 300-288, ED115, ED701,
(Manufactured by Enomoto Kasei Co., Ltd., acid value> amine value)
ED5144W, ED5155W, 300-239, 300-289, ED100S, ED113, ED115, ED116, ED360, ED425, ED701, 300-257,

(Lubrizol, acid value only)
SOLSPERSE (registered trademark. Hereinafter the same.) 3000, SOLSPERSE16000, SOLSPERSE17000, SOLSPERSE21000, SOLSPERSE26000, SOLSPERSE27000, SOLSPERSE28000, SOLSPERSE36000, SOLSPERSE36600, SOLSPERSE38500, SOLSPERSE41000, SOLSPERSE41090, SOLSPERSE43000, SOLSPERSE44000, SOLSPERSE45000, SOLSPERSE46000, SOLSPERSE47000, SOLSPERSE53095, SOLSPERSE54000, SOLSPERSE55000,

(Ajinomoto Finetech, acid value only)
PN411, PN111,
(Ajinomoto Finetech, acid value> amine value)
PB821,

(Kyoeisha Chemical Co., Ltd., acid value only)
FG700, FG900, FG1500,
(Kyoeisha Chemical Co., Ltd., acid value> amine value)
PB821,
Etc.

(Content in colored resin composition)
The content of the dispersant in the solid content in the colored resin composition is usually 5% by mass or less, preferably 3% by mass or less, more preferably 2% by mass or less, and further preferably 1% by mass or less. It is 0.1 mass% or more. By being in the above range, the interaction between the dye and the dispersant is appropriately maintained, and therefore, it tends to be possible to suppress a decrease in luminance during heating.

[Dispersion resin]
The colored resin composition of the present invention may contain, as a dispersion resin, part or all of a resin selected from (D) a binder resin described later or other binder resins.
Specifically, in [Preparation Method of Colored Resin Composition], which will be described later, (D) Binder resin is contained together with the above-described components such as the dispersant, whereby (D) Binder resin and A synergistic effect contributes to the dispersion stability of other pigments. As a result, the amount of dispersant added may be reduced, which is preferable. Further, it is preferable because the developability is improved, the undissolved matter does not remain in the non-pixel portion of the substrate, and the adhesion of the pixel to the substrate is improved.
Thus, (D) binder resin used for a dispersion treatment process may be called dispersion resin. The dispersion resin is preferably used in an amount of about 0 to 200% by mass, more preferably about 10 to 100% by mass, based on the total amount of other pigments in the colored resin composition.

[(D) Binder resin]
(D) What preferable binder resin changes with the hardening means of a colored resin composition.
When the colored resin composition of the present invention is a photopolymerizable resin composition, examples of the (D) binder resin include JP-A-7-207211, JP-A-8-259876, and JP-A-10-300922. The polymer compounds described in JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118, JP-A-2003-233179, and the like can be used. Among them, the following resins (D-1) to (D-5) are preferable.

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

The resins (D-2) to (D-5) may be anything as long as they are dissolved in an alkaline developer and have solubility to the extent that the desired development processing is performed. It is the same as that described as the same item of 2009-025813 gazette. The preferred embodiment is also the same.
(D-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least part of the epoxy group of the copolymer. As one of particularly preferable resins of the alkali-soluble resin resin (D-1) obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction, or an epoxy group, Unsaturated in 10 to 100 mol% of the epoxy group of the copolymer with respect to the copolymer of 5 to 90 mol% of (meth) acrylate and 10 to 95 mol% of other radical polymerizable monomer 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 a hydroxyl group 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 (meta). ) Acrylate glycidyl ether and the like. Of these, glycidyl (meth) acrylate is preferred. These epoxy group-containing (meth) acrylates may be used alone or in combination of two or more.

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

  The repeating unit derived from the mono (meth) acrylate having the structure represented by the following formula (V) contains 5 to 90 mol% among the repeating units derived from “other radical polymerizable monomers”. The content is preferably 10 to 70 mol%, more preferably 15 to 50 mol%.

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

The formula (VI), R ⁹¹ ~R ⁹⁸ independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ⁹⁶ and R ⁹⁸ , or R ⁹⁵ and R ⁹⁷ may be connected to each other to form a ring.
The ring formed by linking R ⁹⁶ and R ⁹⁸ is preferably an aliphatic ring, which may be either a saturated or unsaturated aliphatic ring, and is an aliphatic ring having 5 to 6 carbon atoms. Preferably there is.
Among these, as the structure represented by the formula (VI), a structure represented by the following structural formula (VIa), (VIb), or (VIc) is particularly preferable.

In addition, the mono (meth) acrylate which has a structure represented by said Formula (VI) may be used individually by 1 type, and may use 2 or more types together.
As "other radical polymerizable monomers" other than the mono (meth) acrylate having the structure represented by the formula (VI), the heat resistance and strength excellent in the colored resin composition can be improved. , Styrene, (n-butyl) (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate , (Meth) acrylic acid-2-hydroxyethyl, N-phenylmaleimide, N-cyclohexylmaleimide.

The content of the repeating unit derived from at least one selected from the above 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 radical polymerizable monomer.
In the present invention, as a copolymer of the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer, 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth) acrylate, and others Is preferably composed of 10 to 95 mol% of repeating units derived from the radically polymerizable monomer, more preferably composed of 20 to 80 mol% of the former and 80 to 20 mol% of the latter. What consists of 70 mol% and the latter 70-30 mol% is especially preferable.

Within the above range, the addition amount of the polymerizable component and alkali-soluble component described later is sufficient, and the heat resistance and the strength of the film are sufficient, which is preferable.
The epoxy group portion of the epoxy group-containing copolymer synthesized as described above is reacted with an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali-soluble component).
Here, as an unsaturated monobasic acid added to an epoxy group, a well-known thing can be used, For example, unsaturated carboxylic acid which has an ethylenically unsaturated double bond is mentioned.

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

By adding such components, polymerizability can be imparted to the binder resin used in the present invention.
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%. It is preferable for it to be in the above range since the colored resin composition is excellent in stability over time. In addition, a well-known method is employable as a method of adding unsaturated monobasic acid to the epoxy group of a copolymer.

Furthermore, a well-known thing can be used as a polybasic acid anhydride added to the hydroxyl group produced when an unsaturated monobasic acid is added to the epoxy group of a 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 three or more bases such as tetracarboxylic acid anhydride and biphenyltetracarboxylic acid anhydride. Of these, succinic anhydride and tetrahydrophthalic anhydride are preferred. These polybasic acid anhydrides may be used individually by 1 type, and may use 2 or more types together.

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 group generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer, preferably 20 to 90 mol. %, More preferably 30 to 80 mol%.

Within the above range, the remaining film ratio and solubility during development are sufficient, which is preferable.
In addition, a well-known method is employable as a method of adding a polybasic acid anhydride to the said hydroxyl group.
Furthermore, in order to improve photosensitivity, after adding the above-mentioned polybasic acid anhydride, glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group is added to a part of the generated carboxyl group. May be. Such a resin structure is described in, for example, Japanese Patent Application Laid-Open Nos. 8-297366 and 2001-89533.

3000-100000 are preferable and, as for the weight average molecular weight (Mw) of polystyrene conversion measured by GPC (gel permeation chromatography) of the above-mentioned binder resin (D), 5000-50000 are especially preferable. Within the above range, heat resistance, film strength, and solubility in a developer are preferable.
Moreover, as a standard of molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 2.0 to 5.0.

In addition, the acid value of binder resin (D) is 10-200 mg-KOH / g normally, Preferably it is 15-150 mg-KOH / g, More preferably, it is 25-100 mg-KOH / g. If the acid value is too low, the solubility in the developer may be reduced. Conversely, if it is too high, film roughening may occur.
The content ratio of the (D) binder resin in the colored resin composition is usually 0.1 to 80% by mass, preferably 1 to 60% by mass in the total solid content.
Within the above range, the adhesion to the substrate is good, the permeability of the developer to the exposed area is moderate, and the surface smoothness and sensitivity of the pixels are good.

[(E) Polymerizable monomer]
The colored resin composition of the present invention preferably contains (E) a polymerizable monomer.
(E) The polymerizable monomer is not particularly limited as long as it is a polymerizable low molecular compound, but it may be an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylenic compound”). Is preferred).
The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and cures by the action of a photopolymerization initiation component described later when the colored resin composition of the present invention is irradiated with actinic rays. In addition, the (E) polymerizable monomer in this invention means the concept opposite to what is called a polymeric substance, and also includes a dimer, a trimer, and an oligomer other than a monomer in a narrow sense.

  (E) Examples of the ethylenic compound in the 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 of aromatic polyhydroxy compounds and unsaturated carboxylic acids; Esterification of unsaturated carboxylic acids with polyvalent carboxylic acids and polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds described above An ester obtained by the reaction; an ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound;

  Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (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 include (meth) acrylic acid esters such as acrylate and glycerol (meth) acrylate. In addition, the (meth) acrylic acid portion of these (meth) acrylic acid esters is replaced with an itaconic acid portion, a crotonic acid portion replaced with a crotonic acid portion, or a maleic acid ester replaced with a maleic acid portion, etc. Is mentioned.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone di (meth) acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth) acrylate, and the like.
The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound may be a single substance or a mixture. Representative examples are condensates of (meth) acrylic acid, phthalic acid, and ethylene glycol; condensates of (meth) acrylic acid, maleic acid, and diethylene glycol; condensation of (meth) acrylic acid, terephthalic acid, and pentaerythritol A condensate of (meth) acrylic acid, adipic acid, butanediol, and glycerin.

  Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic rings such as cyclohexane diisocyanate and isophorone diisocyanate. Formula diisocyanates; 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 A reaction product with a group-containing hydroxy compound is exemplified.

In addition, examples of the ethylenic compound used in the present invention include (meth) acrylamides such as ethylene bis (meth) acrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate. .
Among these, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred, pentaerythritol or (meth) acrylic acid esters of dipentaerythritol are more preferred, and dipentaerythritol hexa (meth) acrylate is particularly preferred.

  The ethylenic compound may be a monomer having an acid value. The monomer having an acid value is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having a group is preferable, and in this ester, the aliphatic polyhydroxy compound is at least one of pentaerythritol and dipentaerythritol.

These monomers may be used alone, but since it is difficult to obtain a single compound in production, a mixture of two or more kinds may be used.
Moreover, you may use together the polyfunctional monomer which does not have an acid group, and the polyfunctional monomer which has an acid group as (E) polymeric monomer as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 100 mg-KOH / g, and particularly preferably 5 to 80 mg-KOH / g.

When it is within the above range, the development and dissolution characteristics are hardly deteriorated, and the production and handling are easy. Furthermore, it is preferable because the photopolymerization performance is hardly lowered and the curability such as the surface smoothness of the pixel is good.
In the present invention, a more preferred polyfunctional monomer having an acid group is, for example, a mixture containing succinic acid ester of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate as a main component. It is also possible to use this polyfunctional monomer in combination with another polyfunctional monomer.

  In the colored resin composition of the present invention, the content ratio of these (E) polymerizable monomers is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more in the total solid content. Moreover, it is 80 mass% or less normally, Preferably it is 70 mass% or less, More preferably, it is 50 mass% or less, More preferably, it is 40 mass% or less, More preferably, it is 30 mass% or less, Most preferably, it is 20 mass% or less.

The content ratio of (E) polymerizable monomer to 100 parts by mass of the (A) colorant is usually 1 part by mass or more, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and further preferably 20 parts by mass. More preferably, it is 50 parts by mass or more, and is usually 200 parts by mass or less, preferably 100 parts by mass or less, and more preferably 80 parts by mass or less.
If it is within the above range, photocuring is appropriate, poor adhesion during development is unlikely to occur, the cross-section after development is unlikely to be an inversely tapered shape, and peeling phenomenon and omission failure due to lower solubility are less likely to occur. preferable.

[(F) Photopolymerization initiation component and (F ′) thermal polymerization initiation component]
The colored resin composition of the present invention preferably contains at least one of (F) 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 (D), or contains an ethylenic compound as the component (E), it directly absorbs light, or It is preferable to contain at least one of a photopolymerization initiating component that has a function of generating a polymerization active radical and a thermal polymerization initiating component that generates a polymerization active radical by heat by causing a photosensitization to cause a decomposition reaction or a hydrogen abstraction reaction. . In the present invention, the component (F) as the photopolymerization initiation component refers to a photopolymerization initiator (hereinafter also referred to as “(F1) component”) and a polymerization accelerator (hereinafter, optionally referred to as “(F2) component”. ")" And a sensitizing dye (hereinafter also referred to as "(F3) component").

[(F) Photopolymerization initiation component]
The (F) photopolymerization initiating component in the present invention is usually a mixture of (F1) a photopolymerization initiator and, if necessary, (F2) a polymerization accelerator and (F3) an additive such as a sensitizing dye. And is a component having a function of generating a polymerization active radical by directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction.

  Examples of the photopolymerization initiator (F1) constituting the photopolymerization initiating component include titanocene derivatives described in, for example, JP-A Nos. 59-152396 and 61-151197; JP-A-10-300922 Hexaarylbiimidazole derivatives described in JP-A-11-174224, JP-A-2000-56118, etc .; halomethylated oxadiazole derivatives described in JP-A-10-39503, etc., halomethyl- 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; oxime ester derivatives described in JP 2000-80068 A and the like .

Specific examples include photopolymerization initiators described in International Publication No. 2009/107734 pamphlet and the like.
Among these photopolymerization initiators, α-aminoalkylphenone derivatives, oxime ester derivatives, biimidazole derivatives, acetophenone derivatives, and thioxanthone derivatives are more preferable.

  Further, examples of oxime ester derivatives include 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone, O-acetyl-1- [6- (2-methylbenzoyl) -9. -Ethyl-9H-carbazol-3-yl] ethanone oxime and a compound represented by the following formula (V).

(In formula (VII), R ¹⁰¹ represents 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. An alkyl group, any of which may have a substituent, or R ¹⁰¹ may be bonded to X or Z to form a ring;
R ¹⁰² is an alkanoyl group having 2 to 20 carbon atoms, alkenoyl of 3 to 25 carbon atoms, cycloalkanoyl group having 4 to 8 carbon atoms, aryloyl group having 7 to 20 carbon atoms, 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 heteroaryloyl group having 3 to 20 carbon atoms, or an alkylaminocarbonyl group having 2 to 20 carbon atoms, It may have a substituent.

X represents at least one of a divalent aromatic hydrocarbon ring group and an aromatic hetero group formed by condensation of two or more rings which may have a substituent.
Z represents an aromatic ring group which may have a substituent. )
Of the compounds represented by the formula (VII), compounds in which X is a carbazole ring which may have a substituent are preferred. Specifically, compounds represented by the following formula (VIII) Among them, a compound represented by the following formula (IX) is particularly preferable.

In formula (VIII), R ¹⁰¹ , R ¹⁰² and Z have the same definitions as in formula (VII). R ^{103 to} R ¹⁰⁹ each independently represent a hydrogen atom or an arbitrary substituent.

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

In formula (IXa), R ¹¹⁰ and R ¹¹¹ each independently represents a hydrogen atom, a phenyl group or an N-acetyl-N-acetoxyamino group. * Represents a binding site.

In Formula (IX), 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 having 1 to 4 carbon atoms. Za represents ^a phenyl group which may be substituted with an alkyl group or a naphthyl group which may be substituted with a morpholino group.

  Commercial products may be used as the oxime initiator. Examples of commercially available products include OXE-01, OXE-02 (BASF), TRONLYTR-PBG-304, TRONLYTR-PBG-309, TRONLYTR-PBG-305, TRONLYTR-PBG-314 (Changzhou Powerful Electronic New Materials Co., Ltd.) Ltd. (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD).

  Other photopolymerization initiators include benzoin alkyl ethers, anthraquinone derivatives; acetophenone derivatives such as 2-methyl- (4′-methylthiophenyl) -2-morpholino-1-propanone, 2-ethylthioxanthone, 2 Thioxanthone derivatives such as 1,4-diethylthioxanthone, benzoic acid ester derivatives, acridine derivatives, phenazine derivatives, anthrone derivatives and the like. Commercial products may be used as these initiators.

  Examples of commercially available products include IRGACURE (registered trademark, the same shall apply hereinafter) 651, IRGACURE 184, DAROCURE 1173, IRGACURE 2959, IRGACURE 127, IRGACURE 907, IRGACURE 369, IRGACURE 379EG, IRCIRUCURE EG, 8 , Manufactured by BASF).

Among these photopolymerization initiators, α-aminoalkylphenone derivatives, thioxanthone derivatives, and oxime ester derivatives are more preferable. In particular, oxime ester derivatives are preferable.
Examples of the (F2) polymerization accelerator used as necessary 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 heterocyclic ring such as benzoxazole and 2-mercaptobenzimidazole; mercapto compounds such as aliphatic polyfunctional mercapto compounds.

These (F1) photopolymerization initiators and (F2) polymerization accelerators may be used alone or in combination of two or more.
Further, (F3) sensitizing dye is used for the purpose of increasing the sensitivity as required. A suitable sensitizing dye is used depending on the wavelength of the image exposure light source. For example, xanthene dyes described in JP-A-4-221958 and JP-A-4-219756; No. 239703, JP-A-5-289335, etc., a coumarin dye having a heterocyclic ring; JP-A-3-239703, JP-A-5-289335, etc .; 3-ketocoumarin dye; Pyrromethene dyes described in JP-A-6-19240 and the like; JP-A 47-2528, JP-A 54-155292, JP-B 45-37377, JP-A 48-84183, JP JP 52-112681, JP 58-15503, JP 60-88005, JP 59-56403, JP 2-69, HirakiAkira 57-168088, JP-A No. 5-107761, JP-A No. 5-210240, JP-dyes having a dialkyl aminobenzene skeleton described in JP-A-4-288818 discloses the like.

(F3) A 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 (F) photopolymerization initiating components is usually 0.1% by mass or more, preferably 0.2% by mass or more, more preferably 0.8% by mass in the total solid content. 5% by mass or more, more preferably 1% by mass or more, still more preferably 5% by mass or more, particularly preferably 10% by mass or more, and usually 40% by mass or less, preferably 30% by mass or less, more preferably 20% by mass. % Or less.
Within the above range, the sensitivity to the exposure light beam is good, the solubility of the unexposed portion in the developer is good, and it is preferable in that it is difficult to induce poor development.

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

[Other optional ingredients]
The colored resin composition of the present invention includes, in addition to the above components, at least one of a surfactant, an organic carboxylic acid and an organic carboxylic anhydride, a thermosetting compound, a plasticizer, a thermal polymerization inhibitor, and a storage stabilizer. , Surface protective agents, adhesion improvers, development improvers and the like may be contained. As these optional components, for example, various compounds described in JP-A-2007-113000 can be used. Moreover, when it contains a pigment, you may contain a dispersing agent and a dispersing aid.

[Preparation Method of Colored Resin Composition]
In the present invention, the colored resin composition can be prepared by an appropriate method. For example, the (A) color material containing the compound (I), (C) the dispersant, and (D) the binder resin (B) ) It can be prepared by mixing with a solvent and optional components used as required.

Alternatively, a (A) color material containing compound (I), (C) a dispersant and (B) a color material-containing liquid containing a solvent may be prepared, and (D) a binder resin and an optional component may be mixed therewith. Good.
Moreover, as a preparation method in the case of containing a pigment, in the presence of (C) a dispersing agent and a dispersing aid to be added if necessary, in a solvent containing a pigment, optionally with (D) a part of the binder resin, For example, using a paint shaker, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer or the like, a pigment dispersion is prepared by mixing and dispersing while pulverizing. In the pigment dispersion, (A) a coloring material containing compound (I), (D) a binder resin, and (E) a polymerizable monomer, (F) a photopolymerization initiating component and a thermal polymerization initiating component, if necessary A method of adding at least one or the like and mixing them can be mentioned.
On the other hand, when a pigment is not included, for example, as a preparation method in the case of using only a dye as a coloring material, a dispersing agent and a dispersion aid are not required, and a complicated pigment dispersion step is not required. Things can be manufactured inexpensively.

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

[Colorant-containing liquid]
As described above, when the colored resin composition is produced, a color material-containing liquid containing (A) a color material containing compound (I), (B) a solvent, and (C) a dispersant may be prepared.
As the (A) color material, the (B) solvent, and the (C) dispersant in the color material-containing liquid, those shown as preferred examples in the colored resin composition can be used.

(Content ratio of the triarylmethane compound represented by the formula (I) in the colorant-containing liquid)
In the color material-containing liquid of the present invention, only one type of compound represented by the formula (I) may be included in the color material (A), or two or more types may be included. The compound represented by formula (I) in the total solid content is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 1% by mass or more, and further more preferably 5% by mass. As described above, it can be contained in a proportion of preferably 8% by mass or more, preferably 70% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and particularly preferably 20% by mass or less.
It is preferable for it to be less than or equal to the above upper limit value because the curability of the coating film is unlikely to decrease and the film strength tends to be sufficient. Moreover, since it is sufficient for coloring power to be more than the said lower limit, the chromaticity of a desired density | concentration is easy to be obtained, and since it is hard to become thick, it is preferable.

(Content ratio of the compound represented by the formula (I) in the coloring material)
In the color material-containing liquid of the present invention, the content ratio of the compound represented by formula (I) in (A) the color material is not particularly limited, but is 0.01% by mass or more based on (A) the color material. It is preferably 0.1% by mass or more, more preferably 1% by mass or more, and particularly preferably 5% by mass or more. Moreover, it is 100 mass% or less normally, it is preferable that it is 99 mass% or less, it is more preferable that it is 95 mass% or less, and it is further more preferable that it is 90 mass% or less. It is preferable for it to be less than or equal to the above upper limit value because the curability of the coating film is hardly lowered and the film strength is sufficient. Moreover, since it is sufficient for coloring power to be more than the said lower limit, the chromaticity of a desired density | concentration is easy to be obtained, and since it is hard to become thick, it is preferable.

  In the colorant-containing liquid of the present invention, the content of the (B) solvent is not particularly limited, but the upper limit is usually 99% by mass. When the content of the solvent (B) in the composition exceeds 99% by mass, the concentration of each component excluding the solvent (B) may become too low to form a coating film. On the other hand, the lower limit of the content of the solvent (B) is usually 98% by mass, preferably 95% by mass, and more preferably 90% by mass in consideration of viscosity suitable for coating.

  In the colorant-containing liquid of the present invention, the content of the (C) dispersant is not particularly limited, but is preferably 34% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less, usually 5%. It is at least mass%. This is because by using the dispersant in this range, the interaction between the contained colorant and the dispersant becomes appropriate, and the reduction in luminance during heating can be reduced.

<Color filter>
The color filter of the present invention has a pixel formed from the colored resin composition of the present invention.
The method for forming the color filter of the present invention will be described below.
The pixel of the color filter can be formed by various methods. Here, although the case where it forms by the photolithographic method using a photopolymerizable colored resin composition is demonstrated to an example, a manufacturing method is not limited to this.

  First, on the surface of the substrate, if necessary, a black matrix is formed so as to partition a portion for forming pixels, and after applying the colored resin composition of the present invention on this substrate, pre-baking is performed. The solvent is evaporated to form a coating film. Then, after exposing this coating film through a photomask, developing with an alkali developer, dissolving and removing the unexposed portion of the coating film, and then post-baking, each of red, green, and blue A color filter can be manufactured by forming a pixel pattern.

In the present invention, it is particularly preferable that the pixel formed using the colored resin composition of the present invention is a blue pixel.
The substrate used for forming the pixels is not particularly limited as long as it is transparent and has an appropriate strength. For example, polyester resin, polyolefin resin, polycarbonate resin, acrylic resin, thermoplastic resin Examples thereof include a sheet made, an epoxy resin, a thermosetting resin, and various glasses.

In addition, these substrates may be appropriately subjected to pretreatment as desired, such as thin film formation treatment with a silane coupling agent or urethane resin, surface treatment such as corona discharge treatment or ozone treatment, if desired.
When applying the colored resin composition to the substrate, a spinner method, a wire bar method, a flow coating method, a slit and spin method, a die coating method, a roll coating method, a spray coating method, and the like can be given. Of these, the slit and spin method and the die coating method are preferable.

The thickness of the coating film is usually 0.2 to 20 μm, preferably 0.5 to 10 μm, 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 can be easily adjusted in the pattern development or liquid crystal cell forming step, and a desired color can be easily expressed.
As the radiation used in the exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, and radiation having a wavelength in the range of 190 to 450 nm is preferable.

  A light source for using radiation having a wavelength of 190 to 450 nm used for image exposure is not particularly limited. 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, Lamp light sources such as medium pressure mercury lamp, low pressure mercury lamp, carbon arc, fluorescent lamp; laser light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, semiconductor laser, and the like. An optical filter can also be used when used by irradiating light of a specific wavelength.

Exposure of radiation, 10~10,000J / m ² is preferred.
Examples of the alkaline developer include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, 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-isopropanol Amines, tri - isopropanolamine, ethyleneimine, ethylene diimine, tetramethyl ammonium hydroxide (TMAH), an aqueous solution of an organic alkaline compound such as choline and the like are 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 the like can be added to the alkali developer. In addition, it is usually washed with water after alkali development.
As the development processing method, any method such as an immersion development method, a spray development method, a brush development method, and an ultrasonic development method can be used. The development conditions are preferably 5 to 300 seconds at room temperature (23 ° C.).

There are no particular restrictions on the conditions of the development processing, but the development temperature is usually 10 ° C. or higher, especially 15 ° C. or higher, more preferably 20 ° C. or higher, and usually 50 ° C. or lower, especially 45 ° C. or lower, further 40 ° C. or lower. Is preferred.
The developing method can be any one of immersion developing method, spray developing method, brush developing method, ultrasonic developing method and the like.

  When the color filter thus produced is used in a liquid crystal display device, a transparent electrode such as ITO is formed on the image as it is and used as a part of a component such as a color display or a liquid crystal display device. Although used, in order to improve surface smoothness and durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed. In the vertical alignment type driving method (MVA mode), ribs may be formed. Further, a column structure (photo spacer) by a photolithography method may be formed instead of the bead dispersion type spacer.

<Liquid crystal display device>
The liquid crystal display device of the present invention uses the above-described color filter of the present invention. There is no restriction | limiting in particular about the model and structure of the liquid crystal display device of this invention, It can assemble in accordance with a conventional method using the color filter of this invention.
For example, the liquid crystal display device of the present invention can be formed by the method described in “Liquid Crystal Device Handbook” (Nikkan Kogyo Shimbun, September 29, 1989, Japan Society for the Promotion of Science 142nd Committee).

<Organic EL display device>
When producing an organic EL display device having the color filter of the present invention, for example, as shown in FIG. A multicolor organic EL element is manufactured by laminating the organic light-emitting body 500 through the organic protective layer 30 and the inorganic oxide film 40.

  As a method for laminating the organic light emitter 500, 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 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. The organic EL element 100 manufactured as described above can be applied to both a passive drive type organic EL display device and an active drive type organic EL display device.

Next, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded (synthesis example 1 :). Synthesis of dye A)

  Under a nitrogen atmosphere, N, N-dimethylformamide (DMF) (60 mL) was added to N-ethyl-o-toluidine (21.6 g, 160 mmol) and cooled to 5 ° C. or lower. Potassium t-butoxide (18.0 g, 160 mmol) was added in several portions while maintaining the temperature at 5 ° C. or lower. Next, a solution of 4,4-difluorobenzophenone (8.73 g, 40.0 mmol) in N, N-dimethylformamide (DMF) (35 mL) was added dropwise over 30 minutes, taking care to keep the temperature below 15 ° C. After completion of the dropping, the temperature was raised to room temperature, and the mixture was further heated and stirred at 50 ° C. for 3 hours. After completion of the reaction, the mixture was allowed to cool to room temperature and poured into water (100 mL). This was extracted twice with toluene (50 mL), washed with water (20 mL) three times, and then the solvent was distilled off with an evaporator. The obtained solid was purified by silica gel column chromatography (hexane / ethyl acetate = 100/0 to 66/34 (volume ratio)) to obtain Compound 1 (3.08 g, yield 17%).

  Under a nitrogen atmosphere, the mixture of Compound 1 (610 mg, 1.36 mmol), Compound 2 (336 mg, 1.40 mmol) and toluene (10 mL) was stirred at room temperature until dissolved. Phosphorus oxychloride (312 mg, 2.04 mmol) was added dropwise over 5 minutes. After the addition, the mixture was heated to 80 to 85 ° C., and heated and stirred as it was for 9 hours. Further, phosphorus oxychloride (208 mmol, 1.36 mmol) was added dropwise, and the mixture was heated and stirred as it was for 4 hours, and then allowed to cool to room temperature. Water (10 mL) was added and stirred at room temperature for 1 hour. Chloroform (10 mL) was added to extract the organic layer, which was washed 3 times with water (10 mL), and then the solvent was distilled off with an evaporator. The obtained solid was dissolved in chloroform (10 mL) and purified by silica chromatography (developing solvent: chloroform / methanol = 100/0 to 82/8 (volume ratio)) to obtain a blue solid compound 3 (590 mg, yield). 61%).

  Under a nitrogen atmosphere, a mixed solution of compound 3 (0.59 g, 0.84 mmol), methanol (5 mL) and bis (trifluoromethanesulfonyl) imidolithium (0.24 g, 0.84 mmol) was added at an external temperature of 50 ° C. The mixture was heated and stirred for 5 hours. The mixture was allowed to cool to room temperature, and the solvent was distilled off with an evaporator, followed by washing with a methanol / water = 2/1 (volume ratio) mixed solution (30 mL). The obtained solid was dissolved in chloroform (10 mL) and purified by silica chromatography (developing solvent: chloroform / methanol = 94/6 to 87/13 (volume ratio)) to obtain a blue solid dye A (0.50 g, Yield 62%) was obtained.

Dye A was dissolved in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) by 10 mass ppm. At this time, the maximum absorption wavelength (λmax) was 575 nm, and the Gram extinction coefficient (g) was 81.8 Lg ⁻¹ cm ⁻¹ . The results of liquid chromatography-mass spectrometry of this compound are shown below. In addition, the mass at this time has shown the mass of the triarylmethane cation site | part.
LCMS (ESI, posi) m / z 670 (M + C 48 H 52 N 3)
(Synthesis Example 2: Synthesis of Dye B)

  Compound 4 (2.00 g, 3.40 mmol, synthesized by the method described in WO2011 / 158794) was dissolved in methanol (20 mL) at room temperature under a nitrogen atmosphere, and lithium bis (trifluoromethylsulfonyl) imide (0. 99 g, 3.40 mmol) was added. The mixed solution was stirred at an external temperature of 50 ° C. for 1.5 hours and then allowed to cool to room temperature. The solvent was concentrated with an evaporator and then washed with a mixed solvent (30 mL) of methanol / water = 1/2 (volume ratio). The obtained solid was dissolved in chloroform (10 mL) and purified by silica chromatography (developing solvent: chloroform / methanol = 10/1 to 5/1 (volume ratio)) to obtain a blue solid dye B (1.80 g, Yield 63%) was obtained.

Dye B was dissolved by 10 mass ppm in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio). At this time, the maximum absorption wavelength (λmax) was 628 nm, and the Gram extinction coefficient (g) was 111 Lg ⁻¹ cm ⁻¹ . The results of liquid chromatography-mass spectrometry of this compound are shown below. In addition, the mass at this time has shown the molecular weight mass of the triarylmethane cation site | part.
LCMS (ESI, posi) m / z 546 ((M ⁺ C ₃₈ H ₄₈ N ₃ )

(Synthesis Example 3: Synthesis of Resin A)
145 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) was stirred while being purged with nitrogen, and the temperature was raised to 120 ° C. Here, 5.2 parts by mass of styrene, 132 parts by mass of glycidyl methacrylate, 4.4 parts by mass of monoacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton and 2.2′-azobis-2-methylbutyro A mixture of 8.47 parts by mass of nitrile was added dropwise over 3 hours, and the mixture was further stirred at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was changed to air substitution, 1.1 parts by mass of trisdimethylaminomethylphenol and 0.19 parts by mass of hydroquinone were added to 67.0 parts by mass of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 15.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.2 parts by mass of triethylamine were added and reacted at 100 ° C. for 3.5 hours. The polystyrene equivalent weight average molecular weight Mw measured by GPC of the resin solution thus obtained was about 9000, and the acid value was 25 mg-KOH / g. Propylene glycol monomethyl ether acetate was added to this resin solution so that the solid content was 40% by mass and used as Resin A.

(Synthesis Example 4: Synthesis of Resin B)
“NC3000H” (epoxy equivalent 288, softening point 69 ° C., manufactured by Nippon Kayaku Co., Ltd.) 400 parts by mass, acrylic acid 102 parts by mass, p-methoxyphenol 0.3 part by mass, triphenylphosphine 5 parts by mass, and propylene glycol monomethyl The reaction vessel was charged with 264 parts by mass of ether acetate (PGMEA) and stirred at 95 ° C. until the acid value was 3 mg-KOH / g or less. It took 9 hours for the acid value to reach the target (acid value 2.2 mg-KOH / g). Next, 151 parts by mass of tetrahydrophthalic anhydride was further added and reacted at 95 ° C. for 4 hours to obtain a resin solution having an acid value of 102 mg-KOH / g and a polystyrene-reduced weight average molecular weight (Mw) of 3900 measured by GPC. . Propylene glycol monomethyl ether acetate was added to this resin solution so that the solid content was 44% by mass and used as Resin B.

(Synthesis Example 5: Synthesis of Resin C)
80 parts by mass of methyl methacrylate, 20 parts by mass of n-butyl acrylate, and 26 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) were charged into a reaction vessel and heated to 80 ° C. in a nitrogen atmosphere. A mixed solution of 5.6 parts by mass of 3-mercapto-1,2-propanediol, 0.10 parts by mass of azobisisobutyronitrile and 2 parts by mass of PGMEA was added thereto over 2 hours, and further at 90 ° C. for 5 hours. Then, the mixture was stirred at 110 ° C. for 2 hours. Next, 10 parts by mass of pyromellitic anhydride and 85 parts by mass of PGMEA were added, the temperature was raised to 80 ° C., and 0.20 part by mass of 1,8-diazabicyclo- [5.4.0] -7-undecene was added. Then, the mixture was stirred at 100 ° C. for 5 hours to obtain a resin solution having a solid content of 46% by mass, an acid value of 53 mg-KOH / g, and a polystyrene-reduced weight average molecular weight (Mw) of 7300 measured by GPC.
Propylene glycol monomethyl ether acetate was added to the resin solution so that the solid content was 48.1% by mass and used as Resin C.

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

[Preparation 1 of colored resin composition]
The dye A obtained in Synthesis Example 1 and the resins A to C obtained in Synthesis Examples 3 to 5 are mixed with other components so as to have the composition described in Table 3 below, to obtain a colored resin composition Was prepared.
In addition, the numerical value of the upper stage of Table 3 represents the content rate (mass%) in the colored resin composition of each component to add, and the numerical value of a lower stage is the content ratio (mass%) in the total solid of each component. Represents.
In mixing, the components were stirred for 1 hour or more until they were sufficiently mixed, and finally filtered through a 5 μm piece filter to remove foreign matters.
Resin C was used as the (C) dispersant for the colored resin composition of Example 1, and Resins D to F were used for the colored resin compositions of Comparative Examples 1 to 3.

In addition, each compound in Table 12 is as follows.
LPN6919 (manufactured by BYK): basic dispersant containing tertiary amine LPN21116 (manufactured by BYK): basic dispersant containing tertiary amine and ammonium DB2000 (manufactured by BYK): basic dispersant containing ammonium PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether F559: Perfluoroalkyl group-containing oligomer (manufactured by DIC)
Irganox 1010: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propinate] (manufactured by BASF)
JPP-100: Tetraphenyldipropylene glycol diphosphite (manufactured by Johoku Chemical Industry Co., Ltd.)

[Production of colored resin film and evaluation of heat resistance]
Each colored resin composition prepared in [Preparation of colored resin composition 1] is applied onto a glass substrate cut into 5 cm square by spin coating so that the y value after firing is 0.120 as follows. After drying under reduced pressure, it was pre-baked on a hot plate at 80 ° C. for 3 minutes. Thereafter, the entire surface was exposed at an exposure amount of 60 mJ / cm ^{2 and} then baked at 230 ° C. for 60 minutes in a clean oven. The spectral transmittance of the obtained film was measured with a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.), and the chromaticity (C light source) and luminance in the XYZ color system were calculated. The results are shown in Table 4.

  As shown in Table 4, when baked at 230 ° C. for 60 minutes, Example 1 using an acidic dispersant shows high luminance, whereas in Comparative Examples 1 to 3 using a basic dispersant, the luminance is high. It became clear that it decreased greatly. This indicates that the heat resistance required for the color display manufacturing process is satisfied.

[Preparation 2 of colored resin composition]
The dyes A and B obtained in Synthesis Examples 1 and 2 and the resins A to B obtained in Synthesis Examples 3 and 4 were mixed with other components so as to have the composition described in Table 5 below. A colored resin composition was prepared.
In addition, the numerical value of the upper stage of Table 4 represents the content rate (mass%) in the colored resin composition of each component to add, and the numerical value of a lower stage is the content ratio (mass%) in the total solid of each component. Represents.
In mixing, the components were stirred for 1 hour or more until they were sufficiently mixed, and finally filtered through a 5 μm piece filter to remove foreign matters.

[Production of colored resin film and evaluation of light resistance]
The colored resin composition prepared in Example 1 of [Preparation of colored resin composition 1] and the colored resin composition prepared in [Preparation of colored resin composition 2] on a glass substrate cut into 5 cm squares. After applying by spin coating and drying under reduced pressure, it was pre-baked on a hot plate at 80 ° C. for 3 minutes. Thereafter, the entire surface was exposed at an exposure amount of 60 mJ / cm ² and baked at 230 ° C. for 30 minutes in a clean oven. At this time, the y value was adjusted to 0.120 when baked at 230 ° C. for 30 minutes in a clean oven. Thereafter, the entire surface was exposed at an exposure amount of 60 mJ / cm ^{2 and} then baked at 230 ° C. for 30 minutes. The spectral transmittance of the obtained film was measured with a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.), and the luminance was calculated. The weatherometer Ci4000 (manufactured by Atlas Co., Ltd.) was set through a polarizing plate having the transmittance shown in FIG. 2 and irradiated with simulated sunlight for 20 hours. The color difference (ΔE * ab) before and after irradiation was measured as light resistance, and the evaluation results are summarized in Table 6.

The color change ΔE * ab in Example 1 was smaller than that in Comparative Example 5 in which R ⁵ and R ^{6 in} the formula (I) were not aromatic ring groups. This indicates that the colored resin composition of the present invention has light resistance required for long-term reliability of a color display.
Further, it can be seen that there is almost no difference in color change ΔE * ab depending on the comparison between Example 1 and Reference Example 1 and the presence or absence of a dispersant. For this reason, in Comparative Example 5, it can be inferred that even if the resin C is added as in Example 1, it does not have the light resistance required for long-term reliability of the color display.

  According to the present invention, a decrease in luminance during heating can be significantly suppressed, a colored resin composition having light resistance required for long-term reliability of a color display while satisfying heat resistance required for a color display manufacturing process, A color filter, a liquid crystal display device, and an organic EL display device can be provided. Therefore, the present invention is useful in applications to color filters, liquid crystal display devices, organic EL display devices, and the like.

DESCRIPTION OF SYMBOLS 100 Organic EL element 10 Transparent support substrate 20 Pixel 30 Organic protective layer 40 Inorganic oxide film 50 Transparent anode

Claims (9)

(A) a coloring material, (B) a solvent, (C) a dispersant and (D) a binder resin,
(A) The coloring material contains a triarylmethane compound represented by the following formula (I), and (C) the dispersing agent contains a dispersing agent having an acidic group. Resin composition.

(In the above formula (I),
A ⁻ represents an imide anion or a methide anion.
R ^{1 to} R ⁴ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
R ⁵ and R ⁶ each independently represents an aromatic ring group which may have a substituent.
Further, the benzene ring and naphthalene ring in the above formula (I) may further have an arbitrary substituent. )   The colored resin composition according to claim 1, wherein the dispersant having an acidic group is a dispersant having an acid value larger than an amine value.   (A) The colored resin composition according to claim 1 or 2, wherein the colorant further contains a pigment. The colored resin composition according to claim 1, wherein A ⁻ in the formula (I) is a disulfonylimide anion.   (E) The colored resin composition according to any one of claims 1 to 4, further comprising a polymerizable monomer.   The colored resin composition according to claim 1, further comprising (F) a photopolymerization initiation system and / or (F ′) a thermal polymerization initiation system.   It has a pixel formed using the colored resin composition of any one of Claims 1-6, The color filter characterized by the above-mentioned.   A liquid crystal display device comprising the color filter according to claim 7.   An organic EL display device comprising the color filter according to claim 7.

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