JP2014189663A - Colored resin composition, color filter, liquid crystal display device, and organic el display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored resin composition excellent in adhesiveness between a pixel to be obtained and a substrate, and further to provide a color filter formed using the colored resin composition and a high-quality liquid crystal display device and an organic EL display device.SOLUTION: There is provided a colored resin composition which comprises: (A) a dye; (B) a solvent; (C) a binder resin; and (D) an antioxidant, where the (A) dye contains a xanthene-based compound represented by the specific structural formula (I) and the antioxidant contains a compound represented by the specific structural formula (II) and further a phosphorous acid ester.

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.
Conventionally, as a method for producing a color filter used in a liquid crystal display device or the like, a coating film of a colored radiation-sensitive composition is formed on a substrate or a substrate on which a light-shielding layer having a desired pattern has been previously formed. There is known a method of obtaining pixels of each color by irradiating radiation through a photomask having a pattern (hereinafter referred to as “exposure”), developing and dissolving and removing unexposed portions, and then post-baking. Yes.

Taking into account the trend of energy conservation, 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, when the pigment particles are finely dispersed, cost increases and stability after dispersion become problems.
On the other hand, dyes have been developed as colorants.
For example, in Patent Documents 1 and 2, as a colored resin composition for forming a blue pixel, C.I. I. (Color Index) It is disclosed to use pigment blue 15: 6 and a xanthene dye.

JP 2010-32999 A JP 2010-26334 A

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

However, with the colored resin compositions described in Patent Documents 1 and 2, there are cases where image formation is insufficient or problems such as disconnection may occur when a conductive film such as ITO is formed.
As a result of intensive studies, the present inventors have found that the adhesion between the obtained pixel and the substrate is a cause of the above problem.

That is, an object of the present invention is to provide a colored resin composition having excellent adhesion between the obtained pixel and the substrate.
Furthermore, this invention makes it a subject to provide the color filter containing the pixel formed using the said colored resin composition, a high quality liquid crystal display device, and an organic electroluminescent display device.

As a result of further earnest studies, the present inventors can solve the above problems by containing a specific antioxidant and a phosphite in the case where the dye (A) contains a xanthene compound. The present invention was reached upon finding out.
That is, the present invention includes (A) a dye, (B) a solvent, (C) a binder resin, and (D) an antioxidant, wherein the (A) dye is a xanthene compound represented by the following formula (I) ( The compound (hereinafter, referred to as “xanthene compound (I)”) and the (D) antioxidant is represented by the following formula (II) (hereinafter referred to as “compound (II)”) And (E) a colored resin composition characterized by containing a phosphite, a color filter, a liquid crystal display device, and an organic EL display device.

(In the formula (I),
R ^{1 to} R ⁴ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted aromatic carbon atom having 6 to 18 carbon atoms. Represents a hydrogen ring group.
R ¹ and R ² , and R ³ and R ⁴ may be independently bonded to each other to form a ring, and the ring may have a substituent.

R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent.
R ⁷ represents an arbitrary substituent.
m represents an integer of 0 to 5. When m is an integer of 2 or more, the plurality of R ⁷ may be the same or different.

p represents an integer of 1 to 4. When p is 2 to 4, the structures in [] containing a plurality of xanthene skeletons may be the same or different.
X ^q- represents an arbitrary q-valent anion.
q represents the integer of 1-4.
n represents an integer of 0 to 4. When n is 2-4, several ^Xq- may be the same or different.

When R ^{1 to} R ⁷ are a group containing a sulfonate group or a carboxylate group, or when R ⁷ is a sulfonate group or a carboxylate group, n is 0 and p = 1, and otherwise , P = n × q. )

(In said formula (II), R ^<1a> and R ^<2a> respectively independently represent the C1-C12 alkyl group which may have a substituent.
L represents a hydrogen atom, a carbon atom, an aromatic ring group which may have a substituent, or a heterocyclic group which may have a substituent.
Z is a divalent group consisting of an alkylene group having 1 to 10 carbon atoms and / or an ester bond which may have a substituent.
The benzene ring in the above formula (II) may have an arbitrary substituent other than R ^1a and R ^2a , —OH, and Z.
r represents an integer of 1 to 4.
In addition, when r is 2 to 4, a plurality of molecules contained in one molecule

May be the same structure or different.
* Represents a binding site to L. )

The present invention makes it possible to provide a colored resin composition that is excellent in the adhesion between the obtained pixel and the substrate and that has higher luminance.
Furthermore, this invention can provide the color filter containing the pixel formed using the said colored resin composition, a high quality liquid crystal display device, and an organic electroluminescence display.

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.
Furthermore, “aromatic ring” means both “aromatic hydrocarbon ring” and “aromatic heterocycle”.
Moreover, terms such as “CI Pigment Green” mean a color index (CI).

<Colored resin composition>
The colored resin composition of the present invention, (A) a dye, (B) a solvent, (C) a binder resin, and (D) an antioxidant, wherein the (A) dye contains a xanthene compound (I), and The (D) antioxidant contains compound (II) and further contains (E) a phosphite.
Furthermore, the colored resin composition of the present invention preferably contains (F) a polymerizable monomer, (G) a photopolymerization initiating component and / or a thermal polymerization initiating component, (H) a pigment, and, if necessary, other It may contain components.
First, the (A) dye and the xanthene compound (I) in the present invention will be described in detail.

[(A) Dye]
The colored resin composition of the present invention contains the xanthene compound (I) in the (A) dye.
<Xanthene compound (I)>
The colored resin composition of the present invention contains a xanthene compound represented by the following formula (I).

(In the formula (I),
R ^{1 to} R ⁴ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted aromatic carbon atom having 6 to 18 carbon atoms. Represents a hydrogen ring group.
R ¹ and R ² , and R ³ and R ⁴ may be independently bonded to each other to form a ring, and the ring may have a substituent.

R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent.
R ⁷ represents an arbitrary substituent.
m represents an integer of 0 to 5. When m is an integer of 2 or more, the plurality of R ⁷ may be the same or different.

p represents an integer of 1 to 4. When p is 2 to 4, the structures in [] containing a plurality of xanthene skeletons may be the same or different.
X ^q- represents an arbitrary q-valent anion.
q represents the integer of 1-4.
n represents an integer of 0 to 4. When n is 2-4, several ^Xq- may be the same or different.

When R ^{1 to} R ⁷ are a group containing a sulfonate group or a carboxylate group, or when R ⁷ is a sulfonate group or a carboxylate group, n is 0 and p = 1, and otherwise , P = n × q. )
(For ^R 1 to R ⁴⁾
R ^{1 to} R ⁴ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted aromatic carbon atom having 6 to 18 carbon atoms. Represents a hydrogen ring group.

The alkyl group in R ^{1 to} R ⁴ is a linear, branched or cyclic alkyl group, and the carbon number is usually 1 or more, usually 10 or less, preferably 8 or less, more preferably 5 The following are mentioned.
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.

The aromatic hydrocarbon ring group for R ^{1 to} R ⁴ 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 14, but for example, Examples thereof include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, acenaphthene ring, fluoranthene ring, and fluorene ring having one free valence.
The free valence in the present invention is based on the description of “Organic Chemistry / Biochemical Nomenclature” (Nanedo, published May 20, 1992, translated by Kenzo Hirayama and Kazuo Hirayama, pages 11-12). .

R ¹ and R ² , and R ³ and R ⁴ may be independently bonded to each other to form a ring, and the ring may have a substituent.

The substituent that the alkyl group and the aromatic hydrocarbon ring group in R ^{1 to} R ⁴ may have is not particularly limited as long as the effects of the present invention are not impaired. ).

(Substituent group W)
Alkyl group having 1 to 8 carbon atoms ^(except when R 1 to R ⁴ is an alkyl group), an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, aryl having 6 to 15 carbon atoms Oxy group, aryl group having 6 to 15 carbon atoms, alkylcarbonyloxy group having 2 to 9 carbon atoms, arylcarbonyloxy group having 7 to 16 carbon atoms, alkoxycarbonyl group having 2 to 9 carbon atoms, 7 to 16 carbon atoms Aryloxycarbonyl group, carbamoyl group, alkylcarbamoyl group having 2 to 9 carbon atoms, arylcarbamoyl group having 7 to 16 carbon atoms, sulfamoyl group, alkylsulfamoyl group having 1 to 8 carbon atoms, aryl having 6 to 16 carbon atoms Sulfamoyl group, C2-C9 alkylcarbonyl group, C7-C16 arylcarbonyl group, C1-C8 alkylsulfonylamino group An arylsulfonylamino group having 6 to 16 carbon atoms, an amino group, an alkylamino group in which an alkyl group having 1 to 8 carbon atoms is bonded, a dialkylamino group in which an alkyl group having 1 to 6 carbon atoms is bonded, and the number of carbon atoms An arylamino group having 6 to 16 carbon atoms, an arylalkylamino group formed by bonding an aryl group having 6 to 10 carbon atoms and alkyl having 1 to 4 carbon atoms, an alkylcarbonylamino group having 1 to 8 carbon atoms, and 7 to 16 carbon atoms Arylcarbonylamino group, trifluoromethyl group, C1-C8 trialkylsilyl group, C1-C8 alkylthio group, C6-C16 arylthio group, hydroxy group, nitro group, cyano group, sulfonate Group, sulfo group, salt of sulfo group, carboxy group, carboxylate group, salt of carboxy group, halogen atom such as fluorine atom and chlorine atom.

Specific examples of the aryl group in the substituent group W include those described as aromatic hydrocarbon ring groups in R ^{1 to} R ⁴ and aromatic heterocyclic groups having 3 to 10 carbon atoms. Examples of the aromatic heterocyclic group include groups having one free valence such as a furan ring, a thiophene ring pyrrole ring, a pyrazole ring, an imidazole ring, and a pyridine ring. The aryl group is a lower alkyl group such as methyl group or ethyl group, a lower alkoxy group such as methoxy group or ethoxy group, nitro group, trifluoromethyl group, cyano group, carbamoyl group, sulfamoyl group, C 1-10. A halogen atom such as an alkylsulfamoyl group substituted with an alkyl group, a fluorine atom, or a chlorine atom may further be included as a substituent.

As the substituent that the alkyl group, the aromatic hydrocarbon ring group, and the ring formed by being connected to each other in R ^{1 to} R ⁴ may have, preferably an alkyl group having 1 to 8 carbon atoms, 1 to 1 carbon atoms. 8 alkoxy group, phenyl group, tolyl group, alkylcarbonyloxy group having 2 to 9 carbon atoms, carbamoyl group, sulfamoyl group, alkylsulfamoyl group having 1 to 8 carbon atoms, trifluoromethyl group, cyano group, sulfo group And a fluorine atom.

(About R ⁵ and R ⁶ )
In the xanthene compound (I), R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms.
The halogen atom in R ⁵ and R ⁶ represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Preferably, they are a chlorine atom and a bromine atom.
Alkyl group for R ⁵ and 10 carbon atoms which may have a substituent in ^{R 6 is} the same as the alkyl group in R 1 to R ^4.

(For ^{R 7)}
In the xanthene compound (I), R ⁷ represents an arbitrary substituent.
As an arbitrary substituent in R ⁷ , for example, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, An alkoxy group which may have a substituent, a phenoxy group which may have a substituent, an alkylcarbonyloxy group which may have a substituent, an arylcarbonyloxy which may have a substituent Group, an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, an amino group, an alkylamino group which may have a substituent, and a substituent An arylamino group which may have a substituent, an alkylcarbonylamino group which may have a substituent, an arylcarbonylamino group which may have a substituent, an alkylsulfo which may have a substituent Nylamino group, optionally substituted arylsulfonylamino group, carbamoyl group, optionally substituted alkylcarbamoyl group, optionally substituted arylcarbamoyl group, sulfamoyl group, substituted Alkylsulfamoyl group which may have a group or arylsulfamoyl group which may have a substituent, hydroxyl group, nitro group, cyano group, sulfonate group, sulfo group, sulfo group salt, carboxy group Represents a carboxylate group, a salt of a carboxy group or a halogen atom.

Which may have a substituent an alkyl group having 1 to 10 carbon atoms are the same as the alkyl group for R ¹ to R ^4. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, a hydroxyethyl group, a 1,2-dihydroxypropyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, a 2-butoxyethyl group, Examples include 2- (2-methoxyethoxy) ethyl group, 2- (2-ethoxyethoxy) ethyl group, 2- (2-butoxyethoxy) ethyl group, benzyl group, phenethyl group and the like.

Aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent are the same as the aromatic hydrocarbon group for R ¹ to R ^4. Specific examples of the aromatic hydrocarbon group include a phenyl group, a p-tolyl group, an m-tolyl group, a p-methoxyphenyl group, a naphthyl group, and an anthracenyl group.
The alkoxy group which may have a substituent is represented by —OR ¹¹ , and R ¹¹ represents an alkyl group having 1 to 10 carbon atoms which may have a substituent. R ¹¹ is the same as the alkyl group in R ^{1 to} R ⁴ . Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, n-butoxy group, hydroxyethoxy group, 1,2-dihydroxypropoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2 -Butoxyethoxy group, 2- (2-methoxyethoxy) ethoxy group, 2- (2-ethoxyethoxy) ethoxy group, 2- (2-butoxyethoxy) ethoxy group, benzyloxy group, phenethyloxy group and the like.

The phenoxy group which may have a substituent has 6 to 18 carbon atoms, and examples of the substituent which the phenoxy group may substitute include those described in the section of (Substituent group W). It is done. Specific examples of the phenoxy group include a phenoxy group, a p-tolyloxy group, an m-tolyloxy group, and a p-methoxyphenoxy group.
The alkylcarbonyloxy group which may have a substituent is represented by —O—COR ¹² , and R ¹² represents an alkyl group having 1 to 10 carbon atoms which may have a substituent. R ¹² is the same as the alkyl group in R ^{1 to} R ⁴ . Specific examples of the alkylcarbonyloxy group include an acetoxy group, an ethylcarbonyloxy group, an n-butylcarbonyloxy group, a t-butylcarbonyloxy group, and the like.

The arylcarbonyloxy group which may have a substituent is represented by —O—COR ¹³ , and R ¹³ represents an aryl group having 6 to 15 carbon atoms which may have a substituent. Specific examples of the aryl group include those described as aromatic hydrocarbon ring groups for R ^{1 to} R ⁴ and aromatic heterocyclic groups having 3 to 10 carbon atoms. Examples of the aromatic heterocyclic group include groups having one free valence such as a furan ring, a thiophene ring pyrrole ring, a pyrazole ring, an imidazole ring, and a pyridine ring. The aryl group is a lower alkyl group such as methyl group or ethyl group, a lower alkoxy group such as methoxy group or ethoxy group, nitro group, trifluoromethyl group, cyano group, carbamoyl group, sulfamoyl group, C 1-10. A halogen atom such as an alkylsulfamoyl group substituted with an alkyl group, a fluorine atom, or a chlorine atom may further be included as a substituent. Specific examples of the arylcarbonyloxy group include benzoyloxy group, p-tolylcarbonyloxy group, m-tolylcarbonyloxy group, p-methoxyphenylcarbonyloxy group and the like.

The alkoxycarbonyl group which may have a substituent is represented by —CO ₂ R ¹⁴ , and R ¹⁴ represents an alkyl group having 1 to 10 carbon atoms which may have a substituent. R ¹⁴ is the same as the alkyl group in R ^{1 to} R ⁴ .
Specific examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a phenethyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, a 2-ethoxyethoxycarbonyl group, and a 2- (2-ethoxyethoxy) ethoxycarbonyl group. Can be mentioned.

The aryloxycarbonyl group which may have a substituent is represented by —CO ₂ R ¹⁵ , and R ¹⁵ represents an aryl group having 6 to 15 carbon atoms which may have a substituent. R ¹⁵ is the same as the aryl group in R ¹³ . Specific examples of the aryloxycarbonyl group include phenoxycarbonyl group, naphthoxycarbonyl group, p-tolyloxycarbonyl group, p-methoxyphenoxycarbonyl group and the like.

The alkylamino group which may have a substituent is represented by —NR ¹⁶ R ¹⁷ , R ¹⁶ represents an alkyl group which may have a substituent, and R ¹⁷ represents a hydrogen atom or a substituent. It represents an alkyl group that may have. The alkyl group is the same as the alkyl group in R ^{1 to} R ⁴ . Specific examples of the alkylamino group include an ethylamino group, a dimethylamino group, a diethylamino group, a dibutylamino group, a di (2-ethoxyethyl) amino group, a diphenethylethylamino group, and a cyclohexylethyl group.

The arylamino group which may have a substituent is represented by —NR ¹⁸ R ¹⁹ , where R ¹⁸ represents an aryl group which may have a substituent, and R ¹⁹ represents a hydrogen atom or a substituent. The alkyl group which may have and the aryl group which may have a substituent are represented. The alkyl group is the same as the alkyl group in R ^{1 to} R ⁴ . The aryl group is the same as the aryl group in R ¹³ . Specific examples of the arylamino group include a phenylamino group, a diphenylamino group, a di (p-tolyl) amino group, a di (p-methoxyphenyl) amino group, an ethylphenylamino group, and an n-butylphenylamino group. Can be mentioned.

The alkylcarbonylamino group which may have a substituent is represented by —NH—COR ²⁰ or —N (—COR ²⁰ ) —COR ²¹ , and R ²⁰ and R ²¹ may have a substituent. Represents an alkyl group. The alkyl group is the same as the alkyl group in R ^{1 to} R ⁴ . Specific examples of the alkylcarbonylamino group include acetylamino group, ethyl 2-ethylhexylcarbonylamino group, diacetylamino group and the like.

The arylcarbonylamino group which may have a substituent is represented by —NH—COR ²² or —N (—COR ²² ) —COR ²³ , and R ²² represents an aryl group which may have a substituent. R ²³ represents an alkyl group which may have a substituent or an aryl group which may have a substituent. The alkyl group is the same as the alkyl group in R ^{1 to} R ⁴ . The aryl group is the same as the aryl group in R ¹³ . Specific examples of the arylcarbonylamino group include a benzoylamino group and a dibenzoylamino group.

The alkylsulfonylamino group which may have a substituent is represented by —NH—COR ²⁴ or —N (—COR ²⁴ ) —COR ²⁵ , and R ²⁴ and R ²⁵ may have a substituent. Represents an alkyl group. The alkyl group is the same as the alkyl group in R ^{1 to} R ⁴ . Specific examples of the alkylsulfonylamino group include a methylsulfonylamino group, an ethyl 2-ethylhexylsulfonylamino group, and a dimethylsulfonylamino group.

The arylsulfonylamino group which may have a substituent is represented by —NH—COR ²⁶ or —N (—COR ²⁶ ) —COR ²⁷ , and R ²⁶ represents an aryl group which may have a substituent. R ²⁷ represents an alkyl group which may have a substituent or an aryl group which may have a substituent. The alkyl group is the same as the alkyl group in R ^{1 to} R ⁴ . The aryl group is the same as the aryl group in R ¹³ . Specific examples of the arylsulfonylamino group include p-tolylsulfonylamino group and di-p-tolylsulfonylamino group.

The alkylcarbamoyl group which may have a substituent is represented by —CO—NR ²⁸ R ²⁹ , R ²⁸ represents an alkyl group which may have a substituent, and R ²⁹ represents a hydrogen atom or a substituent. It represents an alkyl group that may have. R ²⁸ and R ²⁹ may be bonded to each other to form a ring, and the ring may have a substituent. Examples of the substituent that the ring may have include those described in the section of (Substituent group W). The alkyl group is the same as the alkyl group in R ^{1 to} R ⁴ . Specific examples of the alkylcarbamoyl group include a methylcarbamoyl group, an ethylcarbamoyl group, a phenethylcarbamoyl group, a 2-ethylhexylcarbamoyl group, a 2-ethoxyethylcarbamoyl group, a 2- (2-ethoxyethoxy) ethylcarbamoyl group, and a diethylcarbamoyl group. , Di-n-butylcarbamoyl group, dicyclohexylcarbamoyl group, pyrrolylcarbonyl group and the like.

The arylcarbamoyl group which may have a substituent is represented by —CO—NR ³⁰ R ³¹ , R ³⁰ represents an aryl group which may have a substituent, R ³¹ represents a hydrogen atom, and a substituent. The aryl group which may have or the alkyl group which may have a substituent is represented. R ³⁰ and R ³¹ may be bonded to each other to form a ring, and the ring may have a substituent. Examples of the substituent that the ring may have include those described in the section of (Substituent group W). The alkyl group is the same as the alkyl group in R ^{1 to} R ⁴ . The aryl group is the same as the aryl group in R ¹³ . Specific examples of the arylcarbamoyl group include phenylcarbamoyl group, naphthylcarbamoyl group, p-tolylcarbamoyl group, p-methoxyphenylcarbamoyl group, ethylphenylcarbamoyl group, n-butylphenylcarbamoyl group, diphenylcarbamoyl group, indolinylcarbonyl Group, 1,2,3,4-tetrahydroquinolinylcarbonyl group and the like.

The optionally substituted alkylsulfamoyl group is represented by —SO ₂ —NR ³² R ³³ , where R ³² is an optionally substituted alkyl group, and R ³³ is a hydrogen atom or The alkyl group which may have a substituent is represented. R ³² and R ³³ may be bonded to each other to form a ring, and the ring may have a substituent. Examples of the substituent that the ring may have include those described in the section of (Substituent group W). The alkyl group is the same as the alkyl group in R ^{1 to} R ⁴ . Specific examples of the alkylsulfamoyl group include methylsulfamoyl group, ethylsulfamoyl group, phenethylsulfamoyl group, 2-ethylhexylsulfamoyl group, 2-ethoxyethylsulfamoyl group, 2- ( 2-ethoxyethoxy) ethylsulfamoyl group, diethylsulfamoyl group, di-n-butylsulfamoyl group, dicyclohexylsulfamoyl group, pyrrolylsulfonyl group and the like.

The arylsulfamoyl group which may have a substituent is represented by —CO—NR ³⁴ R ³⁵ , R ³⁴ represents an aryl group which may have a substituent, R ³⁵ represents a hydrogen atom, The aryl group which may have a group, or the alkyl group which may have a substituent is represented. R ³⁴ and R ³⁵ may be bonded to each other to form a ring, and the ring may have a substituent. Examples of the substituent that the ring may have include those described in the section of (Substituent group W). The alkyl group is the same as the alkyl group in R ^{1 to} R ⁴ . The aryl group is the same as the aryl group in R ¹³ . Specific examples of the arylsulfamoyl group include phenylsulfamoyl group, naphthylsulfamoyl group, p-tolylsulfamoyl group, p-methoxyphenylsulfamoyl group, ethylphenylsulfamoyl group, n- Examples thereof include a butylphenylsulfamoyl group, a diphenylsulfamoyl group, an indolinylsulfonyl group, and a 1,2,3,4-tetrahydroquinolinylsulfonyl group.

Among these, R ⁷ has a sulfonate group, a sulfo group, a salt of a sulfo group, a carboxy group, a carboxylate group, a salt of a carboxy group, an alkoxycarbonyl group that may have a substituent, or a substituent. An optionally substituted aryloxycarbonyl group, an optionally substituted alkylcarbamoyl group, an optionally substituted arylcarbamoyl group, an optionally substituted alkylsulfamoyl group or a substituted group It is more preferably an arylsulfamoyl group that may have a group.

Xanthene compound (I) in which R ⁷ is a sulfonate group, a sulfo group, a salt of a sulfo group, a carboxy group, a carboxylate group or a salt of a carboxy group can form a salt in the molecule and form a strong bond. Since the obtained film has high heat resistance and has a highly polar group, the compatibility between the xanthene compound (I) and the liquid crystal is low, and the xanthene compound (I) is difficult to elute into the liquid crystal. High reliability.

R ⁷ has an optionally substituted alkoxycarbonyl group, an optionally substituted aryloxycarbonyl group, an optionally substituted alkylcarbamoyl group, and a substituent. The xanthene compound (I), which may be an arylcarbamoyl group, an alkylsulfamoyl group which may have a substituent, or an arylsulfamoyl group which may have a substituent, is dissolved in an organic solvent. Since it is highly soluble and can be dissolved in the colored resin composition, the color filter is excellent in manufacturability, and the resulting pixel has a high contrast.

(About m)
m represents an integer of 0 to 5. When m is an integer of 2 or more, the plurality of R ⁷ may be the same or different.
In addition, from the viewpoint of electrical reliability and solubility in an organic solvent, m is preferably 1 or 2 because it preferably has a more preferable group described in the above section (about R ⁷ ). .

(About p)
p represents an integer of 1 to 4. When p is 2 to 4, the structures in [] containing a plurality of xanthene skeletons may be the same or different.
When R ^{1 to} R ⁷ are a group containing a sulfonate group or a carboxylate group, or when R ⁷ is a sulfonate group or a carboxylate group, n is 0 and p = 1, and otherwise , P = n × q.

(About X ^q- and q)
X ^q- represents an arbitrary q-valent anion. q represents the integer of 1-4.
Examples of the anion of X ^q- include halide ions, PF ₆ ⁻ , ClO ₄ ⁻ , CN ⁻ , OH ⁻ , NO ₃ ⁻ , SO ₄ ²⁻ , HSO ₄ ⁻ , PO ₄ ³⁻ , and HPO ₄ ^2−. , _H 2 PO ₄ ^- inorganic ions such as, carboxylato group in the molecule (-COO ^-) or a sulfonato group (--SO3 ^-) organic compounds having an anion derived from an acidic group such as, methide anion, sulfonyl imide anion Organic anions such as

  Among them, a halide ion, an organic compound having a sulfonate group, a sulfonylmethide anion having an optionally substituted alkyl group having 1 to 10 carbon atoms, and an optionally substituted carbon atom having 1 to 1 carbon atoms. A sulfonylimide anion having 10 alkyl groups is preferred. Specific examples of preferred anions include chloride ion, bromide ion, 1-naphthalenesulfonate, bistrifluoromethanesulfonylimide anion, and tristrifluoromethanesulfonylmethide anion.

(About n)
n represents an integer of 0 to 4. When n is 2-4, several ^Xq- may be the same or different. A preferred number of n is 0 or 1.
When n is 0, the structure in [] containing a xanthene skeleton contains a sulfonate group or a carboxylate group, forms a salt in the molecule, and can form a strong bond, so that the resulting film has heat resistance. And high electrical reliability.
Moreover, when n is 1, it has the preferable anion of said ^Xq- , and the heat resistance of the obtained film | membrane is high.

(Structure in [] including xanthene skeleton)
The “structure in [] containing a xanthene skeleton” in the present invention means the following structure in the structure represented by the formula (I).

[Molecular weight]
The molecular weight of the xanthene compound (I) in the present invention is usually 500 or more, preferably 600 or more, and usually 5000 or less, preferably 2000 or less.
It is preferable that it is within the above-mentioned range in terms of good solubility in a solvent and easy production.
[Concrete example]
Although the preferable specific example of a xanthene type compound (I) is shown below, this invention is not limited to these.

Incidentally, in the above embodiment, -SO ₃ ^- group notation, that substitution positions are a plurality, and, synthesis, means or the like can be obtained as a mixture of different substitution positions compound.
In addition to the above structure, C.I. I. Acid Red 50, C.I. I. Acid Red 52, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 289, C.I. I. Acid Red 388, International Publication No. 2011/158747, International Publication No. 2011/158748, International Publication No. 2012/53201, Japanese Unexamined Patent Publication No. 6-230210, Japanese Unexamined Patent Publication No. 2010-32999, Japanese Unexamined Patent Publication No. 2011-28236, Japanese Unexamined Patent Publication No. 2011-2011. And xanthene compounds described in JP-A Nos. 138094, 2011-241372, 2012-107192, 2012-185383, and 2012-233151.

[Synthesis Method of Xanthene Compound (I)]
Xanthene compounds (I) are, for example, “reviewed synthetic dyes” (Horiguchi Hiroshi, Sankyo Publishing, 1968), “theoretical manufacturing dye chemistry” (Toyo Hosoda, Gihodo, 1957), synthesis and application of functional dyes. It can be synthesized according to the method described in the technology (supervised by Masaki Matsui, CMC Publishing, 2007).

Specifically, a xanthene compound can be obtained by the following methods (i) to (iii).
(I) reacting benzaldehydes with N-substituted m-aminophenols.

(Ii) reacting phthalic anhydrides with N-substituted m-aminophenols.
(Iii) A 3,6-dichloroxanthene derivative (for example, fluorescein chloride) is reacted with an N-substituted amine, and the resulting xanthene compound is sulfonated as necessary.
The xanthene compound obtained by said (i)-(iii) can introduce | transduce a substituent as needed. For example, the methods (iv) to (vii) can be mentioned.
(Iv) Sulfonation with sulfuric acid or fuming sulfuric acid, chlorination with thionyl chloride or phosphorus trichloride, amination with N-substituted amine (v) chlorosulfonylation with chlorosulfonic acid, amination with N-substituted amine (vi) Chlorination with thionyl chloride or phosphorus trichloride for compounds substituted with carboxy groups, amination with N-substituted amines (vii) Chloroform with thionyl chloride or phosphorus trichloride for compounds substituted with carboxy groups Esterification with alcohols or phenols

(Other dyes)
The dye (A) in the present invention may contain other dyes other than the xanthene compound (I) as long as the effects of the present invention are not impaired.
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 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disper 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. Pad Blue 5 and the like are quinone imine dyes such as C.I. 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 the triarylmethane dye include those described in International Publication No. 2009/107734, PCT / JP2011 / 64082, and the like.
Furthermore, examples of the cyanine dye include those described in Japanese Patent Application No. 2010-142748, and preferred embodiments thereof are also the same.

(Content)
The content of the total (A) dye in the colored resin composition of the present invention is usually 0.01% by weight or more, preferably 0.05% by weight or more, and more preferably 0% in the total solid content of the colored resin composition. .1% by weight or more, preferably 40% by weight or less, more preferably 30% by weight or less.
In the colored resin composition of the present invention, the xanthene compound (I) is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and particularly preferably 1% by weight or more in the total solid content. Further, it is preferably contained in a proportion of 50% by weight or less, more preferably 40% by weight or less, and particularly preferably 30% by weight or less.
In the colored resin composition of the present invention, the content of the xanthene compound (I) is preferably 30% by weight or more in the solid content of the total (A) dye.

  It is preferable for it to be less than or equal to the above upper limit because the curability of the coating film is unlikely to decrease and the film strength is sufficient. Moreover, since it is sufficient for coloring power to be more than the said minimum, since the chromaticity of a desired density | concentration is easy to be obtained and it is hard to become thick, it is preferable.

[(D) Antioxidant]
The colored resin composition of this invention contains the compound represented by following formula (II) in (D) antioxidant.

(In said formula (II), R ^<1a> and R ^<2a> respectively independently represent the C1-C12 alkyl group which may have a substituent.
L represents a hydrogen atom, a carbon atom, an aromatic ring group which may have a substituent, or a heterocyclic group which may have a substituent.
Z is a divalent group consisting of an alkylene group having 1 to 10 carbon atoms and / or an ester bond which may have a substituent.

The benzene ring in the above formula (II) may have an arbitrary substituent other than R ^1a and R ^2a , —OH, and Z.
r represents an integer of 1 to 4.
In addition, when r is 2 to 4, a plurality of molecules contained in one molecule

May be the same structure or different.
* Represents a binding site to L. )

(About R ^1a and R ^2a )
R ^1a and R ^2a each independently represents an alkyl group having 1 to 12 carbon atoms which may have a substituent.
The alkyl group may be linear or branched, but is preferably a branched alkyl group.
Moreover, carbon number becomes like this. Preferably it is 1-20, More preferably, it is 3-10.

(About L)
L represents a hydrogen atom, a carbon atom, an aromatic ring group which may have a substituent, or a heterocyclic ring which may have a substituent.
When L is a carbon atom, a hydrogen atom is bonded to a bond not bonded to Z.
Examples of the aromatic ring in L include an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
The aromatic hydrocarbon ring 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 5 to 10. For example, an m-valent free valence is obtained. 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 aromatic heterocycle 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. For example, an m-valent free 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, 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, ben Imidazole ring, perimidine ring, a quinazoline ring, a quinazolinone ring, and azulene ring.

On the other hand, the heterocyclic group (that is, non-aromatic heterocyclic group) may be a single ring or a condensed ring.
The heterocyclic group is a non-aromatic ring containing any one of a nitrogen atom, a sulfur atom and an oxygen atom as a hetero atom.
When the heterocyclic group has a plurality of atoms constituting a ring other than carbon, these may be the same or different.

Specific examples include a pyridinyl group, a quinolinyl group, an isoquinolinyl group, a benzothiazolinyl group, a phthalimidoyl group, a piperidinyl group, and a pyrrolidinyl group.
Among the aromatic rings and heterocycles in L, the ring represented by the following <Group A> is excellent in terms of compatibility with the binder resin in the colored resin composition and the point that synthesis is easy. Particularly preferred.

  <Group A>

(In the above formula, * each independently represents a bonding site with Z, a hydrogen atom or an arbitrary substituent.
However, in each ring, at least one of * represents a bonding site with Z. )
Z is a divalent group composed of an alkylene group having 1 to 10 carbon atoms and / or an ester bond.

That is, Z may be formed of only an alkylene group having 1 to 10 carbon atoms, or may be a group in which an alkylene group having 1 to 10 carbon atoms and an ester bond are combined.
Examples of the combined group also include groups such as —CH ₂ —C (═O) O—CH ₂ —.
The number of constituent atoms of Z is preferably 30 or less. The alkylene group may have a substituent such as a carbonyl group.
The benzene ring in the formula (II) may have an arbitrary substituent other than R ^1a , R ^2a , —OH, and Z, but the substituent is high in that it has a high bonding force with a radical. The case where it does not have is preferable.
^Examples of the substituent that the alkyl group in R ^1a and R ^2a , the aromatic ring group and heterocyclic group in L, the alkylene group in Z, and the benzene ring in the formula (II) may have the following (substitution Group W ¹ ), but the present invention is not limited thereto.

(Substituent group W ¹ )
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, alkyl carboxyl group having 2 to 9 carbon atoms, sulfonic acid amide group, sulfone alkylamide 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.

(About r)
R in the formula (II) represents an integer of 1 to 4.
M is preferably 2 to 4 because it is highly soluble in a solvent and the effects of the present invention can be easily obtained.
(Regarding Formula (II ′))
The compound (II) is preferably a compound represented by the following formula (II ′).

(In the above formula, R ^1a and R ^2a , L, and r have the same meanings as in the formula (II)).
n ¹ represents an integer of 1 to 10.
l ¹ represents an integer of 0 to 5.
The benzene ring in the above formula (II) may have an arbitrary substituent other than R ^1a and R ^2a , —OH, and — (CH ₂ ) _n ¹ —.

In addition, when n ¹ and l ¹ are each 1 or more, the order may be random.
In addition, when r is 2 to 4, a plurality of molecules contained in one molecule

May be the same structure or different.
* Represents a binding site to L. )
(About n ¹ )
n ¹ represents an integer of 1 to 10.
Preferably it is 1-5 from a point with high compatibility with binder resin etc.

(About l ¹ )
l ¹ represents an integer of 0 to 5.
Preferably it is 0-1 from a point with high compatibility with binder resin etc.
In addition, when n ¹ and l ¹ are each 1 or more, the order may be random. This means that it may be, for example, —CH ₂ —C (═O) O—CH ₂ —.

(Molecular weight)
The molecular weight of the (D) antioxidant in the present invention is usually 90 or more, preferably 150 or more, more preferably 250 or more, and usually 3000 or less, preferably 2000 or less, more preferably 1300 or less.
It is preferable in the said range at the point with high bond strength with a radical.

(Concrete example)
Preferred examples of the compound (II) are shown below, but the present invention is not limited thereto.

(About content)
The content of the antioxidant in the present invention is usually 0.1% by weight or more, preferably 0.2% by weight or more, more preferably 0.25% by weight or more, and usually 6% in the solid content of the colored resin composition. 0.0% by weight or less, preferably 4.0% by weight or less, more preferably 3.0% by weight or less.
Within the above range, it is preferable in that it is well dispersed in the colored resin composition, the precipitation of unnecessary components is small, and the color characteristics of the obtained color filter are hardly affected.
In the present invention, the antioxidant is preferably compound (II), and the total amount of the above-mentioned antioxidant is preferably compound (II).

[(E) Phosphite]
The colored resin composition of the present invention contains (E) a phosphite.
(E) Among phosphites, it is a compound represented by the following formula (III) (hereinafter sometimes referred to as “compound (III)”) in that the effect of the present invention can be obtained satisfactorily. Is preferred.

(In said formula (III), R ^<1b > -R <^3b> is respectively independently the C1-C12 alkyl group which may have a substituent, and the aromatic ring group which may have a substituent. Or a heterocyclic group which may have a substituent.
R ^{1b to} R ^3b may be bonded to each other to form a ring. )
(About R ^{1b to} R ^3b )
The alkyl group in R ^{1b to} R ^3b may be branched or linear.

Moreover, as an aromatic ring and a heterocyclic group in R ^<1b > -R < ^3b >, the thing as described in the said (about L) term is mentioned. The preferred embodiment is also the same.
Furthermore, examples of the ring formed by combining R ^{1b to} R ^3b with each other include the following partial structures, but the present invention is not limited thereto.

The alkyl group in R ^1b to R ^3b, the aromatic ring group and heterocyclic group substituents which may be possessed include those described in the paragraph of the (substituent group W ^1).
Furthermore, compound (III) may be bonded to any one of R ^{1b to} R ^3b to form a dimer or trimer, for example. In this case, they may be bonded via a linking group (for example, a group consisting of —CH ₂ — and —O—, etc.).

(1-1. Molecular weight)
The molecular weight of the phosphite ester in the present invention is usually 80 or more, preferably 150 or more, more preferably 300 or more, and usually 2,000 or less, preferably 1,500 or less, more preferably 900 or less.
It is preferable at the point which shows the high oxidation effect as it is in the said range.

(Specific examples of phosphites)
Although the preferable specific example of the phosphite in this invention is shown below, this invention is not limited to these.

In the present invention, it is preferable to use a phosphite ester in view of further improving the adhesion in addition to the luminance and heat resistance of the obtained pixel.
(Content)
In the present invention, the content of (E) phosphite to (D) antioxidant is usually 0.05% by weight or more, preferably 0.2% by weight or more in the solid content of the colored resin composition. Preferably it is 0.25% by weight or more, and usually 6.0% by weight or less, preferably 4.0% by weight or less, more preferably 3.0% by weight or less.
Within the above range, it is preferable in that the resin composition is well dispersed in the resin composition, unnecessary components are not precipitated, and color characteristics are not affected.
In addition, the (E) phosphite ester of the present invention may be used in combination of two or more different kinds, and when used in combination, the content in the composition may be within the above range.

[(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.
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, 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.

Of these solvents, glycol monoalkyl ethers are preferred from the viewpoint of solubility of the dye (A) in the present invention in an organic solvent. 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, in the case of containing (H) pigment, which will be described later as an optional component, the balance of coatability, surface tension, etc. is good, and from the viewpoint that the solubility of the constituent components in the colored resin composition is relatively high, It is more preferable to use a mixture of glycol alkyl ether 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 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. .
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. Further, the high boiling point solvent having a boiling point of 180 ° C. or higher is (B) 50% of the solvent.
It is preferable that it is weight% or more. When the ratio of such a high boiling point solvent is less than 50% by weight, 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 weight. When the content of the (B) solvent in the composition exceeds 99% by weight, the concentration of each component excluding the (B) solvent may become too small to form 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) 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 (C) binder resin include JP-A-7-2072111, 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. However, among them, the following resins (C-1) to (C-5) are preferable.

(C-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another 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 of 2009-025813 gazette. 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 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 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.

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. 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 (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.
Content of (C) binder resin in a colored resin composition is 0.1 to 80 weight% normally in a total solid, Preferably it is 1 to 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.

[(F) polymerizable monomer]
The colored resin composition of the present invention preferably contains (F) a polymerizable monomer.
(F) The polymerizable monomer is not particularly limited as long as it is a low molecular weight compound that can be polymerized, but it may be referred to as 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 (F) 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.
(F) 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 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 (F) 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.

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 of these (F) polymerizable monomers 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 (F) polymerizable monomer to the (A) dye is usually 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, and particularly preferably 20% by weight or more. Moreover, it is 200 weight% or less normally, Preferably it is 100 weight% or less, More preferably, it is 80 weight% or less.
Within the above range, photocuring is appropriate, poor adhesion during development is difficult to place, the cross-section after development is difficult to reverse taper, and further, peeling phenomenon and omission failure due to lower solubility are difficult to place. preferable.

[(G) Photopolymerization initiation component and / or thermal polymerization initiation component]
The colored resin composition of the present invention preferably contains (G) 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 contains a resin having an ethylenic double bond as the component (C), or contains an ethylenic compound as the component (F), 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 (G) as the photopolymerization initiation component refers to a photopolymerization initiator (hereinafter also referred to as “(G1) component”), a polymerization accelerator (hereinafter, optionally referred to as “(G2) component”). ")", And a sensitizing dye (hereinafter also referred to as "(G3) component").

[(G) Photopolymerization initiation component]
The (G) photopolymerization initiating component in the present invention is usually a mixture of (G1) a photopolymerization initiator and, if necessary, (G2) a polymerization accelerator and (G3) 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 constituting the photopolymerization initiation component (G1) include titanocene derivatives described in 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-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.

  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 a compound represented by the following formula (XI).

(XI)
(In the formula (XI),
n represents an integer of 0 or 1.
m represents an integer of 0 to 20.
X ¹ represents an aromatic group which may have a substituent.
X ² is 1 selected from the group consisting of —CR ⁹⁴ R ⁹⁵ —, —C (═CR ⁹⁶ R ⁹⁷ ) —, —CR ⁹⁸ = CR ⁹⁹ —, —C≡C— and —C (═O) —. One group or a group formed by bonding two or more of these.

R ^{96 to} R ⁹⁹ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ⁹⁴ and R ⁹⁵ , R ¹⁰¹ are each independently a hydrogen atom, a halogen atom, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, each of which may have a substituent, C2-C20 monovalent non-aromatic heterocyclic group, C1-C20 alkoxy group, C6-C20 aryloxy group, C2-C20 acyl group, C2-C20 Acyloxy group, N-substituted amino group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, carbamoyl group, alkylcarbamoyl group having 2 to 20 carbon atoms, arylcarbamoyl group having 7 to 20 carbon atoms, cyano group A nitro group, an alkylsulfanyl group having 1 to 12 carbon atoms, an arylsulfanyl group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, and an alkenyloxycarbon having 3 to 12 carbon atoms. A sulfonyl group, an alkynyloxycarbonyl group having 3 to 12 carbon atoms, an aryloxycarbonyl group having 7 to 12 carbon atoms, a heteroaryloxycarbonyl group having 3 to 12 carbon atoms, or a group represented by the following formula (2) is represented. .

(R ^30b and R ^31b each independently represent an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms, which may have a substituent.)
R ¹⁰¹ may be bonded to X ¹ to form a ring.
R ¹⁰² may have a substituent, which may have a substituent, an alkylcarbonyl group having 2 to 20 carbon atoms, an alkenylcarbonyl group having 3 to 25 carbon atoms, a cycloalkylcarbonyl group having 4 to 8 carbon atoms, and a carbon number having 7 to 20 An arylcarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroarylcarbonyl group having 3 to 20 carbon atoms, or an alkylaminocarbonyl group having 2 to 20 carbon atoms.

X ¹ represents an aromatic group which may have a substituent. Examples of the aromatic group 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 5 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, indene ring, etc. .

  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, azulene ring, an acridine ring, a xanthene ring, a phenazine ring, a phenothiazine ring, a phenoxazine ring, a benzothiazole ring, groups such as carbazole ring and the like.

Examples of the substituent that the aromatic ring group in X ¹ may have include those described in the above section (Substituent group W).
Of the compounds represented by the formula (XI), compounds in which X ¹ is an optionally substituted carbazole ring are preferred, and specifically, compounds represented by the following formula (XII), etc. Is mentioned.

(In the above formula (XII),
n, m, X ² , R ¹⁰¹ and R ¹⁰² have the same ^{meaning as} in the above formula (XI).
Z represents an aromatic group which may have a substituent.
R ¹⁰³ represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, or an aryl group having 6 to 20 carbon atoms,
R ^{104 to} R ¹⁰⁹ each independently represent a hydrogen atom, a halogen atom, a nitro group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. )
(About n)
n represents an integer of 0 or 1.

(About m)
m represents an integer of 0 to 20.
M is preferably 0 to 5 in that the amount of radically active species generated per gram is high and the production is simple.
(For ^{X 2} and ^{R 101)}
X ² is 1 selected from the group consisting of —CR ⁹⁴ R ⁹⁵ —, —C (═CR ⁹⁶ R ⁹⁷ ) —, —CR ⁹⁸ = CR ⁹⁹ —, —C≡C— and —C (═O) —. One group or a group formed by bonding two or more of these.

When m is 2 or more, the plurality of X ² contained in one molecule may be the same or different.
R ^{96 to} R ⁹⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ^94, R ⁹⁵ and R ¹⁰¹ are each independently a hydrogen atom, a halogen atom, an optionally substituted aryl group having 6 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, carbon C2-C20 monovalent non-aromatic heterocyclic group, C1-C20 alkoxy group, C6-C20 aryloxy group, C2-C20 acyl group, C2-C20 acyloxy Group, an N-substituted amino group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a carbamoyl group, an alkylcarbamoyl group having 2 to 20 carbon atoms, an arylcarbamoyl group having 7 to 20 carbon atoms, a cyano group, A nitro group, an alkylsulfanyl group having 1 to 12 carbon atoms, an arylsulfanyl group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, and an alkenyloxycarbon having 3 to 12 carbon atoms A bonyl group, a C3-C12 alkynyloxycarbonyl group, a C7-C12 aryloxycarbonyl group, a C3-C12 heteroaryloxycarbonyl group, or the group represented by following formula (2) is represented. .

(R ^30b and R ^31b each independently represent an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms, which may have a substituent.)
<Regarding ^{R 94} and ^{R 95, R 101>}
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom, a chlorine atom, and a bromine atom that are relatively stable against a nucleophilic substitution reaction are preferable.
The aryl group having 6 to 20 carbon atoms which may have a substituent preferably has 6 to 12 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the group which may be substituted on the aryl group include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, A sulfo group, a carboxy group, etc. are mentioned. Specific examples of the aryl group include a phenyl group, a p-tolyl group, an m-tolyl group, a p-methoxyphenyl group, a mesityl group, a naphthyl group, and an anthracenyl group.

  The heteroaryl group having 2 to 20 carbon atoms which may have a substituent is an aromatic ring group containing any one of a nitrogen atom, a sulfur atom and an oxygen atom as a heteroatom, preferably having a carbon number. The thing of 2 or more and 12 or less is mentioned. When the heteroaryl group has a plurality of heteroatoms constituting a ring other than a carbon atom, these may be the same or different. The heteroaryl group may be a single ring or a condensed ring, and may be a pyrrolyl group, imidazolyl group, pyrazolyl group, thiazolyl group, oxazolyl group, triazolyl group, thiadiazolyl group, pyridinyl group, pyrimidinyl group, triazinyl group. Quinolinyl group, isoquinolinyl group, benzothiazolinyl group, phthalimidoyl group, benzimidazolonyl group, furyl group, thiophenyl group, pyranyl group, indolinyl group, isoindolinyl group and the like. Examples of the group that may be substituted on the heteroaryl group include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, and a sulfo group. And a carboxy group. Specific examples of the heteroaryl group include 2-pyrrolyl group, 2-imidazolyl group, 1-pyrazolyl group, 2-thiazolyl group, 2-oxazolyl group, 1,2,4-triazol-1-yl group, and 4-pyridinyl. Group, 2-pyrimidinyl group, 4,6-diamino-2-triazinyl group, 8-quinolinyl group, 8-isoquinolinyl group, 2-benzothiazolinyl group, 6-methyl-7-sulfo-2-benzothiazolinyl Group, 1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl group, 1H-benzimidazol-2-yl group, 2-furyl group, 2-thiophenyl group, 1-indolinyl group, 2 -An isoindolinyl group is mentioned.

The monovalent non-aromatic heterocyclic group having 2 to 20 carbon atoms which may have a substituent is a non-aromatic cyclic group containing any one of a nitrogen atom, a sulfur atom and an oxygen atom as a hetero atom. Yes, preferably those having 2 to 12 carbon atoms. When the monovalent non-aromatic heterocyclic group has a plurality of heteroatoms constituting a ring other than a carbon atom, these may be the same or different. The monovalent non-aromatic heterocyclic group may be a single ring or a condensed ring, and examples thereof include a piperidinyl group, a pyrrolidinyl group, an imidazolidinyl group, a pyrazolidinyl group, a piperazinyl group, and a morpholinyl group. Examples of the substituent that the monovalent non-aromatic heterocyclic group may have include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, and diethylamino. Group, halogen atom, sulfo group and carboxy group. Specific examples of the monovalent non-aromatic heterocyclic group include 1-piperidinyl group, 1-pyrrolidinyl group, 1-imidazolidinyl group, 1-pyrazolidinyl group, 1-piperazinyl group and 1-morpholinyl group.

  The alkoxy group having 1 to 20 carbon atoms which may have a substituent is preferably an alkoxy group having 1 to 10 carbon atoms. Examples of the substituent that the alkoxy group may have include an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, a sulfo group, and a carboxy group. Etc. Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, s-butoxy group, t-butoxy group, n-amyloxy group, t-amyloxy group, n- Hexyloxy group, n-heptyloxy group, n-octyloxy group, hydroxyethoxy group, 1,2-dihydroxypropoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2- (2 -Methoxyethoxy) ethoxy group, 2- (2-ethoxyethoxy) ethoxy group, 2- (2-butoxyethoxy) ethoxy group, benzyloxy group, phenethyloxy group, etc., linear or branched alkoxy having 1 to 18 carbon atoms Groups.

  The aryloxy group having 6 to 20 carbon atoms which may have a substituent is preferably an aryloxy group having 6 to 14 carbon atoms. Examples of the aryloxy group include a phenoxy group, a naphthoxy group, and an anthracenyloxy group. Examples of the substituent that the aryloxy group may have include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, and cyano. Group, sulfo group, carboxy group and the like. Specific examples of the aryloxy group include aryls optionally having a substituent such as a phenoxy group, a 1-naphthoxy group, a 2-naphthoxy group, a 3-tolyloxy group, a 4-methoxyphenoxy group, and a 4-cyclohexylphenoxy group. An oxy group is mentioned.

Which may have a substituent alkylcarbamoyl group having 2 to 20 carbon atoms ^is represented by ^{-CO-NR 11b R 12b, R} 11 is an optionally substituted alkyl radical, R ^12b represents a hydrogen atom or an alkyl group which may have a substituent. The alkyl group usually has 1 or more carbon atoms and usually 19 or less, preferably 12 or less. Examples of the group that may be substituted with the alkyl group include an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, a sulfo group, and a carboxy group. Is mentioned. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, cyclohexyl group, hydroxyethyl group, 1,2-dihydroxypropyl group, 2-methoxyethyl group, 2-ethoxyethyl group. 2-butoxyethyl group, 2- (2-methoxyethoxy) ethyl group, 2- (2-ethoxyethoxy) ethyl group, 2- (2-butoxyethoxy) ethyl group, benzyl group, phenethyl group and the like. Specific examples of the alkylamino group include an ethylamino group, a dimethylamino group, a diethylamino group, a dibutylamino group, a di (2-ethoxyethyl) amino group, a diphenethylethylamino group, and a cyclohexylethyl group. Specific examples of the alkylcarbamoyl group include a methylcarbamoyl group, an ethylcarbamoyl group, a phenethylcarbamoyl group, a 2-ethylhexylcarbamoyl group, a 2-ethoxyethylcarbamoyl group, a 2- (2-ethoxyethoxy) ethylcarbamoyl group, and a dimethylcarbamoyl group. Etc.

The arylcarbamoyl group having 7 to 20 carbon atoms which may have a substituent is represented by —CO—NR
It is represented by ^13b R ^14b , and R ^13b represents an aryl group which may have a substituent. R ^14b represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. The preferred carbon number of the alkyl group and examples of the substituent which may be present are the same as those exemplified for the alkyl groups of R ^11b and R ^12b . The aryl group usually has 6 or more carbon atoms, usually 19 or less, preferably 12 or less, and examples thereof include a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the group which may be substituted on the aryl group include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, Examples thereof include a nitro group, a sulfo group, and a carboxy group. Specific examples of the aryl group include a phenyl group, a p-tolyl group, an m-tolyl group, a p-methoxyphenyl group, a naphthyl group, and an anthracenyl group. Specific examples of the arylcarbamoyl group include a phenylcarbamoyl group, a naphthylcarbamoyl group, a p-tolylcarbamoyl group, a p-methoxyphenylcarbamoyl group, and a phenylmethylcarbamoyl group.

Optionally substituted acyl group having 2 to 20 carbon atoms is represented by ^{-COR 15b,} R ^15b may have an optionally substituted alkyl group or a substituted group Represents an aryl group. The preferred carbon number of the alkyl group and examples of the substituent which may be present are the same as those exemplified for the alkyl groups of R ^11b and R ^12b . Examples of the preferable number of carbon atoms of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ⁴⁸ . Specific examples of the acyl group include acetyl group, ethylcarbonyl group, n-butylcarbonyl group, benzoyl group, p-tolylcarbonyl group, m-tolylcarbonyl group, p-methoxyphenylcarbonyl group and the like.

The acyloxy group having 2 to 20 carbon atoms that may have a substituent is represented by -O-COR ^16b , and R ^16b has an alkyl group or a substituent that may have a substituent. Represents a good aryl group. The preferred carbon number of the alkyl group and examples of the substituent which may be present are the same as those exemplified for the alkyl groups of R ^11b and R ^12b . Examples of the preferable carbon number of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ^13b . Specific examples of the acyl group include an acetoxy group, an ethylcarbonyloxy group, an n-butylcarbonyloxy group, a benzoyloxy group, a p-tolylcarbonyloxy group, an m-tolylcarbonyloxy group, and a p-methoxyphenylcarbonyloxy group. Is mentioned.

The optionally substituted N-substituted amino group having 1 to 20 carbon atoms is represented by —NR ^17b R ^18b , where R ^17b is a hydrogen atom, an ^optionally substituted alkyl group, a substituted group. An aryl group which may have a group is represented. R ^18b represents an alkyl group which may have a substituent and an aryl group which may have a substituent. The preferred carbon number of the alkyl group and examples of the substituent which may be present are the same as those exemplified for the alkyl groups of R ^11b and R ^12b . Examples of the preferable carbon number of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ^13b . Specific examples of the N-substituted amino group include an ethylamino group, a dimethylamino group, a diethylamino group, a dibutylamino group, a di (2-ethoxyethyl) amino group, a diphenethylethylamino group, a cyclohexylethyl group, and a phenylamino group. , Diphenylamino group, di (p-tolyl) amino group, di (p-methoxyphenyl) amino group, ethylphenylamino group, n-butylphenylamino group and the like.

The cycloalkyl group having 3 to 20 carbon atoms which may have a substituent is preferably a cycloalkyl group having 3 to 12 carbon atoms. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and a decalinyl group. Examples of the group which may be substituted on the cycloalkyl group include an alkyl group having 1 to 8 carbon atoms and 1 to 8 carbon atoms.
And an alkoxy group, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, a sulfo group, and a carboxy group. Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and a decalinyl group.

The alkylsulfanyl group having 1 to 12 carbon atoms which may have a substituent is represented by —S—R ^22b , and R ^22b represents an alkyl group which may have a substituent. The preferred carbon number of the alkyl group and examples of the substituent which may be present are the same as those exemplified for the alkyl groups of R ^11b and R ^12b . Specific examples of the alkylsulfanyl group include a methylsulfanyl group, an ethylsulfanyl group, a phenethylsulfanyl group, a 2-ethylhexylsulfanyl group, a 2-ethoxyethylsulfanyl group, a 2- (2-ethoxyethoxy) ethylsulfanyl group, and trifluoromethyl. And a sulfanyl group.

The arylsulfanyl group having 6 to 20 carbon atoms which may have a substituent is represented by —S—R ^23b , and R ^23b represents an aryl group which may have a substituent. Examples of the preferable carbon number of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ^13b . Specific examples of the arylsulfanyl group include phenylsulfanyl group, naphthylsulfanyl group, p-tolylsulfanyl group, m-tolylsulfanyl group, o-tolylsulfanyl group, p-methoxysulfanyl group, p-nitrosulfanyl group and the like. It is done.

The C2-C12 alkoxycarbonyl group which may have a substituent is represented by -CO-OR ^24b , and R ^24b represents an alkyl group which may have a substituent. The preferred carbon number of the alkyl group and examples of the substituent which may be present are the same as those exemplified for the alkyl groups of R ^11b and R ^12b . Specific examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, phenethyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, 2-ethoxyethoxycarbonyl group and the like.

The alkenyloxycarbonyl group having 3 to 12 carbon atoms which may have a substituent is represented by —CO—OR ^25b , and R ^25b represents an alkenyl group which may have a substituent. The alkenyl group usually has 1 or more carbon atoms and usually 11 or less, preferably 8 or less. Examples of the group that may be substituted with the alkenyl group include an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, a sulfo group, and a carboxy group. Is mentioned. Specific examples of the alkenyl group include a vinyl group, an allyl group, and a methanyl group. Specific examples of the alkenyloxycarbonyl group include alkenyloxycarbonyl groups having 3 to 12 carbon atoms such as vinyloxycarbonyl group and allyloxycarbonyl group.

Which may have a substituent alkynyloxy group having 3 to 12 carbon atoms is represented by ^{-CO-OR 26b, R 26b} represents an alkynyl group which may have a substituent. The alkynyl group usually has 1 or more carbon atoms and usually 11 or less, preferably 8 or less. Examples of the group which may be substituted on the alkynyl group include an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, a sulfo group and a carboxy group Is mentioned. Specific examples of the alkynyl group include a methynyl group, a propynyl group, and a butynyl group. Specific examples of the alkynyloxycarbonyl group include alkynyloxycarbonyl groups having 3 to 12 carbon atoms such as methynyloxycarbonyl group and propynyloxycarbonyl group.

The optionally substituted aryloxycarbonyl group having 7 to 12 carbon atoms is —CO—.
It is represented by OR ^27b , and R ^27b represents an aryl group which may have a substituent. Examples of the preferable carbon number of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ^13b . Specific examples of the aryloxycarbonyl group include those having 7 to 12 carbon atoms such as phenyloxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, p-tolyloxycarbonyl group, p-methoxyphenyloxycarbonyl group and the like. An aryloxycarbonyl group is mentioned.

Which may have a substituent heteroaryloxy group having 3 to 12 carbon atoms is represented by ^{-CO-OR 28b,} R ^28b represents a heteroaryl group which may have a substituent. Examples of the preferable carbon number of the heteroaryl group and an optionally substituted substituent are the same as those of the preferable carbon number of the heteroaryl group in R ⁵⁴ , R ⁵⁵ and R ^{101 and} an optionally substituted substituent. is there. Specific examples of the heteroaryloxycarbonyl group include 8-quinolinyloxycarbonyl group, 2-furanyloxycarbonyl group, 3-furanyloxycarbonyl group, 2-pyridyloxycarbonyl group, 3-pyridyloxycarbonyl group, 4 -Heteroaryloxycarbonyl groups having 3 to 12 carbon atoms such as a pyridyloxycarbonyl group and a 2-benzothiazolyloxycarbonyl group.

Examples of the alkyl group having 1 to 12 carbon atoms which may have a substituent of R ^30b and R ^31b are the same as those exemplified in the case of the alkyl group of R ^11b and R ^12b . Examples of the aryl group having 6 to 20 carbon atoms which may have a substituent are the same as those exemplified for the aryl group of R ^13b .
R ¹⁰¹ may be bonded to Z to form a ring, and the ring may have a substituent.

<About ^{R 102>}
R ¹⁰² may have a substituent, which may have a substituent, an alkylcarbonyl group having 2 to 20 carbon atoms, an alkenylcarbonyl group having 3 to 25 carbon atoms, a cycloalkylcarbonyl group having 4 to 8 carbon atoms, and a carbon number having 7 to 20 An arylcarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroarylcarbonyl group having 3 to 20 carbon atoms, or an alkylaminocarbonyl group having 2 to 20 carbon atoms.

Examples of the alkylcarbonyl group having 2 to 20 carbon atoms which may have a substituent include an acetyl group, a propanoyl group, a butanoyl group, and the like, and preferably an acetyl group. Carbon number becomes like this. Preferably it is 2-10, More preferably, it is 2-7.
Examples of the alkenylcarbonyl group having 3 to 25 carbon atoms which may have a substituent include a crotonoyl group and an acryloyl group, and a crotonoyl group is preferable. Carbon number becomes like this. Preferably it is 3-12, More preferably, it is 3-7.

Examples of the cycloalkylcarbonyl group having 4 to 8 carbon atoms which may have a substituent include a cyclohexylcarbonyl group, a methylcyclohexylcarbonyl group and a cyclopentylcarbonyl group, and a cyclohexylcarbonyl group is preferable. The number of carbon atoms is preferably 4-7.
Examples of the arylcarbonyl group having 7 to 20 carbon atoms which may have a substituent include a benzoyl group, a methylbenzoyl group, and a naphthoyl group, and a benzoyl group is preferable. Carbon number becomes like this. Preferably it is 7-12, More preferably, it is 7-10.

Examples of the C2-C10 alkoxycarbonyl group which may have a substituent include a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group, and a methoxycarbonyl group is preferable. The number of carbon atoms is preferably 2-8.
Examples of the aryloxycarbonyl group having 7 to 20 carbon atoms which may have a substituent include a phenoxycarbonyl group, a p-methylphenoxycarbonyl group, and a naphthoxycarbonyl group, and a phenoxycarbonyl group is preferable. Carbon number becomes like this. Preferably it is 7-15, More preferably, it is 7-10.

Examples of the heteroarylcarbonyl group having 3 to 20 carbon atoms which may have a substituent include a thiophenecarbonyl group, a pyrrolylcarbonyl group, a pyridinecarbonyl group, and the like, and preferably a thiophenecarbonyl group. Carbon number becomes like this. Preferably it is 5-15, More preferably, it is 7-10.
Examples of the alkylaminocarbonyl group having 2 to 20 carbon atoms which may have a substituent include a morpholinocarbonyl group, a dimethylaminocarbonyl group, and a methylaminocarbonyl group, and a dimethylaminocarbonyl group is preferable. Carbon number becomes like this. Preferably it is 2-12, More preferably, it is 2-10.

Of the above groups, from the viewpoint of exposure sensitivity, R ¹⁰² is preferably an alkylcarbonyl group, a cycloalkylcarbonyl group, or an arylcarbonyl group, and more preferably an alkylcarbonyl group or an arylcarbonyl group.
Examples of the substituent that each group described above as R ¹⁰² may have include those described in the following section (Substituent Group W), and each group described above has a substituent. Particularly preferred are those without.

(Substituent group W)
C1-C8 alkyl group, C1-C10 alkoxy group, phenyl group, hydroxyl group, amino group, dimethylamino group, diethylamino group, halogen atom, cyano group, sulfo group and carboxy group <Regarding ^R103 >
R ¹⁰³ represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

  Examples of the alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, cyclohexyl group, hydroxyethyl group, 1,2-dihydroxypropyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2 -Butoxyethyl group, 2- (2-methoxyethoxy) ethyl group, 2- (2-ethoxyethoxy) ethyl group, 2- (2-butoxyethoxy) ethyl group, benzyl group, phenethyl group and the like can be mentioned. Carbon number becomes like this. Preferably it is 1-10, More preferably, it is 1-6.

Examples of the alkenyl group include allyl group and methanyl group. The number of carbon atoms is preferably 3-4.
The aryl group is the same as that described in the section <About X and R ¹⁰¹ >.
Examples of the substituent that each group described above as R ¹⁰³ may have include those described in the above section (Substituent Group W), and each group described above has a substituent. Particularly preferred are those without.

R ¹⁰³ is preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an ethyl group, from the viewpoint that the generation amount of radical active species per gram is high and the production is simple.
<Regarding ^R 104 ^{to R 109>}
R ^{104 to} R ¹⁰⁹ each independently represent a hydrogen atom, a halogen atom, a nitro group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
R ^{104 to} R ¹⁰⁹ are particularly preferably hydrogen atoms from the viewpoint that the generation amount of radical active species per gram is high and the production is simple.

(About Z)
Z represents an aromatic ring group which may have a substituent.
Examples of the aromatic ring group 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 5 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, indene ring, etc. .

  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, azulene ring, an acridine ring, a xanthene ring, a phenazine ring, a phenothiazine ring, a phenoxazine ring, groups such as a benzothiazole ring.

As the aromatic substituent which may be ring group optionally having in Z, for example, those described in the section below [Substituent Group W ^1].
[Substituent Group W ¹ ]
An alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a sulfo group, and a carboxy group;

[Specific Examples of Compound (XI)]
Although the preferable specific example of compound (XI) in this invention is shown below, this invention is not limited to these.

Commercial products may be used as the oxime initiator. Examples of commercially available products include OXE-01, OXE-02 (manufactured by BASF), TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (Changzhou Powerful Electronic New Materials Co., Ltd.) CHANGZHOOU TRONLYNEW ELECTRONIC MATERI
ALS 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 651, IRGACURE 184, DAROCUR 1173, IRGACURE 2959, IRGACURE 127, IRGACURE 907, IRGACURE 369, IRGACURE 379EG, LUCIRIN TPO, IRGACURE 8 BA, and IRGACURE 8 BA19.

Examples of the (G2) polymerization accelerator used as necessary include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester;
Examples include mercapto compounds having a heterocyclic ring such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole; mercapto compounds such as aliphatic polyfunctional mercapto compounds.

These (G1) photopolymerization initiators and (G2) polymerization accelerators may be used alone or in combination of two or more.
Further, (G3) 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.

(G3) 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 (G) 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, the sensitivity to the exposure light beam is good, the solubility of the unexposed part in the development station is good, and it is preferable in that it is difficult to induce poor development.
[(G) Thermal polymerization starting component]
Specific examples of the thermal polymerization initiating component (G) 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 initiating component described in International Publication No. 2009/107734 can be used.
These thermal polymerization initiating components may be used alone or in combination of two or more.

[Other optional ingredients]
In addition to the above components, the colored resin composition of the present invention comprises a surfactant, an organic carboxylic acid and / or an organic carboxylic acid anhydride, a thermosetting compound, a plasticizer, a thermal polymerization inhibitor, a storage stabilizer, a surface It may contain a protective agent, an adhesion improver, a development improver, and the like. As these optional components, for example, various compounds described in JP-A-2007-113000 can be used. Moreover, when it contains the below-mentioned (H) pigment, you may contain the dispersing agent and the dispersing aid.

[(H) Pigment]
The colored resin composition of the present invention may contain (H) a pigment within a range not impairing the effects of the present invention for the purpose of improving the heat resistance of the color filter to be obtained.
(H) As a 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, 1
5: 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 blue copper phthalocyanine pigment is preferable, and 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 weight% or more with respect to the total content of a blue pigment, Especially 90 weight% or more, Especially 95-100 weight% 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 weight% or more with respect to the total content of a purple pigment, Especially 90 weight% or more, Especially 95-100 weight% 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 (H) pigment used in the colored resin composition of the present invention preferably has a small average primary particle size from the viewpoint of forming a high-contrast pixel. 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 (H) pigment is a value measured and calculated by the following method.

  First, (H) a 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.
The particle diameter of each pigment _{particle: X 1, X 2, X} 3, X 4, ····, X i, ······ X m

{Blending amount}
In this invention, when (H) a pigment is included, content of the pigment in a colored resin composition is 80 weight% or less normally in a total solid, Preferably it is 50 weight% or less.
Moreover, content with respect to 100 weight part of said (A) dye is 2000 weight part or less normally, Preferably it is 1000 weight part or less.
By setting it within the above-mentioned range, it is preferable in that the heat resistance of the obtained pixel is likely to be better without greatly affecting the transmittance of the dye (A).

[Dispersant]
When the colored resin composition of the present invention contains (H) a pigment, it is preferable to further contain a dispersant.
The dispersant in the present invention is not particularly limited as long as the pigment is dispersed and can maintain stability.
For example, cationic, anionic, nonionic or amphoteric dispersants can be used, but polymer dispersants are preferred. Specific examples include block copolymers, polyurethanes, polyesters, alkylammonium salts or phosphate esters of polymer copolymers, and cationic comb graft polymers. Of these dispersants, block copolymers, polyurethanes, and cationic comb graft polymers are preferred. In particular, a block copolymer is preferable, and among these, a block copolymer composed of an A block having solvophilicity and a B block having a functional group containing a nitrogen atom is preferable.

Specifically, the B block having a nitrogen atom-containing functional group includes a unit structure having a quaternary ammonium base and / or an amino group in the side chain, while the solvophilic A block includes a quaternary ammonium. Examples include a unit structure having no base and amino group.
The B block constituting the acrylic block copolymer has a unit structure having a quaternary ammonium base and / or an amino group, and has a pigment adsorption function.

Further, when the B block has a quaternary ammonium base, the quaternary ammonium base may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group. Good.
Examples of such block copolymers include those described in JP-A-2009-025813.

Moreover, the colored resin composition of the present invention may contain a dispersant other than those described above. Examples of other dispersants include those described in JP-A-2006-343648, for example.
When the colored resin composition of the present invention contains (H) a pigment, the content of the dispersant in the total solid content is 2 to 1000% by weight, particularly 5 to 500% by weight of the total content of (H) pigment. %, Particularly 10 to 250% by weight.
By setting it within the above range, (A) it is preferable in that good pigment dispersibility can be ensured without affecting the heat resistance of the dye, and the pigment dispersion stability becomes better.

[Dispersion aid]
The colored resin composition of the present invention may contain a dispersion aid. The dispersion aid here may be a pigment derivative, and examples of the pigment derivative include those disclosed in JP-A-2001-220520.
Various compounds described in JP-A No. 2001-271004, JP-A No. 2002-179976, JP-A No. 2007-113000, and JP-A 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 weight or more, usually 30% by weight or less, preferably 20% by weight or less, based on the total solid content of the pigment. Preferably it is 10 weight% or less, More preferably, it is 5 weight% 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.

[Dispersion resin]
The colored resin composition of the present invention may contain a part or all of the resin selected from the (C) binder resin or other binder resins as the following dispersion resin.
Specifically, in [Preparation Method of Colored Resin Composition], which will be described later, by adding (C) binder resin together with the components such as the above-mentioned dispersant, the (C) binder resin is combined with the dispersant. It contributes to the dispersion stability of the pigment (H) by a synergistic effect. 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, the (C) binder resin used in the dispersion treatment step may be referred to as a dispersion resin. The dispersion resin is preferably used in an amount of about 0 to 200% by weight, more preferably about 10 to 100% by weight, based on the total amount of the pigment in the colored resin composition.

[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) dye and the (C) binder resin containing the xanthene compound (I), the (B) solvent and the necessity It can prepare by mixing with the arbitrary component used according to it.
In addition, as a preparation method in the case of containing (H) pigment, in the solvent containing (H) pigment, in the presence of a dispersing agent and a dispersing aid to be added if necessary, (C) A pigment dispersion liquid is prepared by mixing and dispersing together with the parts, for example, using a paint shaker, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, and the like. In the pigment dispersion, (A) dye containing xanthene compound (I), (C) binder resin, (F) polymerizable monomer, (G) photopolymerization initiating component and / or thermal polymerization initiating as necessary. The method of preparing by adding a component etc. 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. 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.

<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.

  The light source used for image exposure for using radiation having a wavelength of 190 to 450 nm is not particularly limited. 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, more preferably 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. 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. The organic light-emitting body 500 formed on another substrate may be bonded to the inorganic oxide film 40. 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 (IA))
25 g of Acid Red 52 (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 250 mL of water and dialyzed until no chloride ion was detected with an electrodialyzer. This solution was ion-exchanged with a cation exchange resin SK1BH (manufactured by Mitsubishi Chemical Corporation). The obtained aqueous solution was neutralized with an aqueous solution of lithium hydroxide monohydrate until the pH became 7.0, then concentrated, dried, and a dye represented by the following formula (IA) (I-A) A) was synthesized.

  This dye (IA) was a red pigment having a maximum absorption wavelength λmax of 533 nm.

(Reference Synthesis Example 2: Synthesis of Dye (IB))

  Reaction 1: A solution of compound 1 (10 g) in N, N-dimethylformamide (100 ml) was cooled in an ice bath, sodium hydride (60%, 4.3 g) was added, and after stirring for a while, compound 2 (6.5 g) was added. ) Was added in small portions. After stirring at room temperature for 5 hours, water was added, extracted with dichloromethane, and purified by silica gel column chromatography to obtain compound 3 (3.1 g).

  Reaction 2: Phosphorus oxychloride (1.8 ml) was added to a mixture of compound 3 (5.61 g), compound 4 (2.65 g) and toluene (15 ml), and the mixture was stirred at 115 ° C. for 2 hours. After returning to room temperature, saturated brine (30 ml) was added, and the mixture was extracted twice with chloroform. The product was purified by silica gel column chromatography (silica gel 300 g, chloroform / methanol 1 / 0-10 / 1/7/1), and the resulting solid was washed with hexane to obtain compound 5 (9.23 g).

  Reaction 3: A mixture of compound 5 (11.40 g), compound 6 (4.88 g) and methanol (146 ml) was stirred at 50 ° C. for 1 hour, added to water, and the solid was collected by filtration. The solid was washed with methanol / water: 2/1 (220 ml) and again washed with methanol / water: 2/1 (72 ml) to obtain dye (IB) (13.9 g).

[Synthesis of resin]
(Reference Synthesis Example 3: 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, 4.4 parts by weight 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 weight 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, 67.0 parts by weight of acrylic acid, 1.1 parts by weight of trisdimethylaminomethylphenol and 0.19 parts by weight of hydroquinone were added, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, tetrahydrophthalic anhydride (THPA) and triethylamine were added as shown in the table and reacted at 100 ° C. for 3.5 hours. The weight average molecular weight Mw measured by GPC of the resin A thus obtained was about 15000. The structure of Resin A was as shown below (polymer compound containing the following four types of repeating units).

(Reference Synthesis Example 4: Synthesis of Resin B)
114.0 g of propylene glycol monomethyl ether acetate was placed in a 500 ml four-necked flask and heated to 85 ° C. while performing nitrogen bubbling. To this was added 100.1 g (0.55 mol) of cyclohexyl methacrylate, 33.3 g (0.45 also) of methacrylic acid, and 4.925 g (0.03 mol) of 2.2′-azobis (isobutyronitrile) in propylene glycol. It melt | dissolved in 96.45g of monomethyl ether acetate, and was dripped over 4 hours. After the dropwise addition, the reaction solution was further stirred for 2 hours while maintaining the temperature at 85 ° C., and thereafter the nitrogen bubbling was stopped and the temperature was raised to 100 ° C. for 1 hour. The weight average molecular weight Mw measured by GPC of the resin B thus obtained was about 15000, and the acid value was 190 mgKOH / g.
[Synthesis of photopolymerization initiator]
(Reference Synthesis Example 5: Compound (1-I))

The compound (1-I) was synthesized according to the method described in Japanese Patent Application Laid-Open No. 2008-179611.
[Preparation of blue pigment dispersion]
C. I. Pigment Blue 15: 6 is 12.0 parts by weight, the dispersant is BYK-LPN21116 (manufactured by Big Chemie) at 6.0 parts by weight in terms of dispersant solids, and the resin B produced in Reference Synthesis Example 4 is in solids 4.0 parts by weight and 78.0 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed and stirred with a stirrer for 3 hours to prepare a mill base having a solid content concentration of 20% by weight. The mill base was subjected to a dispersion treatment using 600 parts by weight of 0.5 mmφ zirconia beads in a bead mill apparatus at a peripheral speed of 10 m / s and a residence time of 3 hours to obtain a blue pigment dispersion.

[Preparation of colored resin composition]
The dyes synthesized in Reference Synthesis Examples 1 and 2 and the resin synthesized in Reference Synthesis Example 3 were mixed with other components so as to have the composition described in Table 1 to prepare a colored resin composition.
The blending ratio of resin A in each example and comparative example is shown in Table 2.
In addition, the numerical value in Table 1 represents the weight part of each component to add.
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 Tables 1 and 2 is as follows.
DPHA: dipentaerythritol hexaacrylate OXE01: 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)]
F475: Fluorosurfactant PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether [3] Production of colored resin film and evaluation of brightness Each of the colored resin compositions was applied by spin coating so as to have a dry film thickness of 3.2 μm, and dried under reduced pressure. Thereafter, the entire surface was exposed at an exposure amount of 40 mJ / cm ² , and then spray development was performed using a 0.04 wt% aqueous potassium hydroxide solution at a developer temperature of 26 ° C. and a pressure of 0.25 MPa. The development time was set to dissolution time + 20 seconds. After development, it is washed with sufficient pure water, dried with clean air, measured with a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.), and measured for chromaticity (C light source) in the XYZ color system. Calculated.

Subsequently, after the substrate was baked at 230 ° C. for 60 minutes in a clean oven, the spectral transmittance was measured as described above, and the chromaticity (C light source) in the XYZ color system was calculated.
The results are summarized in Table 2.

As for the antioxidant, IRGANOX 1010 (both manufactured by BASF) was used as the compound (II-1).
As for the phosphite, compound (III-1) is JPP100 (manufactured by Johoku Chemical Co., Ltd.),
As the compound (III-2), HP10 (manufactured by Adeka) was used.
In addition, the structure of each compound is as follows.

As shown in Table 2, the pixels formed using the colored resin composition of the present invention have high adhesion.
More specifically, in the colored resin composition containing the dye (IB), when containing an antioxidant and a phosphite (Comparative Example 3) and when containing only the antioxidant (Comparative Example 2) There is no difference in adhesion. However, in the colored resin composition containing the dye (IA), the case where the antioxidant and the phosphite are included (Examples 1 to 4) is the case where only the antioxidant is included (Comparative Example 1). Compared with the substrate, the adhesion to the substrate is remarkably improved.

That is, in the colored resin composition containing the compound (I), it can be seen that when the antioxidant and the phosphite are contained, the adhesion is specifically improved.
Thus, according to the present invention, the color filter, the liquid crystal display device and the organic EL display device formed using the colored resin composition 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 (9)

(A) a dye, (B) a solvent, (C) a binder resin and (D) an antioxidant,
The (A) dye contains a xanthene compound represented by the following formula (I), and
The (D) antioxidant contains a compound represented by the following formula (II),
Further, (E) a colored resin composition comprising a phosphite.

(In the formula (I),
R ^{1 to} R ⁴ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted aromatic carbon atom having 6 to 18 carbon atoms. Represents a hydrogen ring group.
R ¹ and R ² , and R ³ and R ⁴ may be independently bonded to each other to form a ring, and the ring may have a substituent.
R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent.
R ⁷ represents an arbitrary substituent.
m represents an integer of 0 to 5. When m is an integer of 2 or more, the plurality of R ⁷ may be the same or different.
p represents an integer of 1 to 4. When p is 2 to 4, the structures in [] containing a plurality of xanthene skeletons may be the same or different.
X ^q- represents an arbitrary q-valent anion.
q represents the integer of 1-4.
n represents an integer of 0 to 4. When n is 2-4, several ^Xq- may be the same or different.
When R ^{1 to} R ⁷ are a group containing a sulfonate group or a carboxylate group, or when R ⁷ is a sulfonate group or a carboxylate group, n is 0 and p = 1, and otherwise , P = n × q. )

(In said formula (II), R ^<1a> and R ^<2a> respectively independently represent the C1-C12 alkyl group which may have a substituent.
L represents a hydrogen atom, a carbon atom, an aromatic ring group which may have a substituent, or a heterocyclic group which may have a substituent.
Z is a divalent group consisting of an alkylene group having 1 to 10 carbon atoms and / or an ester bond which may have a substituent.
The benzene ring in the above formula (II) may have an arbitrary substituent other than R ^1a and R ^2a , —OH, and Z.
r represents an integer of 1 to 4.
In addition, when r is 2 to 4, a plurality of molecules contained in one molecule

May be the same structure or different.
* Represents a binding site to L. ) The colored resin composition according to claim 1 or 2, wherein the (E) phosphite is a compound represented by the following formula (III).

(In said formula (III), R ^<1b > -R <^3b> is respectively independently the C1-C12 alkyl group which may have a substituent, and the aromatic ring group which may have a substituent. Or a heterocyclic group which may have a substituent.
R ^{1b to} R ^3b may be bonded to each other to form a ring. )   The content of the (E) phosphite with respect to the (D) antioxidant is 0.05% by weight or more and 6.0% by weight or less in the total solid content, The colored resin composition according to 1 or 2.   Furthermore, (F) polymerizable monomer is contained, The colored resin composition as described in any one of Claims 1-3 characterized by the above-mentioned.   The colored resin composition according to claim 1, further comprising (G) a photopolymerization initiation component and / or a thermal polymerization initiation component.   Furthermore, (H) A pigment is contained, The colored resin composition as described in any one of Claims 1-5 characterized by the above-mentioned.   It has a pixel formed using the colored resin composition as described in 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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