JP6206548B2 - 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 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 brightness and higher contrast.
For the color filter, a colored resin composition using a pigment is mainly used. In order to obtain high brightness and high contrast, for example, in Non-Patent Document 1, the particle diameter of pigment particles is set to 1 of the coloration wavelength. Disclosed is a method of finely dispersing to / 2 or less.
However, since the blue pigment has a shorter coloration wavelength than other red and green pigments in particular, further fine dispersion is required in this case, which causes a problem of cost increase and stability after dispersion.

On the other hand, dyes have been developed as colorants.
For example, Patent Document 1 discloses using a triarylmethane derivative as a dye. However, brightness and heat resistance were insufficient. In order to improve this, for example, Patent Documents 2 and 3 disclose that the triarylmethane salt is further subjected to molecular modification such that the anion has a specific structure.

  On the other hand, as a method for improving the heat resistance of a dye without molecular modification, for example, Patent Documents 4 and 5 describe that an antioxidant is contained in a colored resin composition.

JP 2008-304766 A JP 2011-132492 A JP 2011-133844 A JP 2009-122650 A JP 2010-134278 A

Kiyoshi Hashizume “Journal of Color Material Association” (December 1967, page 608)

However, even the dyes described in Patent Documents 2 and 3 are insufficient in luminance and heat resistance.
Further, the pixels formed of the colored resin compositions described in Patent Documents 4 and 5 also have insufficient luminance and heat resistance.
Here, in view of the above problems, an object of the present invention is to provide a colored resin composition in which the luminance and heat resistance of the obtained pixel are good.
It is an object of the present invention to provide a color filter with high pixel luminance, a high-quality liquid crystal display device, and an organic EL display device.

As a result of intensive studies, the present inventors have found that the above problems can be solved by setting the water content within a specific range in a colored resin composition containing a specific dye, and have reached the present invention. .
That is, the present invention is a colored resin composition containing (A) a dye, (B) a solvent, and (C) a binder resin, wherein the (A) dye is a compound represented by the following formula (I) ( A colored resin composition, a color filter, and a liquid crystal display, characterized in that the water content of the colored resin composition is 1050 ppm or more and less than 11000 ppm. Devices and organic EL display devices.

[Z ^m− ] _n [A ^{n +} ] _m (I)
(In the above formula (I), Z ^m− represents an m-valent anion.
A ^{n +} represents a cation of an n-valent dye.
m and n represent the integer of 1-4. )

ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the colored resin composition with the favorable brightness | luminance and heat resistance of the pixel obtained.
By using such a colored resin composition, it is possible to provide a color filter with high pixel brightness, a high-quality liquid crystal display device, and an organic EL display device.

It is a section schematic diagram showing an example of an organic EL device which has a color filter of the present invention.

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 “acryl and / or methacryl”, “acrylate and / or methacrylate” and the like, for example, “(meth) acrylic acid” "Means" acrylic acid and / or 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.
In the present invention, “coloring material” means both “dye” and “pigment”. Furthermore, “aromatic ring” means “aromatic hydrocarbon ring” and “aromatic heterocyclic ring”. It shall mean both.

Moreover, terms such as “CI Pigment Green” mean a color index (CI).
The present invention is a colored resin composition containing (A) a dye, (B) a solvent, and (C) a binder resin, and having a water content of 1050 ppm or more and less than 11000 ppm, preferably (D) polymerization. The photopolymerization monomer, (E) a photopolymerization initiating component, and / or a thermal polymerization initiating component are included, and other components blended as necessary.
First, the (A) dye in the present invention will be described.

[(A) Dye]
The colored resin composition of the present invention contains a compound represented by the following formula (I) as a dye (A).
[Z ^m− ] _n [A ^{n +} ] _m (I)
(In the above formula (I), Z ^m− represents an m-valent anion.

A ^{n +} represents a cation of an n-valent dye.
m and n represent the integer of 1-4. )
Z ^m− represents an m-valent anion.
The m-valent anion is not particularly limited as long as the effects of the present invention are not impaired, but disulfonyl is advantageous in that the production is easy and the anion is stable because the negative charge is delocalized. It is preferably an imide anion.

A ^{n +} represents a cation of an n-valent dye.
The cation of the dye is not particularly limited as long as the effect of the present invention is not performed. For example, it is described in “Industrial Dyes-Chemistry, Properties, Applications (Wiley-VCH, 2003, edited by Klaus Hunger)”. Dyes.
More specifically, compounds having a dye skeleton (Chromophore) such as triarylmethanes, cyanines, styryls and azines can be mentioned, and can be appropriately selected depending on a desired color.

Especially when blue is desired, triarylmethanes are preferable from the viewpoint of excellent color density, luminance and heat resistance, and when purple is desired, color density, luminance and heat resistance are excellent. Triarylmethanes and cyanines are particularly preferred.
Hereinafter, triarylmethanes will be described in detail.
(About the compound represented by Formula (II))
Among the triarylmethanes, the compound represented by the formula (I) is a compound represented by the following formula (II) (hereinafter, referred to as the following formula (II), in that the obtained pixel has high luminance and good heat resistance. It may be referred to as “compound (II)”.

(In the above formula (II), m and Z ^m− are as defined in the above formula (I).
R ^{1 to} R ⁶ each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted aromatic ring group.
Adjacent R ^{1 to} R ⁶ may be bonded to form a ring, and the ring may have a substituent.

R ⁷ and R ⁸ represent a hydrogen atom or an arbitrary substituent.
R ⁷ and R ⁸ may be connected to each other to form a ring, and the ring may have a substituent.
Moreover, the benzene ring in the above formula (II) may further have an arbitrary substituent.
R ¹⁰¹ and R ¹⁰² have a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted alkenyl group having 2 to 6 carbon atoms, and a substituent. Represents an aromatic ring group which may be substituted, or a fluorine atom.

R ¹⁰¹ and R ¹⁰² may be bonded to each other to form a ring, and the ring may have a substituent.
In addition, multiple molecules in one molecule

May be the same structure or different structures. )
(About R ^{1 to} R ⁶ )
R ^{1 to} R ⁶ each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted aromatic ring group.
Examples of the alkyl group in R ^{1 to} R ⁶ include linear, branched or cyclic alkyl groups, and the number of carbon atoms is usually 1 or more, and usually 8 or less, preferably 5 or less. . Specific examples include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group and the like.

Examples of the aromatic ring group in R ^{1 to} R ⁶ include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
The aromatic hydrocarbon ring group may be a single ring or a condensed ring, and is not particularly limited as long as the number of carbon atoms forming the ring is 6 to 18, but for example, one free valence Benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring, and the like.
The free valence in the present invention is based on the description in “Organic Chemistry / Biochemical Nomenclature” (Nanedo, published May 20, 1992, translated by Kenzo Hirayama and Kazuo Hirayama, pages 11-12). It is.

  In addition, the aromatic heterocyclic group may be a single ring or a condensed ring, and is not particularly limited as long as the number of carbon atoms forming the ring is 3 to 10, but for example, one free atom Having a valence, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, 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, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, Synoline ring, quinoxaline ring, phenanthridine ring, Zone imidazole ring, perimidine ring, a quinazoline ring, a quinazolinone ring, groups such as azulene ring.

Adjacent R ^{1 to} R ⁶ 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 chemical stability, R ^{1 to} R ⁶ are preferably each independently a hydrogen atom, a C 1-8 alkyl group which may have a substituent, or a substituent. It is a good phenyl group, or when adjacent R ^{1 to} R ⁶ are connected to each other to form a ring. It has the C1-C8 alkyl group or substituent which may have a substituent more preferably at the point which improves the heat resistance of compound (II) and the heat resistance of the color filter obtained is excellent. It may be a phenyl group.

When R ^{1 to} R ⁶ are alkyl groups having 1 to 8 carbon atoms, it is presumed that the charges in the cation are dispersed by hyperconjugation and the cation is stabilized.
Moreover, when R < ¹ > -R < ⁶ > is the phenyl group which may have a substituent, since a conjugated system is extended, the electric charge in a cation will disperse | distribute and a cation will be stabilized. Thus, as a result of stabilization of the cation, the resulting color filter is more excellent in heat resistance.
Examples of the substituent that the alkyl group, aromatic ring group, and ring formed by connecting to each other in R ^{1 to} R ⁶ may have include those described in the following (Substituent Group W) section. Can be mentioned.

(Substituent group W)
Fluorine atom, chlorine atom, alkyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms, alkoxy group having 1 to 8 carbon atoms, phenyl group, mesityl group, tolyl group, naphthyl group, acetyloxy group, carbon C2-C9 alkoxycarbonyl group, phenoxycarbonyl group, carbamoyl group, C2-C9 alkylcarbamoyl group, phenylcarbamoyl group, sulfamoyl group, C1-C8 alkylsulfamoyl group, phenylsulfamoyl group An alkylcarbonyl group having 2 to 9 carbon atoms, a benzoyl group, an alkylsulfonyl group having 1 to 8 carbon atoms, a trifluoromethanesulfonyl group, a phenethyl group, a hydroxyethyl group, an acetylamino group and an alkyl group having 1 to 4 carbon atoms. A dialkylaminoethyl group, a trifluoromethyl group, Kirushiriru group, a nitro group, a cyano group, a carboxy group, an alkylthio group having 1 to 8 carbon atoms.

Among them, as the substituent that the alkyl group, the aromatic ring group, and the ring formed by connecting to each other in R ^{1 to} R ⁶ may have, preferably an alkyl group having 1 to 8 carbon atoms, or 2 to 2 carbon atoms. An alkoxyl group having 8 carbon atoms, a cyano group, an acetyloxy group, an alkyl carboxyl group having 2 to 8 carbon atoms, a sulfonic acid amide group, a sulfone alkylamide group having 2 to 8 carbon atoms, and a fluorine atom.

(About R ⁷ and R ⁸ )
R ⁷ and R ⁸ represent a hydrogen atom or an arbitrary substituent.
As this arbitrary substituent, the C1-C8 alkyl group which may have a halogen atom, a substituent, the aromatic ring group which may have a substituent, etc. are mentioned, for example.
R ⁷ and R ⁸ may be connected to each other to form a ring. When R ⁷ and R ⁸ are bonded to each other to form a ring, these may be a ring bridged with a heteroatom. Specific examples of this ring include the following. These rings may have a substituent.

(In the above, R ^1a and R ^2a each independently represents a hydrogen atom or an alkyl group.)
From the viewpoint that the obtained color filter is blue and has high luminance, it is preferable that R ⁷ and R ⁸ are not connected to each other to form a ring.
Moreover, the benzene ring in the above formula (II) may further have an arbitrary substituent.
Examples of the substituent that the benzene ring may have include those described in the above section (Substituent group W).

(About ^R101 and ^R102 )
R ¹⁰¹ and R ¹⁰² have a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted alkenyl group having 2 to 6 carbon atoms, and a substituent. Represents an aromatic ring group which may be substituted, or a fluorine atom.
Examples of the alkyl group and the aromatic ring group include those described in the above section (for R ^{1 to} R ⁶ ).

Examples of the alkenyl group include those having usually 2 or more and usually 6 or less carbon atoms. Specific examples include a vinyl group, an allyl group, and a 1-butenyl group.
Further, R ¹⁰¹ and R ¹⁰² are connected to form a part of the ring, so that R ^{10 is in a} plane composed of the benzene ring adjacent to the sp2 carbon atom at the center of the triarylmethane structure.
^Since the benzene ring to which ¹ and R ¹⁰² are bonded has a twisted positional relationship, it has blue absorption, which improves the spectral characteristics of the colored resin composition for color filters using this, and the contrast of the blue display member Is preferable in that it is easy to improve.
Examples of the structure of the linking moiety of R ¹⁰¹ and R ¹⁰² include the following.

The structure of the linking moiety of R ¹⁰¹ and R ¹⁰² may have a substituent. Examples of the substituent include those described in the above section (Substituent group W).
Moreover, the benzene ring in the above formula (I) may further have an arbitrary substituent. That is, it may have substituents other than those specified in formula (II) as long as the effects of the present invention are not impaired, but it is specified in formula (II) from the viewpoint of easy production. It is preferable not to have any other substituent.

Examples of such a substituent include the substituents described in the above section (Substituent Group W).
[Compound represented by formula (II-1)]
The compound represented by the formula (II) is preferably a compound represented by the following formula (II-1).

(In said formula (II-1), R < ¹ > -R < ⁸ >, R < ¹⁰¹ > and R ^<102> are synonymous with the definition in said Formula (II).
The benzene ring in the above formula (II-1) may further have an arbitrary substituent.
R ²¹ and R ²² are each independently an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted alkenyl group having 2 to 6 carbon atoms, or a substituent. The C3-C8 cycloalkyl group which may have is represented.

R ²¹ and R ²² may be connected to each other to form a ring, and the ring may have a substituent. )
(For R ²¹ and R ²²⁾
R ²¹ and R ²² are each independently an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted alkenyl group having 2 to 6 carbon atoms, or a substituent. The C3-C8 cycloalkyl group which may have is represented.

R ²¹ and R ²² may be connected to each other to form a ring, and the ring may further have a substituent.
Examples of the substituent that the alkyl group, alkenyl group, cycloalkyl group, and ring formed by connecting to each other in R ²¹ and R ²² may have include those described in the above (Substituent group W) section. Can be mentioned.

Among them, as the substituent of the alkyl group, alkenyl group or cycloalkyl group in R ²¹ and R ²² , the fluorine atom is a substituent in that the anion charge is more delocalized and the heat resistance of the dye is improved. It is preferable to have as.
Among them, R ²¹ and R ²² are preferably a group containing a fluorine atom, particularly a perfluoroalkyl group having 1 to 8 carbon atoms, in that the anion charge is dispersed and the anion is stabilized. Preferably there is.

[Specific Example of Compound Represented by Formula (II)]

[Compound represented by Formula (III)]
The compound represented by the formula (I) is a compound represented by the following formula (III) among triarylmethanes in that the obtained pixel has high luminance and good heat resistance. Is preferred.

(In said formula (III), m and ^Zm- are synonymous with the said formula (I).
R ^{11 to} R ¹⁶ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
R ^{11 to} R ¹⁴ may be connected to each other to form a ring, and the ring may have a substituent.

R ¹⁷ and R ¹⁸ each independently represents a hydrogen atom or an arbitrary substituent. R ¹⁷ and R ¹⁸ may be bonded to each other to form a ring.
Further, the benzene ring and indole ring in the above formula (III) may further have an arbitrary substituent.
In addition, multiple molecules in one molecule

May be the same structure or different structures. )
(For R ¹¹ to R ¹⁶⁾
R ^{11 to} R ¹⁶ each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted aromatic ring group.
Examples of the alkyl group having 1 to 8 carbon atoms and the aromatic ring group are the same as those described in the above section (for R ^{1 to} R ⁶ ).

Further, when adjacent R ^{11 to} R ¹⁶ , that is, R ¹¹ and R ¹² , R ¹³ and R ^14, and R ¹⁵ and R ¹⁶ are bonded to each other to form a ring structure, the above (R ^{1 to} R ⁶ ).
(About R ¹⁷ and R ¹⁸ )
R ¹⁷ and R ¹⁸ represent a hydrogen atom or an arbitrary substituent. Examples of the optional substituents include those described in the R ¹ to R ^6.

R ¹⁷ and R ¹⁸ may be connected to each other to form a ring.
In the case where R ¹⁷ and R ¹⁸ are bonded to each other to form a ring, these may be a ring bridged with a heteroatom, and specific examples thereof are described in the above section (for R ⁷ and R ⁸ ). It is the same as that. These rings may have a substituent.
From the viewpoint that the obtained color filter is purple and has high luminance, it is preferable that R ⁷ and R ⁸ are not connected to each other to form a ring.

In addition, it is preferable that the obtained color filters are red and have high luminance, so that they are connected to each other to form a ring.
In compound (III), the benzene ring and the indole ring may further have a substituent. That is, you may have a substituent other than having specified in Formula (III) in the range which does not impair the effect of this invention.
Examples of such a substituent include the substituents described in the above section (Substituent Group W).

In addition, in the benzene ring in formula (III), when a bulky group is bonded to the carbon atom located at the center of the triarylmethine structure, the planarity of the molecule is inhibited, and the compound Color purity may be reduced. Accordingly, it is preferable that the o-position does not have a substituent or is substituted with a halogen atom or an alkyl group having 1 to 4 carbon atoms.
In addition, compound (III) may form a dimer, trimer, or the like by extending a linker from R ^{11 to} R ¹⁸ , for example.
(About the compound represented by Formula (III-1))
In the compound (III), particularly preferably, the anion is a disulfonylimide anion. In the formula (III), a compound represented by the following formula (III-1) (hereinafter referred to as “compound (III-1)”) It may be referred to as “.

(Wherein R ^{11 to} R ¹⁸ are the same as those in formula (III). R ³¹ and R ³² are each independently an alkyl having 1 to 8 carbon atoms which may have a substituent. Represents a group, an alkenyl group having 2 to 6 carbon atoms which may have a substituent, or a cycloalkyl group having 3 to 8 carbon atoms which may have a substituent.
R ³¹ and R ³² may be bonded to each other to form a ring. (About R ³¹ and R ³² )
R ³¹ and R ³² are each independently an alkyl group having 1 to 8 carbon atoms which may have a substituent, an alkenyl group having 2 to 6 carbon atoms which may have a substituent, or a substituent. The C3-C8 cycloalkyl group which may have is represented.

R ³¹ and R ³² may be bonded to each other to form a ring. R ³¹ and R ³² are the same as R ²¹ and R ²² in the formula (II-1), and preferred embodiments are also the same.
Although the preferable specific example of the compound represented by Formula (III) in this invention is shown below, this invention is not limited to these.
[Specific Examples of Compound (III)]

((A) Dye content)
The content of the (A) dye contained in the colored resin composition of the present invention varies depending on the desired pixel color. For example, the content is usually 1% by weight or more, preferably 3% by weight or more, based on the total solid content. Preferably, it is 5% by weight or more, usually 50% by weight or less, more preferably 40% by weight or less, more preferably 30% by weight or less.

When it is within the above range, the film thickness is appropriate with respect to the color density, and it is easy to control the gap when forming a liquid crystal cell. Furthermore, the dispersion stability is high, and reaggregation and thickening are difficult to place, which is preferable.
In addition, also when it contains dye other than compound (I) as (A) dye, it is preferable that it is in the said range, and (A) dye is compound (A) at the point which is easy to acquire the effect of this invention. It is particularly preferred that only I).

[(B) Solvent]
The (B) solvent in the present invention has a function of adjusting the viscosity by dissolving or dispersing each component contained in the colored resin composition.
The solvent (B) may be any solvent as long as it can dissolve or disperse each component constituting the colored resin composition, and a solvent having a boiling point in the range of 100 to 200 ° C. is preferably selected. 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, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as butyl, 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.

Among the above solvents, glycol monoalkyl ethers are preferred from the viewpoint of the solubility of the dye (A) according to the present invention. Among these, propylene glycol monomethyl ether is particularly preferable from the viewpoint of the solubility of various components in the composition.
In addition, for example, when a pigment described later is included as an optional component, glycol alkyl ether acetates are further used as a solvent from the viewpoint that the balance of coatability, surface tension, etc. is good and the solubility of the constituent components in the composition is relatively high. It is more preferable to use a mixture of these. In a composition containing a pigment, glycol monoalkyl ethers have a high polarity, tend to aggregate the pigment, and may reduce storage stability such as increasing the viscosity of the colored resin composition. For this reason, it is preferable that the amount of the glycol monoalkyl ether used is not excessively large, and the proportion of the glycol monoalkyl ether in the solvent (B) is preferably 5 to 50% by weight, more preferably 5 to 30% by weight. .

  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 such a high boiling point solvent is preferably 3 to 50% by weight, more preferably 5 to 40% by weight, and particularly preferably 5 to 30% by weight based on 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. .
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 weight. When the content of the (B) solvent in the composition exceeds 99% by weight, the concentration of each component excluding the (B) solvent becomes too small and may be inappropriate for forming a coating film. . On the other hand, the lower limit of the content of the solvent (B) is usually 75% by weight, preferably 80% by weight, and more preferably 82% by weight in consideration of viscosity suitable for coating.

[(C) Binder resin]
(C) The preferred resin for the binder resin differs depending on the curing means.
When the colored resin composition of the present invention is a photopolymerizable resin composition, examples of the (C) binder resin include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, 11-14144, JP-A No. 11-174224, JP-A No. 2000-56118, JP-A No. 2003-233179, and the like can be used. C-1) to (C-5) resins and the like.

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

The resins (C-2) to (C-5) may be anything as long as they are dissolved in an alkaline developer and are soluble to the extent that the desired development processing is performed. It is the same as that described as the same item in 2009-025813. The preferred embodiment is also the same.
(C-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 a part of the epoxy group of the copolymer. As one of particularly preferable resins of the alkali-soluble resin resin (C-1) obtained by adding a polybasic acid anhydride to at least a part of the 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 (meth) acrylate. ) 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 (7) Acrylate is preferred.

  The repeating unit derived from the mono (meth) acrylate having the structure represented by the following formula (7) 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 (7), R ⁸⁹ represents a hydrogen atom or a methyl group, and R ⁹⁰ represents a structure represented by the following formula (8).

The formula (8), R ⁹¹ ~R ⁹⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ⁹⁶ and R ⁹⁸ may be connected to each other to form a ring.
The ring formed by connecting R ⁹⁶ and R ⁹⁸ is preferably an aliphatic ring, may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.
Among these, among the structures represented by the formula (8), those represented by the following structural formulas (8a), (8b), or (8c) are particularly preferable.

In addition, the mono (meth) acrylate which has a structure represented by the said Formula (8) 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 (8), 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 strength 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.

  The polystyrene-reduced weight average molecular weight (Mw) of the above-described binder resin (C-1) measured by GPC (gel permeation chromatography) is preferably 3000 to 100,000, and particularly preferably 5000 to 50000. If the molecular weight is less than 3000, heat resistance and film strength may be inferior, and if it exceeds 100,000, the solubility in a developer tends to be insufficient. 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 (C-1) 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.
(C) Content of binder resin is 0.1-80 weight% normally in a total solid, Preferably it is 1-60 weight%.
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.

<Moisture content of the colored resin composition>
The water content of the colored resin composition of the present invention is a value measured by the following [Method for measuring water content of colored resin composition], usually 1060 ppm or more, preferably 1100 ppm or more, more preferably 1500 ppm or more, and usually less than 11000 pp. , Preferably less than 9000 ppm and less than 7100 ppm.
It is preferable at the point which is within the said range by the effect of this invention being favorable.
The water added to bring the water content within the above range is not particularly limited as long as the effects of the present invention are not impaired. For example, in addition to ultrapure water, clean water, distilled water, and ion-exchanged water may be used. Can be mentioned.

[Method for measuring water content of colored resin composition]
In the present invention, the water content of the colored resin composition is measured by the standard method described in the manual under the following conditions by the Karl Fischer method.

Apparatus: Karl Fischer moisture meter CA-21 (Mitsubishi Chemical Analytech)
・ Injection amount: 0.1 mg
・ Temperature: 23 degrees ・ Anolyte: Aquamicron AX
-Catholyte: Aquamicron CXU
The measuring device for specifying the present invention is not particularly limited as long as the same measurement as that of the above apparatus is possible, but it is preferable to use the above apparatus.

[Method for adjusting water content of colored resin composition]
What is necessary is just to adjust using the various means, in order to make the moisture content of a colored resin composition into the said range.
Specifically, the water content of the colored resin composition may be appropriately measured while adding water to the colored resin composition so as to be within the scope of the present invention.

The addition time of water may be added while mixing the above (A) dye, (B) solvent and (C) binder resin, and may be mixed after adding water to each material before mixing. .
When mixing after adding water to each material, there is no restriction | limiting in particular in the order of mixing.
Further, when water is excessively added, dehydration may be performed using various means.
The timing of dehydration is not particularly limited, and when water addition is performed before the dispersion treatment, the dehydration may be continued or may be dehydrated after the dispersion treatment.

Examples of the dehydration means include a method using a porous material such as molecular sieve, or a dehydrating agent such as sodium sulfite (Na ₂ SO ₃ ) or calcium chloride. In this case, these porous materials and dehydrating agents are added to each component before mixing and the colored resin composition after mixing, mixed by a technique such as stirring, and after dehydration, the porous materials and dehydrating agents are added. What is necessary is just to remove by means, such as filtration.

  The detailed conditions of dehydration are not particularly limited, and may be adjusted as appropriate according to the dehydration technique and dehydration timing. For example, when a molecular sieve is mixed with the colored resin composition after mixing and dehydration is performed, Molecular Sieves 3A 1/16 (manufactured by Wako Pure Chemical Industries, Ltd.) or the like can be used as the molecular sieve.

<Reason for effect>
With the configuration of the present invention, the reason why the resulting pixel has high luminance and excellent heat resistance is presumed as follows.
The following is a description of factors that decrease the luminance of a pixel obtained when a pixel is formed using a colored resin composition containing the compound represented by the formula (1) as a dye.
After the coating film is formed using the colored resin composition, heat curing is performed. At this heating, the compound represented by the formula (1) is a peripheral molecule (for example, binder resin, polymerizable monomer, photopolymerization start). One of the factors is that the structural change of the dye occurs due to chemical reaction with the components.

Here, when an appropriate amount of water molecules is present in the colored resin composition, intermolecular hydrogen bonds are formed between the dye and the water molecules. The dyes having water molecules and intermolecular hydrogen bonds easily associate with each other, and aggregates are formed. That is, when the dye forms an aggregate, the reaction with surrounding molecules is hindered, and the luminance reduction of the obtained pixel is suppressed.
On the other hand, if the amount of water molecules is too large, the probability of reaction between the dye and water molecules increases, resulting in a decrease in luminance of the resulting pixel.

[(D) Polymerizable monomer]
The colored resin composition of the present invention preferably contains (D) a polymerizable monomer because the crosslink density in the film can be easily controlled.
(D) Although a well-known material can be used as a polymerizable monomer, It is preferable that it is a compound which has an ethylenically unsaturated double bond at the point that the dark reactivity in a colored resin composition is low.

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 (D) 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.
Examples of the ethylenic compound include unsaturated carboxylic acid such as (meth) acrylic acid; ester of monohydroxy compound and unsaturated carboxylic acid; ester of aliphatic polyhydroxy compound and unsaturated carboxylic acid; aromatic polyhydroxy An ester of a compound and an unsaturated carboxylic acid; an ester obtained by an esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound such as the above-mentioned aliphatic polyhydroxy compound or aromatic polyhydroxy compound; And an ethylenic compound having a urethane skeleton obtained by reacting an isocyanate compound with 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 is not necessarily a single substance but may be 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, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, pentaerythritol or (meth) acrylic ester of dipentaerythritol is more preferable, and dipentaerythritol hexa (meth) acrylate is particularly preferable.

  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 pentaerythritol and / or 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 (D) polymeric monomer as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g. If the acid value of this polyfunctional monomer is too low, the development and dissolution properties tend to be lowered, and if it is too high, production and handling may be difficult, and photopolymerization performance may deteriorate, and the surface smoothness of the pixel, etc. Curability may be inferior. Accordingly, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer should be adjusted so as to fall within the above range. Is preferred.

  In the present invention, more preferred polyfunctional monomers having acid groups are dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinic acid ester of dipentaerythritol pentaacrylate, which are commercially available as “TO1382” manufactured by Toagosei Co., Ltd. It is a mixture containing the 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 of the polymerizable monomer (D) is usually 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more in the total solid content. Further, it is usually 80% by weight or less, preferably 70% by weight or less, more preferably 50% by weight or less, and particularly preferably 40% by weight or less.
The ratio of the (D) polymerizable monomer to the total colorant including the above-mentioned dye (A) is usually 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, and particularly preferably 20%. It is usually not more than 200% by weight, preferably not more than 100% by weight, more preferably not more than 80% by weight.
If it is within the above range, the light effect is sufficient, and it is difficult to cause adhesion failure at the time of development, and the cross section after development is difficult to have a reverse taper shape. It is preferable in that a defect or the like hardly occurs.

[(E) Photopolymerization initiation component and / or thermal polymerization initiation component]
The colored resin composition of the present invention preferably contains (E) a photopolymerization initiation component and / or 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 includes a resin having an ethylenic double bond as the component (C), or includes an ethylenic compound as the component (D), it directly absorbs light, or It is preferable to contain a photopolymerization initiating component that has a function of generating a polymerization active radical and / or a thermal polymerization initiating component that generates a polymerization active radical by heat. In the present invention, the component (E) as the photopolymerization initiation component is a photopolymerization initiator (hereinafter arbitrarily referred to as (E1) component) or a polymerization accelerator (hereinafter arbitrarily referred to as (E2) component). , Means a mixture in which an additive such as a sensitizing dye (hereinafter, arbitrarily referred to as component (E3)) is used in combination.

(Photopolymerization initiation component)
The colored resin composition of the present invention preferably contains (E) a photopolymerization initiation component. The photopolymerization initiating component is usually used as a mixture of (E1) a photopolymerization initiator, and (E2) a polymerization accelerator added as necessary, (E3) an additive such as a sensitizing dye, and the like. It is a component having a function of generating a polymerization active radical by directly absorbing or photosensitizing to cause a decomposition reaction or a hydrogen abstraction reaction.

  Examples of (E1) photopolymerization initiator constituting the photopolymerization initiating component include titanocene derivatives described in JP-A Nos. 59-152396 and 61-151197, etc .; 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-s -Radical activators such as 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 And oxime ester derivatives described in JP-A No. 2000-80068 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, and oxime ester derivatives are particularly preferable.

The oxime ester derivatives include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (o-benzoyloxime), ethanone, 1- [9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime), and the like.
In addition, benzoin alkyl ethers, anthraquinone derivatives; acetophenone derivatives such as 2-methyl- (4′-methylthiophenyl) -2-morpholino-1-propanone, 2-ethylthioxanthone, 2,4-diethylthioxanthone, etc. Examples also include thioxanthone derivatives, benzoate derivatives, acridine derivatives, phenazine derivatives, anthrone derivatives and the like.

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 (E2) 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.
Each of these (E1) photopolymerization initiator and (E2) polymerization accelerator may be used alone or in combination of two or more.

  Further, (E3) sensitizing dye is used for the purpose of increasing the sensitivity as required. As the sensitizing dye, an appropriate one is used according to 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. Coumarin dyes having a heterocyclic ring; JP-A-3-239703, JP-A-5-289335, etc .; 3-ketocoumarin dyes; 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-A-52-112681 JP, 58-15503, JP 60-88005, JP 59-56403, JP 2-69, JP 57-168088, JP 5-10. 761 No., JP-A-5-210240, dyes having a dialkyl aminobenzene skeleton described in JP-A 4-288818 Patent JP-like.

(E3) 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 of these (E) photopolymerization initiating components is usually 0.1% by weight or more, preferably 0.2% by weight or more, more preferably 0.8% by weight in the total solid content. It is 5% by weight or more, usually 40% by weight or less, preferably 30% by weight or less, and more preferably 20% by weight or less.
Within the above range, it is preferable in that the sensitivity to the exposure light beam is good, the solubility of the unexposed portion in the developer is sufficient, and poor development is unlikely to occur.

(Thermal polymerization initiation component)
Specific examples of the thermal polymerization initiation component (thermal polymerization initiator) 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, a thermal polymerization initiator described in International Publication No. 2009/107734 pamphlet or the like can be used.
These thermal polymerization initiators may be used individually by 1 type, and may use 2 or more types together.

[Optional ingredients]
The colored resin composition of the present invention includes a surfactant, an organic carboxylic acid and / or an organic carboxylic acid anhydride, a thermosetting compound, a plasticizer, and the above-described (A) according to the present invention, in addition to the components described above. It may contain dyes other than dyes, thermal polymerization inhibitors, storage stabilizers, surface protective agents, adhesion improvers, development improvers and the like. Moreover, when a pigment is contained as a coloring matter, a dispersant or a dispersion aid may be contained. As these optional components, for example, various compounds described in JP-A-2007-113000 can be used.

[Preparation Method of Colored Resin Composition]
In the present invention, the colored resin composition can be prepared by an appropriate method. For example, (A) a dye containing compound (I), (C) a binder resin and water are mixed together with a solvent and other additives. Can be prepared.
In addition to (A) the dye, a preparation method in the case of further containing a pigment is as follows. In the solvent containing the pigment, in the presence of a dispersing agent and, if necessary, a dispersing aid, (C) a binder. A pigment dispersion is prepared by mixing and dispersing together with a part of the resin while pulverizing using, for example, a paint shaker, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer and the like. In the pigment dispersion, (A) dye containing compound (I), (C) binder resin and water, and (D) polymerizable monomer, (E) photopolymerization initiating component and / or thermal polymerization initiating as necessary. The method of preparing by adding additives, such as a component, and mixing can be mentioned.

[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. This colored resin composition is supplied onto the substrate to form components such as a color filter, a liquid crystal display device, and an organic EL display device.
That is, the colored resin composition of the present invention is preferably a colored resin composition for color filters.
Hereinafter, as an application example of the colored resin composition of the present invention, an application as a color filter, and a liquid crystal display device (panel) and an organic EL display device using them will be described.

<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.

The substrate used for forming the pixel is not particularly limited as long as it is transparent and has an appropriate strength. For example, a polyester resin, a polyolefin resin, a polycarbonate resin, an acrylic resin, or a thermoplastic resin is used. A sheet, an epoxy resin, a thermosetting resin, various glass, etc. are mentioned.
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.
For example, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like can be used as the radiation used when forming the pixels, but 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-di- or tri-ethanolamine, mono-di-, or tri -Methylamine, mono-, di-, or tri-ethylamine, mono-, or di-isopropylamine, n-butylamine, mono-, di-, or tri-isopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium Hydroxide (TMAH) Aqueous solution of an organic alkaline compound choline are preferred.

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 is used as a part of a color display, a liquid crystal display device, or the like. 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 photolithography 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 including the color filter of the present invention, for example, as shown in FIG. 1, on a blue color filter in which pixels 20 are formed on a transparent support substrate 10 by the colored resin composition of the present invention. 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.

EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to description of a following example, unless the summary is exceeded.
<Synthesis of dyes>
(Reference Synthesis Example 1: Synthesis of Dye A)

  Compound 1 (6.0 g, 25 mmol, synthesized by the method described in International Publication No. 2008003604), Compound 2 (6.4 ml, 50 mmol: manufactured by Tokyo Chemical Industry Co., Ltd.), potassium carbonate (6.9 g, 50 mmol), N-methyl A mixture of -2-pyrrolidone (25 ml) was heated and stirred at 110 to 125 ° C. for 4 hours. After cooling to room temperature, water was added and extracted with toluene. The toluene layer was washed with dilute hydrochloric acid and saturated brine, and dried over anhydrous sodium sulfate. Concentration under reduced pressure gave 9.2 g of a light brown oil. This was dissolved in ethanol (40 ml), a solution of sodium hydroxide (2 g, 52.3 mmol) in water (25 ml) was added, and the mixture was stirred at 85 ° C. for 1 hour. The mixture was allowed to cool and extracted with toluene, and the toluene layer was washed with saturated brine and dried over anhydrous sodium sulfate. After concentration under reduced pressure, the residue was purified by silica gel column chromatography (hexane / ethyl acetate = 3/1) to obtain Compound 3 (5.95 g, yield 94%) as a white powder.

  Compound 4 (1.47 g, 4.34 mmol, synthesized by the method described in International Publication No. 2009107734), Compound 3 (1.1 g, 4.34 mmol), toluene (30 ml), phosphorus oxychloride (0.6 ml) The mixture was heated to reflux for 4 hours, cooled to room temperature, water was added, and the mixture was extracted with chloroform. The chloroform layer was concentrated under reduced pressure and purified by silica gel column chromatography (developing solvent: chloroform / methanol = 15/1 to 10/1), and the obtained solid was washed with hexane to obtain compound 5 (1.32 g, collected). 50%).

A mixture of compound 5 (8.9 g, 14.6 mmol), compound 6 (4.2 g, 14.6 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) and methanol (50 ml) was stirred at 50 ° C. for 1.5 hours, and then concentrated under reduced pressure. The obtained solid was washed with methanol / water = 1/2 to obtain Dye A (11.5 g, yield 92.3%).
<Resin synthesis>
(Reference Synthesis Example 2: Synthesis of Resin A)
145 parts by weight of propylene glycol monomethyl ether acetate was stirred while purging with nitrogen, and the temperature was raised to 120 ° C. Here, 5.2 parts by weight of styrene, 132 parts by weight of glycidyl methacrylate, and 4.4 parts by weight of monoacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were dropped, and 2.2′-azobis-2 -8.47 weight part of methylbutyronitrile was dripped over 3 hours, and also it stirred at 90 degreeC for 2 hours. Next, the inside of the reaction vessel was changed to air substitution, 1.1 parts by weight of trisdimethylaminomethylphenol and 0.19 parts by weight of hydroquinone were added to 67.0 parts by weight of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 15.2 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.2 parts by weight of triethylamine were added and reacted at 100 ° C. for 3.5 hours. The weight average molecular weight Mw in terms of polystyrene measured by GPC of the resin A thus obtained was about 9000, and the acid value was 25 mg-KOH / g.

(Reference Synthesis Example 3: Synthesis of Resin B)
“NC3000H” (manufactured by Nippon Kayaku Co., Ltd.) (epoxy equivalent 288, softening point 69 ° C.) 400 parts by weight, acrylic acid 102 parts by weight, p-methoxyphenol 0.3 part by weight, triphenylphosphine 5 parts by weight, and propylene glycol The reaction vessel was charged with 264 parts by weight of monomethyl ether acetate and stirred at 95 ° C. until the acid value became 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 weight of tetrahydrophthalic anhydride was further added and reacted at 95 ° C. for 4 hours, and a solution of resin B having an acid value of 102 mg-KOH / g and a polystyrene-equivalent weight average molecular weight (Mw) 3900 measured by GPC was added. Obtained.

<Preparation of colored resin composition>
The dye A obtained in Reference Synthesis Example 1 and the resins A and B obtained in Reference Synthesis Examples 2 and 3 are mixed with other components so as to have the composition described in Table 1 below, to obtain a colored resin. A composition was prepared.
The mixing was carried out while adding the amount of water shown in Table 2.
The numerical values in Table 1 represent parts by weight of each component to be added.
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.

The numerical values in Tables 1 and 2 both represent parts by weight of each component to be added.
Each compound in Table 1 is as follows.
PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether

<Measurement / Evaluation>
[1] Method for Measuring Water Content of Colored Resin Composition Using CA-21 (manufactured by Mitsubishi Chemical Analytech Co., Ltd.), the water content in the colored resin composition was measured by the Karl Fischer coulometric titration method. Aquamicron AX was used for the anolyte and Aquamicron CXU for the catholyte. The measurement was performed according to the procedure described in the CA-21 manual.

The amount of the colored resin composition added for measurement was about 0.1 mg.
The results are summarized in Table 3.
[2] Production of colored resin film and evaluation of heat resistance On a glass substrate cut into 5 cm square, each colored resin composition was applied by spin coating so that the y value after drying was 0.112, 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 with an exposure amount of 60 mJ / cm ² . Thereafter, the spectral transmittance was measured with a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.), and the chromaticity (C light source) in the XYZ color system was calculated (luminance: value before heating). Subsequently, baking was performed at 230 ° C. for 30 minutes in a clean oven, the spectral transmittance was measured with a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.), and the chromaticity (C light source) in the XYZ color system was calculated. (Luminance: Value after 230 ° C. × 30 min).

The results are summarized in Table 3.
In Table 3, ΔEab represents the difference between “luminance: value before heating” and “luminance: value after 230 ° C. × 30 min”, and the smaller the value, the higher the heat resistance.

As shown in Table 3, the pixels formed using the colored resin composition of the present invention have high luminance and high heat resistance.
That is, a color filter including pixels formed using the colored resin composition of the present invention, and a liquid crystal display device and an organic EL display device including the color filter are of high quality.

DESCRIPTION OF SYMBOLS 100 Organic EL element 20 Pixel 30 Organic protective layer 40 Inorganic oxide film 500 Organic light-emitting body 51 Hole injection layer 54 Electron injection layer

Claims (5)

A colored resin composition containing (A) a dye, (B) a solvent, and (C) a binder resin,
The (A) dye contains a compound represented by the following formula (I),
And moisture content of the colored resin composition, more 1060Ppm, Ri der than 11000Ppm,
Furthermore, (D) The coloring resin composition characterized by containing a polymerizable monomer .
[Z ^m− ] _n [A ^{n +} ] _m (I)
(In the above formula (I), Z ^m− represents an m-valent disulfonylimide anion .
A ^{n +} represents an n-valent cation of a compound having a dye skeleton of triarylmethanes .
m and n represent 1 . ) The colored resin composition according to claim 1 , further comprising (E) a photopolymerization initiating component and / or a thermal polymerization initiating component. It has a pixel formed using the colored resin composition of Claim 1 or 2 , The color filter characterized by the above-mentioned. A liquid crystal display device comprising the color filter according to claim 3 . An organic EL display device comprising the color filter according to claim 3 .

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